図書

Encyclopedia of radicals in chemistry, biology and materials

editors, Chryssostomos Chatgilialoglu, Armido Studer

詳細情報

タイトル	Encyclopedia of radicals in chemistry, biology and materials
著者	editors, Chryssostomos Chatgilialoglu, Armido Studer
出版地（国名コード）	GB
出版地	Chichester, West Sussex, United Kingdom
出版社	John Wiley & Sons Ltd
出版年月日等	2012
大きさ、容量等	4 volumes : illustrations (some colour) ; 26 cm
注記	機器種別 : unmediated
注記	キャリア種別 : volume
注記	表現種別 : text
注記	Includes bibliographical references and index
ISBN（set）	9780470971253
LC番号	2011040417
部分タイトル	v. 1. Basic concepts and methodologies -- v. 2. Synthetic strategies and applications -- v. 3. Chemical biology -- v. 4. Polymers and materials
出版年(W3CDTF)	2012
件名（キーワード）	Free radicals (Chemistry)
件名（キーワード）	Radicals (Chemistry)
件名（キーワード）	SCIENCE / Chemistry / Industrial & Technical
NDLC	PA47
LCC	QD471
DDC	541/.224
要約・抄録	"In recent years, free radicals have played an important role in various disciplines, ranging from organic synthesis to biology and medicine, polymer chemistry and materials science. The aim of this handbook is to offer for the first time a description of free radicals within an interdisciplinary and multidisciplinary context, connecting structural characteristics and chemical properties to their applications in different areas of chemistry and related disciplines. The Handbook covers not only basic concepts and chemical synthesis, but also touches on various aspects concerning the role of free radicals in materials and life sciences. The reader will find a balanced contribution of topics related to free radicals covering for example, their role in proteomics, genomics and lipidomics as well as their enormous potential in synthesis and technology. The Handbook will be interesting for anybody working in the field of free radicals in the broadest sense. It will address scientists who want to enter the interdisciplinary field of free radicals. In particular, it is aimed primarily at chemists and life science researchers who want to gain a wider and deeper understanding of free radicals which will allow them to apply free radicals in their own scientific field. The book consists of four themed volumes: Basic Concepts & Methodologies, Synthetic Strategies & Applications, Chemical Biology, Polymers & Materials. Within the volumes the chapters will also be thematically structured"--
対象利用者	一般
資料の種別	図書
関連資料（URI形式）	http://catalogimages.wiley.com/images/db/jimages/9780470971253.jpg
言語（ISO639-2形式）	eng : English

Encyclopedia of radicals in chemistry, biology and materials
Contents
VOLUME 1:　BASIC CONCEPTS AND METHODOLOGIES
VOLUME 1:　Preface　ix
VOLUME 1:　List of Contributors　xi
VOLUME 1:　Abbreviations and Acronymns　xix
VOLUME 1:　1　The History of Free Radical Chemistry　Thomas T.Tidwell　1
VOLUME 1:　2　Overview of Radical Initiation　Jacques Lalevée，Jean Pierre Fouassier　37
VOLUME 1:　3　Basic Concepts on Radical Chain Reactions　Michael S.Sherburn　57
VOLUME 1:　4　Thermochemistry and Hydrogen Transfer Kinetics　Andreas A.Zavitsas　81
VOLUME 1:　5　Radical Kinetics and Clocks　Martin Newcomb　107
VOLUME 1:　6　Radical Rearrangements: Ester-Substituted Radicals and Hydrogen Atom Migrations　Kaname Sasaki，Ian Cumpstey，David Crich　125
VOLUME 1:　7　Analysis of Radicals by EPR　John C.Walton　147
VOLUME 1:　8　Structures and Reactivity of Radicals Followed by Magnetic Resonance　Alexandra Yurkovskaya，Olga Morozova，Georg Gescheidt　175
VOLUME 1:　9　Matrix Isolation of Radicals　Artur Mardyukov，Wolfram Sander　207
VOLUME 1:　10　Supramolecular Radical Chemistry　Marco Lucarini　229
VOLUME 1:　11　Redox Properties of Radicals　David C.Magri，Mark S.Workentin　249
VOLUME 1:　12　Photo Induced Radical Reactions　Julia Pérez-Prieto，Miguel A.Miranda　275
VOLUME 1:　13　Radical Cation/Anion and Neutral Radicals: A Comparison　Amber N.Hancock，J.M.Tanko　301
VOLUME 1:　14　The SRN1 Reaction　Javier I.Bardagí，Victoria A. Vaillard，Roberto A.Rossi　333
VOLUME 1:　15　Photoinduced Reactions of Radical Ions via Charge Separation　Shunichi Fukuzioni，Kei Ohkubo　365
VOLUME 1:　16　Radiation-Induced Radical Reactions　Krzysztof Bobrowski　395
VOLUME 1:　17　Free Radical Chemistry in Room-Temperature Ionic Liquids　Ilya A.Shkrob，James F.Wishart　433
VOLUME 1:　18　Radical Stability-Thermochemical Aspects　Johnny Hioe，Hendrik Zipse　449
VOLUME 1:　19　Radical Chemistry in the Gas Phase　Christian Alcaraz，Ingo Fischer，Detlef Schröder　477
VOLUME 1:　20　Atmospheric Radical Chemistry　Paul H.Wine，J.Michael Nicovich　503
VOLUME 2:　SYNTHETIC STRATEGIES AND APPLICATIONS
VOLUME 2:　Preface　ix
VOLUME 2:　List of Contributors　xi
VOLUME 2:　Abbreviations and Acronymns　xix
VOLUME 2:　21　Tin Hydrides and Functional Group Transformations　Hannelore Jasch，Markus R.Heinrich　529
VOLUME 2:　22　Silanes as Reducing Reagents in Radical Chemistry　Chryssostomos Chatgilialoglu，Vitaliy I.Timokhin　561
VOLUME 2:　23　Boron in Radical Chemistry　Philippe Renaud　601
VOLUME 2:　24　Intramolecular Homolytic Substitutions in Synthesis　Sara H.Kyne，Carl H.Schiesser　629
VOLUME 2:　25　Stereoselective Radical Reactions　Yong-Hua Yang，Mukund P.Sibi　655
VOLUME 2:　26　Unusual Cyclizations　Kerry Gilmore，Igor V.Alabugin　693
VOLUME 2:　27　Radical Cascade Reactions　Alexandre Baralle，Abdulkader Baroudi，Marion Daniel，Louis Fensterbank，Jean-Philippe Goddard，Emmanuel Lacôte，Marie-Hélène Larraufie，Giovanni Maestri，Max Malacria，Cyril Ollivier　729
VOLUME 2:　28　Main-Group Elements in Radical Chemistry　Alexandre Baralle，Abdulkader Baroudi，Marion Daniel，Louis Fensterbank，Jean-Philippe Goddard，Emmanuel Lacôte，Marie-Hélène Larraufie，Giovanni Maestri，Max Malacria，Cyril Ollivier　767
VOLUME 2:　29　Organic Electron Donors　John A.Murphy　817
VOLUME 2:　30　Organic Synthesis Using Samarium Diiodide　Susannah C.Coote，Robert A.Flowers II，Troels Skrydstrup，David J.Procter　849
VOLUME 2:　31　Manganese(III) Acetate, CAN, and Fe(III) Salts in Oxidative Radical Chemistry　Jonathan W.Burton　901
VOLUME 2:　32　Halogen and Chalcogen Transfer Chemistry　Chaozhong Li　943
VOLUME 2:　33　Xanthates and Related Derivatives as Radical Precursors　Samir Z.Zard　965
VOLUME 2:　34　Epoxides in Titanocene-Mediated and -Catalyzed Radical Reactions　Andreas Gansäuer，André Fleckhaus　989
VOLUME 2:　35　Transition Metals and Radicals　Hideki Yorimitsu　1003
VOLUME 2:　36　Unusual Radical Acceptors　Piero Spagnolo，Daniele Nanni　1019
VOLUME 2:　37　Radical Arylations　Santiago E.Vaillard，Annido Studer　1059
VOLUME 2:　38　Nitroxides in Synthetic Radical Chemistry　Chittreeya Tansakul，Rebecca Braslau　1095
VOLUME 2:　39　Radicals and Carbohydrates　Inés Pérez-Martín，Ernesto Suárez　1131
VOLUME 2:　40　Electrochemically Initiated Radical Reactions　Martin A.Bohn，Anna Paul，Gerhard Hilt　1175
VOLUME 2:　41　Synthetic Radical Photochemistry　Emmanuel Riguet，Norbert Hoffmann　1217
VOLUME 2:　42　Radical Chemistry by Using Flow Microreactor Technology　Takahide Fukuyama，Ilhyong Ryu　1243
VOLUME 3:　CHEMICAL BIOLOGY
VOLUME 3:　Preface　ix
VOLUME 3:　List of Contributors　xi
VOLUME 3:　Abbreviations and Acronymns　xix
VOLUME 3:　43　Biological Chemistry of Reactive Oxygen Species　Christine C.Winterbourn　1259
VOLUME 3:　44　Reactions of Small Reactive Species with DNA　Nicholas E.Geacintov，Vladimir Shafirovich　1283
VOLUME 3:　45　Oxidatively Generated Nucleobase Modifications in Isolated and Cellular DNA　Jean Cadet，Thierry Douki，Didier Gasparutto，Jean-Luc Ravanat，J.Richard Wagner　1319
VOLUME 3:　46　Oxidatively Formed Sugar Radicals in Nucleic Acids　Thanasis Gimisis，Chryssostomos Chatgilialoglu　1345
VOLUME 3:　47　Understanding DNA Radicals Employing Theory and Electron Spin Resonance Spectroscopy　Amitava Adhikary，Anil Kumar，David Becker，Michael D.Sevilla　1371
VOLUME 3:　48　Charge Transfer in DNA　Mamoru Fujitsuka，Tetsuro Majima　1397
VOLUME 3:　49　Oxidative Damage to Proteins　Michael J. Davies　1425
VOLUME 3:　50　Radical-Based Damage of Sulfur-Containing Amino Acid Residues　Christian Schöneich　1459
VOLUME 3:　51　Electron Transfer in Peptides and Proteins　Bernd Giese，Sonja Eckhardt，Miriam Lauz　1475
VOLUME 3:　52　Radical Enzymes　Wolfgang Buckel，Bernard T.Golding　1501
VOLUME 3:　53　Theoretical Studies of Radical Enzymes　Gregory M.Sandala，David M.Smith，Leo Radom　1547
VOLUME 3:　54　Lipid Peroxidation　Etsuo Niki　1577
VOLUME 3:　55　Lipid Isomerization　Carla Ferreri，Chryssostomos Chatgilialoglu　1599
VOLUME 3:　56　Antioxidants in Chemistry and Biology　Luca Valgimigli，Derek A.Pratt　1623
VOLUME 3:　57　Free Radicals and Metabolic Disorders　Guy Cohen，Yael Riahi，Shlomo Sasson　1679
VOLUME 4:　POLYMERS AND MATERIALS
VOLUME 4:　Preface　ix
VOLUME 4:　List of Contributors　xi
VOLUME 4:　Abbreviations and Acronymns　xix
VOLUME 4:　58　Radical Polymerization in Industry　Peter Nesvadba　1701
VOLUME 4:　59　Kinetics of Polymerizations　Michael Buback，Gregory T.Russell　1737
VOLUME 4:　60　Fundamentals of Controlled/Living Radical Polymerization　Krzysztof Matyjaszewski　1785
VOLUME 4:　61　Nitroxide-Mediated Polymerization and its Applications　Didier Gigmes，Sylvain R.A.Marque　1813
VOLUME 4:　62　Atom Transfer Radical Polymerization (ATRP) and Addition (ATRA) and Applications　Tomislav Pintauer，Krzysztof Matyjaszewski　1851
VOLUME 4:　63　Reversible Addition Fragmentation Chain Transfer (RAFT) Polymerization: Mechanism, Process and Applications　Christopher Barner-Kowollik，James P.Blinco，Mathias Destarac，Kristofer J.Thurecht，Sébastien Perrier　1895
VOLUME 4:　64　Sb, Bi, Te, and I-Transfer Polymerization and Applications　Shigeru Yamago，Eiichi Kayahara　1931
VOLUME 4:　65　Spin Labels and Spin Probes　David Bardelang，Micaël Hardy，Olivier Ouari，Paul Tordo　1965
VOLUME 4:　66　Radical Thiol-X Click Chemistry　Niels ten Brummelhuis，Helmut Schlaad　2017
VOLUME 4:　67　Conducting Polymers: Applications in Electronics and Photovoltaics　Huanli Dong，Wenping Hu　2057
VOLUME 4:　68　Silicon Radical Surface Chemistry　Bart Rijksen，Mabel A.Caipa Campos，Jos M.J.Paulusse，Han Zuilhof　2081
VOLUME 4:　69　Persistent and Stable Silyl Radicals　Boris Tumanskii，Miriam Karni，Yitzhak Apeloig　2117
VOLUME 4:　70　Physical Properties of Thiazyl Radicals Toward Conductive and Magnetic Materials　Kunio Awaga　2147
VOLUME 4:　71　Polyradicals in Batteries　Kenichi Oyaizu，Hiroyuki Nishide　2163
VOLUME 4:　72　Radical Chemistry on Fullerenes　Manolis D.Tzirakis，Michael Orfanopoulos　2171
VOLUME 4:　73　A Paradigm for the Radical-Mediated Photochemical Synthesis of Metal Nanostructures　Juan C.Scaiano，Kevin G.Stamplecoskie，Katherine L.McGilvray，Natalia L.Pacioni　2197
Author Index　2211
Subject Index　2213
Author Index
Adhikary, Amitava　3:1371-1396
Alabugin, Igor V.　2:693-728
Alcaraz, Christian　1:477-502
Apeloig, Yitzhak　4:2117-2146
Awaga, Kunio　4:2147-2162
Baralle, Alexandre　2:729-766,2:767-816
Bardagí, Javier I.　1:333-364
Bardelang, David　4:1965-2016
Barner-Kowollik, Christopher　4:1895-1930
Baroudi, Abdulkader　2:729-766,2:767-816
Becker, David　3:1371-1396
Blinco, James P.　4:1895-1930
Bobrowski, Krzysztof　1:395-432
Bohn, Martin A.　2:1175-1216
Braslau, Rebecca　2:1095-1130
Brummelhuis, Niels ten　4:2017-2056
Buback, Michael　4:1737-1784
Buckel, Wolfgang　3:1501-1546
Burton, Jonathan W.　2:901-942
Cadet, Jean　3:1319-1344
Caipa Campos, Mabel A.　4:2081-2116
Chatgilialoglu, Chryssostomos　2:561-600,3:1345-1370,3:1599-1622
Cohen, Guy　3:1679-1700
Coote, Susannah C.　2:849-900
Crich, David　1:125-146
Cumpstey, Ian　1:125-146
Daniel, Marion　2:729-766,2:767-816
Davies, Michael J.　3:1425-1458
Destarac, Mathias　4:1895-1930
Dong, Huanli　4:2057-2080
Douki, Thierry　3:1319-1344
Eckhardt, Sonja　3:1475-1500
Fensterbank, Louis　2:729-766,2:767-816
Ferreri, Carla　3:1599-1622
Fischer, Ingo　1:477-502
Fleckhaus, André　2:989-1002
Flowers II, Robert A.　2:849-900
Fouassier, Jean Pierre　1:37-56
Fujitsuka, Mamoru　3:1397-1424
Fukuyama, Takahide　2:1243-1258
Fukuzumi, Shunichi　1:365-394
Gansäuer, Andreas　2:989-1002
Gasparutto, Didier　3:1319-1344
Geacintov, Nicholas E.　3:1283-1318
Gescheidt, Georg　1:175-206
Giese, Bernd　3:1475-1500
Gigmes, Didier　4:1813-1850
Gilmore, Kerry　2:693-728
Gimisis, Thanasis　3:1345-1370
Goddard, Jean-Philippe　2:729-766,2:767-816
Golding, Bernard T.　3:1501-1546
Hancock, Amber N.　1:301-332
Hardy, Micaël　4:1965-2016
Heinrich, Markus R.　2:529-560
Hilt, Gerhard　2:1175-1216
Hioe, Johnny　1:449-476
Hoffmann, Norbert　2:1217-1242
Hu, Wenping　4:2057-2080
Jasch, Hannelore　2:529-560
Karni, Miriam　4:2117-2146
Kayahara, Eiichi　4:1931-1964
Kumar, Anil　3:1371-1396
Kyne, Sara H.　2:629-654
Lacôte, Emmanuel　2:729-766,2:767-816
Lalevée, Jacques　1:37-56
Larraufie, Marie-Hélène　2:729-766,2:767-816
Lauz, Miriam　3:1475-1500
Li, Chaozhong　2:943-964
Lucarini, Marco　1:229-248
Maestri, Giovanni　2:729-766,2:767-816
Magri, David C.　1:249-274
Majima, Tetsuro　3:1397-1424
Malacria, Max　2:729-766,2:767-816
Mardyukov, Artur　1:207-228
Marque, Sylvain R.A.　4:1813-1850
Matyjaszewski, Krzysztof　4:1785-1812,4:1851-1894
McGilvray, Katherine L.　4:2197-2210
Miranda, Miguel A.　1:275-300
Morozova, Olga　1:175-206
Murphy, John A.　2:817-848
Nanni, Daniele　2:1019-1058
Nesvadba, Peter　4:1701-1736
Newcomb, Martin　1:107-124
Nicovich, J. Michael　1:503-528
Niki, Etsuo　3:1577-1598
Nishide, Hiroyuki　4:2163-2170
Ohkubo, Kei　1:365-394
Ollivier, Cyril　2:729-766,2:767-816
Orfanopoulos, Michael　4:2171-2196
Ouari, Olivier　4:1965-2016
Oyaizu, Kenichi　4:2163-2170
Pacioni, Natalia L.　4:2197-2210
Paulusse, Jos M.J.　4:2081-2116
Paul, Anna　2:1175-1216
Pérez-Martín, Inés　2:1131-1174
Pérez-Prieto, Julia　1:275-300
Perrier, Sébastien　4:1895-1930
Pintauer, Tomislav　4:1851-1894
Pratt, Derek A.　3:1623-1678
Procter, David J.　2:849-900
Radom, Leo　3:1547-1576
Ravanat, Jean-Luc　3:1319-1344
Renaud, Philippe　2:601-628
Riahi, Yael　3:1679-1700
Riguet, Emmanuel　2:1217-1242
Rijksen, Bart　4:2081-2116
Rossi, Roberto A.　1:333-364
Russell, Gregory T.　4:1737-1784
Ryu, Ilhyong　2:1243-1258
Sandala, Gregory M.　3:1547-1576
Sander, Wolfram　1:207-228
Sasaki, Kaname　1:125-146
Sasson, Shlomo　3:1679-1700
Scaiano, Juan C.　4:2197-2210
Schiesser, Carl H.　2:629-654
Schlaad, Helmut　4:2017-2056
Schöneich, Christian　3:1459-1474
Schröder, Detlef　1:477-502
Sevilla, Michael D.　3:1371-1396
Shafirovich, Vladimir　3:1283-1318
Sherbum, Michael S.　1:57-80
Shkrob, Ilya A.　1:433-448
Sibi, Mukund P.　2:655-692
Skrydstrup, Troels　2:849-900
Smith, David M.　3:1547-1576
Spagnolo, Piero　2:1019-1058
Stamplecoskie, Kevin G.　4:2197-2210
Studer, Armido　2:1059-1094
Suárez, Ernesto　2:1131-1174
Tanko, J. M.　1:301-332
Tansakul, Chittreeya　2:1095-1130
Thurecht, Kristofer J.　4:1895-1930
Tidwell, Thomas T.　1:1-36
Timokhin, Vitaliy I.　2:561-600
Tordo, Paul　4:1965-2016
Tumanskii, Boris　4:2117-2146
Tzirakis, Manolis D.　4:2171-2196
Vaillard, Victoria A.　1:333-364
Vaillard, Santiago E.　2:1059-1094
Valgimigli, Luca　3:1623-1678
Wagner, J. Richard　3:1319-1344
Walton, John C.　1:147-174
Wine, Paul H.　1:503-528
Winterbourn, Christine C.　3:1259-1282
Wishart, James F.　1:433-448
Workentin, Mark S.　1:249-274
Yamago, Shigeru　4:1931-1964
Yang, Yong-Hua　2:655-692
Yorimitsu, Hideki　2:1003-1018
Yurkovskaya, Alexandra　1:175-206
Zard, Samir Z.　2:965-988
Zavitsas, Andreas A.　1:81-106
Zipse, Hendrik　1:449-476
Zuilhof, Han　4:2081-2116
Subject Index
A ring construction, 1,22-dihydroxynitiane nitiol analogs, Norrish reactions,　2:1228
AB ring synthesis, azadirachtin, stereoselective radical cascade,　2:730
ab initio emulsion polymerization, reversible addition fragmentation chain transfer,　4:1920-1921
ab initio methods, radical enzyme theoretical studies,　3:1548,1550-1551,1552,1555,1557-1558
ab initio values
bond dissociation enthalpies,　1:84
enthalpies of formation,　1:84
EPR parameters,　1:152,155
hydrogen transfer kinetics,　1:100-101
absolute cross-section, photoionization of gas phase radicals,　1:491
absorption spectra, electron paramagnetic resonance, principles,　1:149
AC see alternating current
acceptors see radical acceptors
α-acetamido tetralins, metal-dependent synthesis,　2:918
acetate anions, room-temperature ionic liquids,　1:441
acetic acid/derivatives, γ-lactone synthesis, manganese(III) acetate-mediated,　2:904-906
acetone
photochemical radical generation, metal nanostructures synthesis,　4:2199-2200
radiolysis,　1:414-415
acetonitrile, radiolysis,　1:413-414
acetophenone coupling, samarium diiodide,　2:854-855
acetoxylated C60 derivatives, one-pot synthesis,　4:2179-2180
acetylene additions, carbamotelluroates,　2:961
p-acetyl-L-phenylalanine, orthogonal spin labeling,　4:1967,1970
acetyl radicals, acetylium transition, ionization energy,　1:489-490
acid effects, nitroxide-mediated polymerization,　4:1835-1836
acid fluoride monolayers, silicon surfaces,　4:2109-2110
Acr+-Mes see 9-mesityl-10-methylacridinium ion
acridinium ions, chromophore/electron acceptor, photocatalytic reactions,　1:366
acrylamides
polymerization
nitroxide-mediated,　4:1838
reversible addition fragmentation chain transfer,　4:1903-1904
synthesis, tin hydride-mediated,　2:552-553
acrylates
polymerization
organoheteroatom-mediated radical living polymerization,　4:1940,1941-1943
reversible addition fragmentation chain transfer,　4:1903-1904
production, biotechnological applications of radical enzymes,　3:1539-1540
acrylic acid, nitroxide-mediated polymerization,　4:1838
acrylonitrile
additions, glycos-l-yl radicals, stereoelectronic effects,　2:1131-1132
nitroxide-mediated polymerization,　4:1838
activated alkanes, SRN1 reactions,　1:354-355
activated alkenes, epoxide radicals additions,　2:993-995
activated allyl derivatives, SRN1 reactions,　1:361
activated benzyl derivatives, SRN1 reactions,　1:355-358
activated benzyl halides, SRN1 reactions,　1:360-361
activating passivation, silicon surfaces, hydrogen,　4:2082
activating (Z) groups, reversible addition fragmentation chain transfer agents,　4:1896,1897,1904
activation/deactivation mechanisms, persistent radical effect, controlled/living radical polymerization,　4:1786-1787,1953-1956
activation energies,　1:81
bond dissociation enthalpies,　1:82-83
reactive oxygen species,　3:1267,1268,1271
activation rate constants, atom transfer radical polymerization,　4:1864-1865
activation of sulfatases, alcohol oxidation to aldehyde, SAM radical enzymes,　3:1520
activators generated by electron transfer (AGET), atom transfer radical polymerization,　4:1862
activators regenerated by electron transfer (ARGET)
atom transfer radical addition/cyclization,　4:1879-1880
atom transfer radical polymerization,　4:1862-1863
industrial processes,　4:1729-1730
active esters, silicon surfaces, functionalized monolayers,　4:2106-2109
(-)-acutumine, synthesis, intramolecular homolytic aromatic substitutions,　2:1085
acyclic 1,2-inductions, substrate controlled,　2:655-656
acyclic phosphonylated a-hydro nitroxides, nitroxide-mediated polymerization, industrial processes,　4:1728
acyclic sugar derivatives
carbocycle synthesis,　2:1149-1155
carbofuranose synthesis,　2:1149-1153
acyl-CoA dehydrogenases, ketyl radicals,　3:1530-1531
acyl derivatives, decarbonylations, tris(trimethylsilyl)silane,　2:563-565
N-acyl hydrazones, enantioselective additions, organoboranes,　2:618
acylhypohalogenites, fullerene reactions,　4:2182
β-acyloxyalkyl radicals, rearrangements,　1:126,127,128
γ-acyloxyalkyl radicals, non-rearrangement,　1:126,127
N-acyloxyamine radical initiators, industrial radical polymerization,　4:1710-1711
β-acyloxyaryl radicals, non-rearrangement,　1:126,127
acyloxy rearrangements,　1:126-130
cyclic transition states,　1:126,127
fragmentation/recombination mechanism,　1:126,127
acyloxy rearrangements (continued)
shift away from nucleoside 1'-position　1:129,130
shift to anomenc centers,　1:128-129,130
acyl radicals
additions, alkyl azides,　2:770
arrunyl radical generation,　2:769-770
cascade chain reactions,　2:731-733
clocks,　1:118
cyclizations
aliphatic azides,　2:1022
7-exo/6-exo cascade,　2:732
electrophrlic nitrogen effects　2:713
decatungstate catalyzed addition to fullerenes,　4:2173-2174
lactam synthesis,　2:721-722
ring closures
at silicon,　2:648-649
at sulfur　2:636
acyl substitutions, conjugated Reformatsky reactions, samarium diiodrde mediated,　2:889
acyl telluride radicals, generation,　2:960
acyl throhydroxamates
radical chain reactions,　1:68,76-77
see also Barton esters
addinon-cyclizations
aryl rings,　2:910-913
cenum(IV) ammonium nitrate-mediated,　2:911-913
iron(III) salt-mediated,　2:910-913
manganese(III) acetate-mediated,　2:911-913
addition-rearrangement-cyclizations, chhydronaphthalene synthesis,　2:912-913
additions
acetylenes, carbamotelluroates　2:961
acrylonitrile, glycos-1-yl radicals, stereoelectronic effects,　2:1131-1132
activated alkenes, epoxide radicals,　2:993-995
acyl radicals, alkyl azides,　2:770
aldehydes, ketones,　2:906-907
alkenes
azinclinyl radicals,　2:773-774
carboxylic acids, γ-lactone synthesis,　2:904-906
β-chcarbonyl compounds,　2:907-918
diethylthiophosphite,　2:604
epoxide radicals,　2:993-995
β-keto esters,　2:902
kinetics,　1:121-122
organoboranes,　2:603-604
samarium diiodide-mediated,　2:877-879
2,2,6,6-tetramethylpiperidine-1-oxyl malonate,　2:1247
xanthates,　2:976
alkyl azides
acyl radicals,　2:770
alkyl radicals,　2:770
alkylcatecholboranes, nitroxrdes, carbon radical generation,　2:1097
B-alkylcatecholboranes, quinones,　2:611
alkyl radicals
alkyl azides,　2:770
isothiocyanates,　2:1049-1050
unsaturated carbohydrates, α-C-glycosides synthesis,　2:1137-1139
alkynes
organoboranes,　2:603-604
samarium diiodide-mediated,　2:877-879
allylboron derivatives, α-iodoesters,　2:622
arenes, aryl radicals, spirocyclic cyclohexachenone synthesis,　2:1063-1064
aromatic azides, aryl radicals,　2:770-771
aryl radicals
arenes, spirocyclic cyclohexachenone synthesis,　2:1063-1064
aromatic amides,　2:770-771
olefins, synthetic applications,　2:1066-1067,1080-1082
2-arylsulfinylcyclopentenones, tnalkylboranes,　2:609
azindinyl radicals, alkenes,　2:773-774
C60, scandine,　2:1217-1218
carbamotelluroates, acetylenes,　2:961
carbon carbon multiple bonds, fluoroalkyl radicals, tris(trimethylsilyl)silane mediated,　2:585-586
carbonyl groups, N-stannylammyl radicals,　2:768-769
carboxylic acids, alkenes γ-lactone synthesis,　2:904-906
catecholboranes, nitroxides, synthetic applications,　2:1097
cerium(IV) ammonium nitrate-mediated,　2:913-917,1142
conjugate
B-alkylcatecholboranes,　2:610-612
chiral oxazolichnone auxiliaries,　2:664-665
5-endo-trig cyclizations,　2:703-705
trialkylboranes,　2:607-609
cyanamides, N-stannylaminyl radicals,　2:768
β-chcarbonyl compounds
alkenes,　2:907-918
enamines, pyrrole synthesis,　2:915
dihydrofuran, α-xanthate-α-fluoroacetate,　2:606
enammes, β-dicarbonyl compounds, pyrrole synthesis,　2:915
enantioselectwe, N-acyl hydrazones, organoboranes,　2:618
enones, organoboranes,　2:611
fluoroalkyl radicals, carbon-carbon multiple bonds, tris(trimethylsilyl)silane-mediated,　2:585-586
glycals, malonates, cenum(IV) ammonium nitrate-mediated　2:1142
glycos-1-y1 radicals, unsaturated acceptors, C-glycoside synthesis,　2:1144
halogens to radicals, history,　1:17
heteroatom centered radicals, isonitriles,　2:1038
imine derivatives, nitrogen-centered radical formation,　2:780-781
imines, trialkylboranes,　2:609
indium-aminyl radicals nitrites,　2:769
indoles, ketyl radicals radical/anionic sequences,　2:893-894
α-iodoesters, allylboron derivatives,　2:622
isonitriles
heteroatom centered radicals,　2:1038
imidoyl radical formation,　2:1037-1038
telluro derivatives,　2:1046
isothiocyanates, alkyl radicals,　2:1049-1050
ketene, mtroxides,　2:1104
β-keto esters, alkenes,　2:902
ketones, aldehydes,　2:906-907
ketyl radicals, indoles radrcal/anionic sequences,　2:893-894
kinetics,　1:121-122
malonates,　2:947
glycals,　2:1142
malononitriles,　2:947
manganese(III) acetate-mediated,　2:913-917
multiple bonds, sulfur centered radicals,　2:798-803
nitriles
indium-aminyl radicals,　2:769
nitrogen-centered radical formation,　2:780-781
N-stannylammyl radicals　2:768
nitrones, tnalkylboranes,　2:609
nitroxides
alkylcatecholboranes carbon radical generation　2:1097
ketene, synthetic applications　2:1104
olefins
aryl radicals synthetic applications,　2:1066-1067,1080-1082
oxoammonium cations, alkoxyamme synthesis,　2:1096
xanthates,　2:976-977
organoboranes, enones　2:611
oxidative
cobalt-catalyzed　2:1008-1012
manganese-catalyzed　2:1014
nickel-catalyzed,　2:1006-1008
palladium-catalyzed　2:1004-1006
silver-catalyzed,　2:1014
titanium-catalyzed,　2:1014-1015
zirconium catalyzed reactions,　2:1015-1016
oxoammonium cations, olefins alkoxyamine synthesis,　2:1096
8-oxo-7,8-dihydroguanine radical cation,　3:1309-1311
oxygen-centered radicals π-systems,　2:787-790
photochemical electron transfer-induced　2:1217-1221
alkynes, silylated tertiary amines　2:1218-1219
C60, scanchne,　2:1217-1218
silylated tertiary ammes alkynes　2:1218-1219
tertiary amines, pyrrolizadine synthesis,　2:1220
photoinduced radicals,　1:287-288
π-systems, oxygen-centered radicals,　2:787-790
primary amidyl radicals, C=C bonds,　2:772
quinones
B-alkylcatecholboranes,　2:611
trialkylboranes　2:609
radical chain reactions　1:60,61-62,63,66,69-71,75
atom transfer　1:66,75
intermolecular radical additions to multiple bonds,　1:69-71
regroselective, thryl radicals, vrnyhdenecyclopopane,　2:800
scandine C60　2:1217-1218
selenium-centered radicals, insaturations,　2:808-809
SOMO catalysis, styrenes,　2:681-682
N-stannylammyl radicals　2;768
carbonyl groups,　2:768-769
cyanamides,　2:768
nitriles,　2:768
stereoelectronic effects, acrylonitrile, glycos-1-y1 radicals,　2:1131-1132
styrenes, SOMO catalysis,　2:681-682
sulfanyl radicals, isonitriles five-membered heterocycle synthesis,　2:1045
sulfur-centered radicals, multiple bonds,　2:798-803
telluro derivatives, isonitriles,　2:1046
tetranitromethane, B-alkylcatecholboranes　2:615
thiols to unsaturated compounds
click chemistry applications,　4:2017,2021-2053
mechanisms,　4:2017,2018-2020
tin radicals, unsaturated systems, radical generation　2:551-554
unsaturated carbohydrates
alkyl radicals, α-C-glycosides synthesis,　2:1137-1139
tethered radicals branched-chain sugar synthesis,　2:1146-1149
α,β-unsaturated esters, L-fucos-1-y1 radicals,　2:1133
unsaturated systems tin radicals, radical generation,　2:551-554
vinyl epoxides xanthates,　2:619
α-xanthate-α-fluoroacetate, dihydrofuran,　2:606
xanthates
alkenes,　2:976
olefins,　2:976-977
addition-elimination (A/E)
coenzyme B12-dependent enzyme mechanism,　3:1552-1553,1555
lipid isomerization　3:1601
additives
atom transfer radical polymerization,　4:1860
organoheteroatom-mediated radical living polymerization,　4:1935-1937,1956-1958
adenine (A)
hydroxyl radical reactions,　3:1292:1328
oxidation
5',8-cyclonucleosides　3:1338
DNA charge transfer,　3:1398
hydroxyl radicals,　3:1292,1328
one-electron transfer,　3:1293-1294,1333
adenosylcobalamin see coenzyme B12
S-adenosylmethionine (SAM) radical enzymes,　3:1501,1514-1525
activation of sulfatases, alcohol oxidation,　3:1520
biotin synthase,　3:1501
C-C bond formation,　3:1524
fragmentations and rearrangements,　3:1520-1523
glycyl-ractical enzymes,　3:1517-1520,1562
irreversible,　3:1517-1525
mechanisms,　3:1501,1502,1503
primary versus secondary,　3:1502
recycling,　3:1501,1515-1517
sulfur insertion,　3:1523-1524
adhesives
organotellurium-mediated radical living polymerization,　4:1960
UV-curing, industrial processes,　4:1711
adiabatic electron detachment energres (EDEad), anions, room-temperature ionic liquids,　1:441
adiabatic temperature increase, industrial radical polymerization,　4:1719-1720
adipose tissue, oxidative stress,　3:1690-1692
AdoCb1 (5'-deoxyadenosylcobalamin) see coenzyme B12
advanced glycation end products (AGEs),　3:1681,1682,1684-1685
adventitious oxides, activation by glass reaction vessels, monolayer generation on silicon surfaces　4:2091-2092
A/E see addition-elimination
aerobic oxidations, alcohols,　2:1113,1119-1121
aerobic respiration
electron transfer in proteins,　3:1475,1476
reactive oxygen species generation,　3:1261-1262
AGEs see advanced glycation end products
AGET see activators generated by election transfer
AGE-RAGE-induced free radicals, hyperglycemia,　3:1684-1685
aggregated silyllithium radicals, persistent and stable,　4:2138-2140
alcohols
aerobic oxidations
cerium ammonium nitrate-mediated,　2:1113
copper-catalyzed, nitroxide-mediated,　2:1119-1121
iron-catalyzed, nitroxide-mediated,　2:1119-1121
metal catalyzed, nitroxide-mediated,　2:1119-1121
ruthenium-catalyzed, rutroxide-mediated,　2:1119-1121
Anelli oxidations synthetic applications,　2:1113-1114
Barton-McCombie deoxygenations,　2:621,970
chemoselective oxidations, oxoammonium salts,　2:1108-1117
conversions, thiols, Barton-McCombre deoxygenations,　2:971-972
enthalpies of formation,　1:91-93
formations, epoxide reductive opening,　2:990-993
hydrogen abstractions, metal-catalyzed, nitroxide-mediated,　2:1119-1121
alcohols (continued)
non-anomeric, deoxygenations, carbohydrate synthesis,　2:1158-1160
oxidation to aldehydes, activation of sulfatases SAM radical enzymes,　3:1520
radical generation, Barton-McCombie deoxygenations,　2:965-967
racholysis,　1:410-412
tertiary allylic, oxidative rearrangements oxoammonium salts,　2:1110
aldehydes
additions, ketones,　2:906-907
aldol reactions, ketones, samarium diiodide-mediated,　2:888
asymmetric α-alkylations,　2:1224-1225
azidations, iodine azide,　2:1035
α-benzylations SOMO catalysis,　2:682-683
carbene-catalyzed oxidations, carboxylic ester formation,　2:1105-1106
cyclizations, metal-dependent,　2:919
3-exo/4-exo cychzations, epoxides,　2:995-997
fullerene reactions,　4:2182
glycosyl pyridyl sulfone reductions, 1,2-trans-C-glycostdes synthesis,　2:1137
intermolecular pinacol coupling, samarium diiodide,　2:866
lipid peroxidation products,　3:1585
human physiological levels,　3:1591
α-oxyaminations, SOMO catalysis,　2:680-681
reductions, samarium diiodide, synthetic applications,　2:857-860
α-vinylations, SOMO catalysis,　2:681-682
aldimines cyclizations, vinyl radicals,　2:720-721
aldols, stereoselective synthesis,　2:661-662
aldol-type reactions
aldehydes
aziridinyl ketones, samarium diiodide-mediated,　2:888
oxiranyl ketones, samarium diiodide-mediated,　2:888
aziridinyl ketones, aldehydes samarium diiodide-mediated,　2:888
cyclizations, conjugated reductions, samarium diiodide-mediated　2:888-889
manganese-catalyzed,　2:1014
oxiranyl ketones, aldehydes samarium diiodide-mediated,　2:888
samarium diiodide-mechated synthetic applications,　2:884,887-889
aldosterone, Barton's synthesis, hydrogen atom migration,　1:131,132,133-134
aliphatic amine radical canons, hyperconjugative stabilization,　1:308
aliphatic amines, 2-iodobenzyl protected, iron-catalyzed arylations,　2:1013
aliphatic azides
aminyl radical generation,　2:1032
cyclizations
acyl radicals,　2:1022
alkyl radicals,　2:1021
lactam synthesis,　2:1023-1024
iminyl radical generation,　2:1032
light-induced reactions, allenylindium dichloride,　2:1027
as radical acceptors
carbon radicals,　2:1020-1023
heteroatom-centered radicals,　2:1023-1027
reductions
dichlorindium bromide　2:1026
stannylaminyl radicals,　2:1023
tris(trimethylsilyl)silane,　2:1026
aliphatic cations
ionic liquids, ionization,　1:437
room-temperature ionic liquids,　1:434,444
aliphatic N-cyclopropylamme radical cations, cyclopropane ring opening,　1:307-308
aliphatic free radicals, discovery　1:6-7
aliphatic ketyl radical anions, cyclopropylcarbinyl→homoallyl-type rearrangements,　1:303-306
aliphatic nitroso compounds, spin trapping,　4:2002,2005
aliphatic radicals, history,　1:6-9
aliphatic substrates, SRN1 reactions,　1:348-361
alkali-metal-monosubstituted silyl radicals, stable anion radicals,　4:2137-2138
alkali metals SRN1 reaction initiation,　1:335
alkali metal substituted aggregated silyl radicals, persistent and stable,　4:2138-2140
alkaloids
indolizidine, synthesis, Barton ester photochemical cleavage,　2:1236-1237
pentacyclic, synthesis, tris(trimethylsilyl)silane,　2:580
synthesis, nitrite ester remote functionalizations photochemical,　2:1232
alkanes, carbonylations, flow microreactor experiments,　2:1254-1255
alkene radical cation/carboxyl anion pairs, radical rearrangements by fragmentation/recombination,　1:126-127
alkenes
addition-cyclizations, manganese(III) acetate-mediated,　2:913
additions
alkyl iodides,　2:947
azindinyl radicals,　2:773-774
α-bromo esters　2:953
carboxylic acids, γ-lactone synthesis,　2:904-906
β-dicarbonyl compounds,　2:907-918
diethylthiophosphite,　2:604
β-keto esters,　2:902
kinetics,　1:121-122
organoboranes,　2:603-604
samarium diiodide-mediated,　2:877-879
tertiary amines,　1:291-292
2,2,6,6-tetramethylpiperidine-l-oxyl-malonate,　2:1247
thiols,　4:2018-2019
xanthates,　2:976
aminomethylations, xanthates,　2:975
atmospheric ozone reactions,　1:516,525
carboaminoxylations, flow microreactor experiments,　2:1247,1249
carbodiazenylations, aryldiazonium salts,　2:747-748
conjugate additions, B-alkylcatecholboranes,　2:612
[2+2] cycloadchtions, ruthenium-mediated photocatalysis,　2:1223-1224
electron-deficient, reductions, samarium diiodide,　2:863
hydrosilylations, tris(tnmethylsilyl)silane,　2:566-568
intermolecular additions, epoxide radicals,　2:993-995
ketone-bearing, reductive cyclizations, electrochemically initiated,　2:1206-1207
photoinduced electron transfer,　1:291-292
photosensitized alkylation,　1:288-289
reductive coupling, ethyl 2-(benzenesulfonylammo)acrylate,　2:613
silicon surface attachment, self-assembled monolayers,　4:2085-2086
substitutions, 4-exo-trig cyclizations,　2:699-700
victual hydroxysulfones, xanthate Barton-McCombie deoxygenations,　2:971
alkenylations, organoboranes,　2:606-607
alkenylboron derivatives, radical trapping,　2:622-623
alkenylindium, stereospecific styrylations,　2:606
alkenyl isothiocyanates, cyclizations, tin radical-mediated,　2:1050
alkenyl substituted 1,3-diketones, reductive cyclizations,　2:1207-1208
β-alkoxyacrylates, cyclizations, tris(trimethylsilyl)silane,　2:575,577
alkoxyamines
C-ON bond homolysis,　4:1829-1831
C-ON bond reformation,　4:1831-1833
CO-N bond homolysis,　4:1833
homolysis, nitroxides,　2:1102-1103
nitroxide-mechated polymerization,　4:1813,1828-1837
calculations,　4:1836-1837
chain length effect,　4:1835
penultimate unit effect,　4:1834-1835
reaction pathway,　4:1836-1837
side reactions　4:1833-1834
persistent radical effect,　4:1816
preparation,　4:1828-1829
structures,　4:1814-1815
synthesis, oxoammonium cation/olefin additions,　2:1096
N-alkoxyamines, synthesis, tris(trimethylsilyl)silane-mediated,　2:586-587
alkoxyamines, thermolysis,　1:42,4:1834
alkoxy-base anions, room-temperature ionic liquids,　1:440
N-alkoxy compounds, N-O bonds, photoinduced α-cleavage,　1:279-280
alkoxyl radical fragmentations (ARF)
carbohydrates,　2:1165-1169
oxidative conditions,　2:1166-1168
reductive conditions,　2:1168-1169
alkoxyl radicals, protein radicals,　3:1431-1432
alkoxyl radicals
Brook rearrangements,　2:785-787
3-exo-trig cyclizations,　2:717-718
enthalpies of formation,　1:91-93
formation, RO-X compounds,　2:781-782
fragmentations, hydroazulenone synthesis,　2:734-735
generation, photo-irrachation of thiazole-2[3H]-thione derivatives,　2:1238
1,5-hydrogen abstraction,　1:131-134
hydrogen atom transfers,　2:782-783
β-scission,　2:783-785
α-alkoxy radicals, stereoselective reductions,　2:656
alkylated imidazolium cations, room-temperature ionic liquids,　1:433-434
alkylations
benzothiazole, alkyl bromides, nickel catalyzed,　2:1007
cobalt-catalyzed, styrene,　2:1010-1011
ethyl pyruvate,　2:613
nickel-catalyzed, benzothiazole alkyl bromides,　2:1007
pyrroles, synthetic applications,　2:1078
reductive, stereoselective, chiral Lewis acids,　2:672-676
styrene, cobalt-catalyzed,　2:1010-1011
titanium-catalyzed, styrene,　2:1014-1015
α-alkylations
asymmetric, aldehydes,　2:1224-1225
ketones, N-sdoxyenamine,　2:606
alkyl azides, additions, acyl/alkyl radicals,　2:770
alkyl-base anions, room-temperature ionic liquids,　1:440
9-alkyl-9-borabicyclo[3.3.1]nonanes, cross-coupling, alkyl iodides,　2:1004-1005
alkylborane radical traps,　2:624
alkyl bromides
benzothiazole alkylations,　2:1007
nickel-catalyzed cross coupling,　2:1006-1007
reduction by tin hydride, radical chain reaction steps,　1:108
tin hydride-mediated radical generation,　2:543-544
alkylcatecholboranes additions, nitroxides, carbon radical generation,　2:1097
B-alkylcatecholboranes,　2:610-616
additions, tetranitromethane,　2:615
allylations,　2:613
cascade addition-allylations　2:613
chalcogenattons　2:613-616
conjugate additions,　2:610-612
cyanations,　2:614
formylations,　2:614
β-fragmentations,　2:612-613
halogenations,　2:613-616
modified,　2:616
oxygenations,　2:613-616
radical reactions,　2:610-613
tandem enannoselective conjugate addition-radical alkoxyaminations　2:615
vinylations,　2:614
alkyl halides
allylations
cobalt-catalyzed,　2:1008-1009
silver-catalyzed,　2:1014
arylations, cobalt-catalyzed,　2:1009
benzylations
cobalt-catalyzed,　2:1008-1009
silver-catalyzed,　2:1014
carbonylations, high pressure carbon monoxide gas,　2:1246-1248
cross coupling
cobalt-catalyzed,　2:1008-1009
iron-catalyzed,　2:1012-1013
nickel-catalyzed,　2:1006-1008
fullerene additions,　4:2189
high gas pressure carbonylanons, alkyl halides,　2:1246-1248
Mizoroki-Heck reactions, cobalt-catalyzed,　2:1010-1011
photocatalytic reductions, ruthenium-mediated,　2:1225-1226
reductions
nickel-mediated, electrochemically initiated,　2:1208-1211
ruthenium-mediated photocatalysis,　2:1225-1226
samarium diiodide, synthetic applications,　2:856-857
tris(trimethylsilyl)silane-mediated, flow microreactor experiments,　2:1244-1246
reductive cleavage, tris(trimethylsilyl)silane　2:569-570
SRN1 reactions,　1:333,348-354
styrene double alkylations, titanium-catalyzed,　2:1014-1015
alkyl iodides
atom transfer radical additions,　2:946-947
atom transfer radical cyclizations,　2:948
cross-coupling, 9-alkyl-9-borabicyclo[3.3.1]nonanes,　2:1004-1005
hydroxymethylations, organoboranes,　2:621
radical generation, un hydride mediated,　2:544-545
alkyl monolayers on silicon, radical chain propagation,　4:2084-2089
alkyloxy radicals, fullerene reactions,　4:2180-2182
alkyl radicals
additions
alkyl azides,　2:770
isothiocyanates,　2:1049-1050
alkyl radicals (continued) unsaturated carbohydrates, α-C-glycosides synthesis,　2:1137-1139
arylations, protonated pyridines, relative rates,　2:1076
azidations pyrrolidinone synthesis,　2:804
clocks,　1:114,115,116
cyclizations aliphatic azides,　2:1021
cyclopentane derivative synthesis,　2:1152-1153
generation, thiol desulfurations,　2:1047
hydrogen abstraction,　1:139,141
matrix isolation spectroscopy,　1:210-214
reductions, tin-hydride mediated,　2:542
scavengers, persistent radical effect modeling,　4:1816,1817
stability,　1:454-463
sulfinate ring-closures,　2:637
sultine synthesis,　2:638
alkyl selenides, arylations, whitasomnine synthesis,　2:1066
alkyl substituted benzenes, biaryl compound synthesis,　2:1184-1195
alkyl substrates, SRN1 reactions,　1:354-355
alkylthio radicals, fullerene reactions,　4:2180-2181
alkyne derivatives, ketone-bearing reductive cyclizations,　2:1206-1207
alkyne radicals 1,2-thiophosphinoylations phosphorus-centered radicals　2:793-794
alkynes
additions
organoboranes,　2:603-604
samarium diiodide-mediated,　2:877-879
carbotellurations,　2:958-959
hydrositylations, tris(trimethylsilyl)silane,　2:567-568,570-571
photoinduced additions silylated tertiary amines,　2:1218-1219
radical thiol addition reactions, mechanism,　4:2018,2019-2020
silicon surface attachment self-assembled monolayers,　4:2086-2087
alkynyl isonitriles, cyclizations, indole synthesis,　2:1045-1046
allenylindium dichloride, light-induced reactions, aliphatic azides,　2:1027
(-) alliacol A, synthesis,　2:1182
(-)-allo muscarine, synthesis, oxygen-centered radicals,　2:790
all-trans compounds, lipid isomerization,　3:1603
allylations
B-alkylcatecholboranes,　2:613
alkyl halides, silver catalyzed,　2:1014
allyl alcohol denvates, xanthates,　2:983
allylindium dichloride, alkyl azides　2:769
cross-coupling, alkyl halides cobalt-catalyzed,　2:1008-1009
cyclohexannone, SOMO catalysis,　2:684
diastereoselective,　2:660-661
enantioselective
cerium(IV) ammonium nitrate mediated,　2:906-907
SOMO catalysis,　2:680-681
α-halo carbonyl compounds, zirconium-catalyzed,　2:1015-1016
1,3-inductions,　2:656-657
malonyl radicals, chiral auxiliaries,　2:660,662
organoboranes,　2:606-607
silver-catalyzed, alkyl halides,　2:1014
SOMO catalysis, cyclohexannone,　2:684
sulfonamidyl radicals,　2:1028
tris(trunethylsilyl)silane-mediated,　2:584-585
xanthates,　2:981-982
zirconium-catalyzed α-halo carbonyl compounds,　2:1015-1016
C-allylations, stereocontrol, hydrogen bonding,　2:657
allylboron derivatives, additions, α-iodoesters,　2:622
allyl derivatives, activated, SRN1 reactions　1:361
C-allyl glycosides synthesis, glycos-1-y1 radical intermolecular trapping allystannanes,　2:1133-1134
allylic alcohols
allylations, xanthates,　2:983
synthesis, β-hydroxyepoxide deoxygenations,　2:989-990
tertiary oxidative rearrangements, oxoammonium salts,　2:1110
allylic C-N bonds, thiol-mediated cleavage,　2:798
allylic stannanes, fullerene additions,　4:2189-2190
allytic O-stannylketyl radicals 2,3-disubstiluted indole synthesis,　2:553-554
allyl iodoacetate
5-exo cyclizations,　2:950
oligomenzation/deoligomerization,　2:952
allylpinacolborane, xanthate transfers,　2:623
allyl radicals
3-exo-trig cyclizations,　2:696
matrix isolation spectroscopy,　1:218
stability,　1:454
allylsilane enol ethers, oxidations, electrochemically initiated,　2:1176-1177
allylsilyloximes cascade reactions, haloesters,　2:741-742
allylsulfones, B-alkylcatecholborane allylations,　2:613
N-allylsulfonyl compounds, nitrogen centered radical generation,　2:773
allyltributylstannane
C-glycoside synthesis,　2:1132-1133
C-ketoside synthesis,　2:1141-1142
α-functionalized polymers, nitroxide-mediated polymerization,　4:1840
α-particles,　1:395
alternating copolymers
atom transfer radical polymerization,　4:1871
industrial radical polymerization,　4:1714
organoheteroatom-mediated tactical living polymerization,　4:1943,1944-1945,1949
alternating current (AC), second harmonic voltammetry　1:255
aluminosilicates (zeolites)
radiation-induced radicals,　1:421-423
radical reactions inside framework,　1:245
aluminum-centered radicals, electron patamagnetic resonance,　1:161,162
amide bonds, stepping stones, electron transfer in peptides/proteins,　3:1490-1493
amides
benzoic acid derivatives, silane-mediated synthesis,　2:594-595
reductions, samarium diiodide,　2:860
amiltyl radicals
cascade reactions, indolizidine/pyrrolizidine skeleton synthesis,　2:730-731
formation
copper(I) mediated,　2:774
N-O bond cleavage,　2:776
spontaneous homolytic cleavage,　2:774-775
tin hydride-mediated,　2:554-556
xanthates,　2:976-977
hydrogen atom migration,　1:131,132
trapping, xanthates,　2:976-977
amine-bearing electron-rich olefins, oxidations,　2:1177-1178
amine-bearing thioenol ethers, cyclizations,　2:1177-1178
amine radical cations, cyclopropane ring opening,　1:307-308
amines
addition to fullerenes,　4:2186-2189
cyclic, synthesis, tris(trimethylsilyl)silane,　2:576-577
enthalpies of formation,　1:95-97
polymerization, reversible addition fragmentation chain transfer,　4:1906
secondary, synthesis, tris(trimethylsilyl)silane,　2:565
tandem racemizations, sulfur-centered radicals,　2:798
aminium cation-radical salts, organic electron donor activations,　2:842-844
aminium radical cations, hydrogen atom extraction,　1:135,137
amino acids
electron transfer to guanosyl radicals, non enzymatic DNA repair, time resolved chemically induced dynamic nuclear polarization studies,　1:196-197
functionalized peptides, radical thiol addition click reactions,　4:2022,2024-2025,2026,2027,2028
oxidant reaction rates,　3:1426,1427
oxidation products,　3:1432,1433-1436
oxidations α-keto acid synthesis, Fremy's salt　2:1123
radical reactions,　3:1428
residues, electron transfer in proteins and peptides,　3:1477-1478,1479-1487
selenium-containing, radical reactions,　3:1459,1460,1461,1466-1467,1472
spin labels,　4:1967
sulfur-containing, radical reactions,　3:1459-1474
thioethers/selenothioethers,　3:1467-1472
thiols/selenols,　3:1460-1467
α-aminoalkyl radicals photochemical synthesis of metal nanostructures,　4:2197,2200,2203
α-aminoamides, radical Strecker synthesis,　2:747-748
2-amino-1-hydroxyalkyl radicals water/ammonia elimination reactions,　3:1509,1510
aminomethylations, alkenes, xanthates,　2:975
ammomutases
coenzyme B12-dependent,　3:1508,1513-1514,1516,1526
SAM-dependent,　3:1513-1514,1515-1516,1526
aminopyrene (APy), DNA conjugation, excess election transfer,　3:1419,1420-1421
amino-substituted bis(silyl) silicon-centered radicals persistent and stable,　4:2134
aminosugars, synthesis, sulfur-centered radicals,　2:800
aminoxyl-mediated polymerization
use of term,　4:1726,1799
see also nitroxide-mediated polymerization
aminoxyl radical-mediated reactions, electrochemically initiated,　2:1202-1203
aminoxyl radicals, see also nitroxides
α-(aminyloxy)ketones, synthesis, radical adchtion-alkoxy aminations,　2:614
aminyl radicals
cyclizations, sp-hybridized carbons,　2:717-718
formation,　2:768,769-770
copper(I)-mediated,　2:774
N-C bond cleavage,　2:778-779
N-O bond cleavage,　2:776
organic azides,　2:1020
tin hydride-mediated,　2:554-556
ammonia, radiation-induced radicals in gaseous systems,　1:398
(-)-amphidinolide K, core tetrahydrofuran synthesis, relay cyclizations,　2:736
anellated tetrahydrofurans synthesis, oxygen centered radicals,　2:788-789
Anelli oxidations, alcohols,　2:1113-1114
angiotensin ieceptor agonists, selenium-containing,　2:643-644
anhydroalditols, synthesis,　2:1155-1156
anhydrovinblastine, synthesis, epoxide deoxygenations,　2:989-990
anilides, hydrogen abstraction,　1:139
anilinamides, oxidations, IBX-mediated,　2:779
animal studies, lipid peroxidation,　3:1589
anionic/anionic sequences, carbon-carbon bond sequential formation,　2:895
anionic polymerization systems, RAFT,　4:1901-1902
anionic radicals
cation/neutral radical comparison,　1:301-3332
cyclopropylcarbinyl→homoallyl-type rearrangements,　1:302-306
DNA, ionizing radiation formation,　3:1371-1372
from ketones,　1:302-306
fullerenes,　4:2186-2190
ring opening,　1:302-304
room-temperature ionic liquids,　1:433,434,438-444
silyl anion radicals, persistent and stable,　4:2135-2138
SRN1 reactions,　1:333,334,335
sulfur-containing amino acids,　3:1460,1461,1467
anionic/radical sequences, carbon-carbon bond sequential formation,　2:895
anions, organic, room-temperature ionic liquids,　1:440-442
anisole, anodic coupling, veratrol, triphenylene core synthesis,　2:1191-1192
anisole derivatives, enol-ether, cyclizations,　2:1183
anisotropic hyperfine interactions, DNA radicals,　3:1375,1376-1381
[3+2] annulations
chastereoselectivity,　2:658,660
pyrrolidine synthesis,　2:605
[4+1] annotations
iminyl radicals, isonitriles,　2:1043-1044
vinyl radicals, isonitriles,　2:1043
annotations
aryl radicals, isothiocyanates,　2:1050-1051
iodomethylaziridine derivatives, pyrrolidine derivative synthesis,　2:604
isothiocyanates, aryl radicals,　2:1050-1051
malonates,　2:947
malononitriles,　2:947
anodic oxidations
carboxylic acids,　2:1196-1202
substrate substitution patterns,　2:1196
coupling,　2:1205-1207
protected dicarboxylic acids,　2:1197
anodic processes, electrochemically initiated reactions,　2:1176-1206
anomeric effect radical rearrangements,　1:128,129
anomeric radicals, chastereoselective hydrogen quenching,　2:1156-1157
Antarctic ozone hole,　1:511-513,517-518,525
anthracene
photocatalytic chmenzation,　1:388,389
photocatalytic oxygenation via radical ion coupling,　1:370-372
anlibonding species, hydrogen transfer kinetics,　1:101-102
antiferromagnetic ordering versus spin-gap formation, thiazyl radicals,　4:2151-2152
anti-Markovnikov addition
peroxide effect,　4:1851,1852
radical thiols to unsaturated compounds,　4:2018,2019
antimony, organostibine-mechated living radical polymerization,　4:1932-1958,1960
antimony-based nucleophiles SRN1 reactions,　1:339-340
antioxidant responsive elements (AREs),　3:1627
antioxidants,　3:1623-1677
biological defences,　3:1425
chase-breaking,　3:1623,1627-1672
antioxidants (continued)
definition,　3:1623
enzymes and proteins,　3:1625-1627
hydroxyl reaction rate constants,　3:1426
indirect antioxidants,　3:1623,1626-1627
lipid isomerization inhibition,　3:1616-1617
lipid peroxidation inhibition,　3:1578,1583-1584,1589,1593,1594
natural products,　3:1669-1672,1673
nitrogen-containing,　3:1661-1665,1673
phenolic compounds,　3:1627-1661
preventive antioxidants,　3:1623,1624-1626
protein-derived radicals,　3:1448-1449
reactive oxygen species defence,　3:1277
small molecules,　3:1624-1625,1627
sulfur-containing,　3:1625,1665-1667,1673
superoxide dismutases,　3:1626
synergism and cooperativity,　3:1667-1669
vitamins,　3:1669-1672,1673
see also radical scavengers
anti-Stokes Raman spectroscopy, combustion engine research,　1:479
(-)-aphanophine, synthesis, carbamoyl diethyldithiocarbamate cyclizations,　2:1235
apolipoprotein B-containing lipoproteins, the metabolic syndrome,　3:1685
aqueous dispersed media
industrial polymerization,　4:1722-1723
nitroxide-mediated polymerization,　4:1821,1822,1840
see also emulsion...;microemulsion...;miniemulsion...
aqueous environments, photochemical radical-mediated metal nanostructure synthesis,　4:2197,2198,2200,2209
aqueous-phase oxidants, troposphere,　1:504,519
aqueous solutions, radiation-induced radical reactions,　1:400-410
arachidonic acid/arachidonates
enzymatic lipid peroxidation,　3:1579,1580
free-radical-mediated lipid peroxidation,　3:1582-1583
arenediazonium salts
aryl radical generation,　2:824
oxidations,tetrathiafulvalenes,　2:819-826
reductions, tetrakisdimethylaminoethene,　2:828
arenes
additions, aryl radicals, spirocyclic cyclohexadienone synthesis,　2:1063-1064
borylations,　2:1086-1087
phosphonations,　2:1086-1087
AREs see antioxidant responsive elements
ARF see alkoxyl radical fragmentations
ARGET see activators regenerated by electron transfer
argon
matrix isolation,　1:207
radiation-induced radicals in gaseous systems,　1:399
A ring construction, 1,22-dihydroxynitiane nitiol analogs, Norrish reactions,　2:1228
aromatic aldehydes, photocatalytic oxygenation of aromatic compounds,　1:374-375
aromatic amines, antioxidant action,　3:1661-1663
aromatic amino acids, relay stations in electron transfer,　3:1481-1484
aromatic anions, room-temperature ionic liquids,　1:442-444
aromatic azides
additions, aryl radicals,　2:770-771
cyclizations, dichlorindium bromide,　2:1026-1027
cyclohexadieniminyl radical formation,　2:1033-1034
as radical acceptors
carbon radicals,　2:1020-1023
heteroatom-centered radicals,　2:1023-1027
reductions
dichlorindium bromide,　2:1026
stannylaminyl radicals,　2:1023
triethylsilane,　2:1025-1026
tris(trimethylsilyl)silane,　2:1026
spirocyclic azidocyclohexadienyl radical formation,　2:1032-1033
aromatic cations
ionic liquids, ionization,　1:437,438
room-temperature ionic liquids,　1:434,444-446
aromatic α-chloroacetamides, photoinduced mesolytic cleavage,　1:295
aromatic compounds
photocatalytic oxygenation to aromatic aldehydes,　1:374-375
reduction, radical enzymes,　3:1534-1536
SRN1 reactions,　1:333,336-347
synthesis, xanthates,　2:978-981
aromatic ethers/esters, C-O bonds, photoinduced α-cleavage,　1:280-281
aromatic homolytic substitutions, cascade reactions with cyclizations,　2:737
aromatic ketyl radical anions, cyclopropylcarbinyl→homoallyl-type rearrangements,　1:302-303,305
aromatic nitroso compounds, spin trapping,　4:2002,2005
aromatic radical cations, one-electron oxidation, guanine,　3:1295-1297
aromatic rings
3-exo-trig cyclizations,　2:697
electron-rich, oxidations, electrochemically initiated,　2:1180-1183
aromatic substitutions
free-radicals, history,　1:28-29
homolytic, tris(trimethylsilyl)silane-mediated,　2:586-587
aromatic thiols
coupling, anodic oxidations,　2:1205-1207
radical addition to unsaturated compounds,　4:2018
aromatizations
cyclohexadienyl radicals, isonitriles,　2:1044
nitroxide-mediated, Hantzsch 1,4-dihydropyridines,　2:1105-1106
photochemical, Hantzsch 1,4-dihydropyridines, nitroxide-mediated,　2:1105-1106
arrested growth, radical-mediated metal nanostructure synthesis,　4:2204
Arrhenius activation energies,　1:81
bond dissociation enthalpy measurement,　1:82-83
arsenic-based nucleophiles, SRN1 reactions,　1:339-340
artificial DNA structures, charge transfer,　3:1397-1398,1407-1411,1412-1413
artificial nucleobases, charge transfer effects,　3:1397,1398
arylations
alkyl radicals, protonated pyridines, relative rates,　2:1076
aryl radicals
cyclizations,　2:1082-1086
olefin additions,　2:1066-1067,1080-1082
axanthate, organoboranes,　2:607
borylations, synthetic strategies,　2:1086-1087
carbon-centered radicals,　2:1059-1069,1074-1079
cobalt-catalyzed, alkyl halides,　2:1009
β-dicarbonyl compounds,　2:910
homolytic aromatic substitutions
carbon-centered radicals,　2:1059-1069,1074-1079
intermolecular,　2:1074-1079
intramolecular,　2:1059-1074
radical aryl migrations,　2:1069-1074
synthetic strategies,　2:1059-1080
tris(trimethylsilyl)silane-mediated,　2:586-587
ipso substitutions,　2:1079
iron-catalyzed, benzene,　2:1013-1014
organoboranes,　2:607
phosphonations,　2:1086-1087
radical, axanthate, organoboranes,　2:607
synthetic strategies,　2:1059-1093
α-arylations
cerium(IV) ammonium nitrate-mediated,　2:924-927
iron(III) salt-mediated,　2:924-927
SOMO catalysis, enantioselective,　2:680-681
arylative cyclizations,　2:1008-1009,1082-1086
arylboronic acids, biaryl synthesis,　2:616
aryl bromides, radical generation, tin hydride-mediated,　2:544
arylcyclopropanes, ring expansions,　1:308-309
aryldiazonium salts, carbodiazenylations, alkenes,　2:747-748
aryl esters, samarium diiodide mediated reactions,　2:860
aryl ethers
anodic coupling, biaryl synthesis,　2:1191
hydrogen abstraction,　1:138
aryl iodides, chiral radical generation, tin hydride-mediated,　2:544-545
arylmethyl radicals, history,　1:2-6
aryl migrations
homolytic aromatic substitutions,　2:1069-1074
intramolecular tin to carbon,　2:948
aryl nitroxides, nitroxide-mediated polymerization,　4:1827-1828
aryloxyl radicals, phenolic antioxidant action,　3:1628,1643,1651,1655-1657
aryloxy radicals, history,　1:14-15
aryl radicals
additions
arenes, spirocyclic cyclohexadienone synthesis,　2:1063-1064
aromatic azides,　2:770-771
olefins, synthetic applications,　2:1066-1067,1080-1082
annulations, isothiocyanates,　2:1050-1051
arylations, synthetic strategies,　2:1080-1087
clocks,　1:116
5-endo-trig cyclizations,　2:705-706
cyclizations
aldimines,　2:721
cyclic alcohol effects,　2:714
ketimines,　2:721
organic azides,　2:1020
synthetic strategies,　2:1082-1086
tris(trimethylsilyl)silane,　2:579
unusual pathways,　2:713-714
endocyclic closure,　2:713-714
fullerene reactions,　4:2179-2180
generation
arenediazonium salts,　2:824
aryl iodides, tin hydride-mediated,　2:544-545
hydrogen abstraction,　1:137,141,142
matrix isolation spectroscopy,　1:218-225
ring-closures, at sulfur,　2:636-637
sulfinamide ring-closures,　2:637
sulfinate ring-closures,　2:637
trapping, nitroxides,　2:1101-1102
aryl rings, addition-cyclizations,　2:911-913
2-arylsulfinylcyclopentenones, additions, trialkylboranes,　2:609
aryltelluro groups, atom transfer radical additions/cyclizations,　2:958-961
ascorbic acid/ascorbate (vitamin C)
antioxidant action,　3:1623,1669-1670
coantioxidant,　3:1668
radical scavenging,　3:1268,1271,1277
related compounds, antioxidant action,　3:1670
α-tocopherol synergism,　3:1667,1669
(±)-aspidospermine, synthesis, organic electron donors,　2:819,822
astrobiology (exobiology), atmospheric chemistry,　1:480
astrochemistry (interstellar chemistry), low temperature studies,　1:481-482,496-497
asymmetric α-alkylations, aldehydes,　2:1224-1225
asymmetric atom transfer radical cyclizations, bromine atoms,　2:954
asymmetric conformation, chiral methylthiofullerenes,　4:2181
asymmetric electron transfers
chiral ligand-assisted,　2:686-689
samarium-mediated,　2:686-687
titanium-mediated,　2:687-688
asymmetric reductions, ketones, samarium diiodide, synthetic applications,　2:859
A-tensor, anisotropic hyperfine interactions, DNA radicals,　3:1378-1380
atherosclerosis, lipid peroxidation,　3:1577
atmospheric chemistry,　1:480,503-528
anthropogenic effects,　1:504-505,513-514,515-516,523
condensed phase processes,　1:503-504,519
CRESU,　1:497
extraterrestrial bodies,　1:480
matrix isolation spectroscopy,　1:212
oxygen, evolution of life,　3:1261
ozone depletion mechanisms,　1:506,508-509,510-513
photochemical reaction rates,　1:503,505-506
pollutants, oxidative cleansing mechanisms,　1:514-525
radical families,　1:505
stratosphere,　1:505,506-513
troposphere,　1:505,513-525
vertical layers,　1:504-505
atmospheric effects, radical-mediated metal nanostructure synthesis,　4:2205-2206
atom abstraction rates, substituent effects,　1:102-103
atom transfer processes
iodoalkane carbonylations, flow microreactor experiments,　2:1254
organoheteroatom-mediated living radical polymerization,　4:1932-1960
radical chain reactions,　1:65-66,75-76
sequential radical addition/cyclization,　4:1882-1884
atom transfer radical addition (ATRA),　4:1851-1894
alkenes
alkyl iodides,　2:947
α-bromo esters,　2:953
alkyl iodides,　2:946
alkenes,　2:947
carbon monoxide,　2:946
applications,　4:1879-1887
aryltelluro groups,　2:958-961
bromine atoms,　2:952-954
α-bromo esters, alkenes,　2:953
carbon monoxide, alkyl iodides,　2:946
catalyst regeneration processes,　4:1880-1887
chain reactions,　1:66,75
chalcogens,　2:943-963
atom transfer radical addition (ATRA) (continued)
copper-catalyzed,　2:955-956
enanuoselective, iodine atoms,　2:952
fundamentals,　4:1851-1854
halogens,　2:943-963
α-heteroatom-stabilized radicals　2:957
ICAR/ARGET processes,　4:1879-1880
iodine atoms　2:945-947
Kharasch-type,　2:1003-1004
Lewis-acid catalyzed, bromines,　2:953
mechanisms,　2:943-945
nitrogen-centered radicals,　2:774-775
non-transitionmetal-catalyzed,　4:1851,1852
organic ttansformations,　4:1884-1887
perfluoroalkyl iodides,　2:946
peroxide effect,　4:1851,1852
phenylseleno groups,　2:956-958
ruthenium-catalyzed,　2:955-956
sequential processes,　4:1882-1887
stereoselective, organoselerudes,　2:958
transition metal-catalyzed,　2:1003-1004,4:1851,1853-1854,1879-1880
atom transfer radical cyclization (ATRC),　4:1854
alkyl iodides,　2:948
applications,　4:1879-1885
aryltelluro groups,　2:958-961
asymmetric, bromine atoms,　2:954
bromine atoms,　2:954
catalyst regeneration processes,　4:1880-1887
chain reactions,　1:65,66
chalcogens,　2:943-963
chlorine atoms,　2:954-956
copper-catalyzed,　2:955-956
halogens　2:943-963
ICAR/ARGET processes,　4:1879-1880
iodine atoms,　2:947-952
α-iodoesters,　2:949
ketones,　2:949
malonyl radicals,　2:949
organic transformations,　4:1884-1887
phenylseleno groups,　2:956-958
ruthenium-catalyzed,　2:955-956
sequential processes,　4:1882-1887
stereoselective, organoselerndes,　2:958
transition metal catalyzed,　4:1854,1880-1382
atom transfer radical polymerization (ATRP),　4:1802-1805,1854-1879
activation rate constants,　4:1864-1865
activators generated by electron transfer,　4:1862
activatois regenerated by electron transfer,　4:1862-1863
additives,　4:1860
advantages/limitations,　4:1807
alternating copolymers,　4:1871
applications,　4:1878-1879
alchitecture control,　4:1804-1805
block copolymers, 4:1871-1872　1878
chain end functionality,　4:1794-1797
chain reactions,　1:76
complexing ligands,　4:1856-1857,1858
components,　4:1855-1860
composition control,　4:1869-1873
control of topology/composition/functionality,　4:1804-1805,1855,1869-1878
copolymers,　4:1870-1873,1874-1875
applications,　4:1878-1879
copper catalysts,　4:1854-1855,1856-1857,1853,1861,1862-1863
deactivation rate constants,　4:1865-1866
equilibrium constants,　4:1864
flow microleactor expenments,　2:1248-1250
fullerenes,　4:2180
functional polymers,　4:1794-1797,1877-1878,1879
gradient copolymers,　4:1871
homopolymers,　4:1869-1870
industrial processes,　4:1726,1729-1730
initiation,　4:1860-1861
initiators,　4:1794-1797,1804,1856
initiators for continuous activator regeneration,　4:1863
iron complexes,　4:1858-1860
kinetics,　4:1861,1863-1864
linear segmented copolymers,　4:1871-1872
mechanistic features,　4:1863-1869
monomers,　4:1803,1855-1856
non-copper transition metal catalysts,　4:1857-1860
outer-sphere versus inner-sphere electron transfer,　4:1869
peisistent radical effect,　4:1786,1787,1797-1799
radical nature of propagating species,　4:1868-1869
redox potential/equilibrium constant correlation,　4:1866-1868
reverse process　4:1861-1862
reversible addition fragmentation chain transfer combination,　4:1902
reversible addition fragmentation chain transfer comparison,　4:1902,1903
ruthenium complexes,　4:1859,1860
SFRP comparison,　4:1802
statistical copolymers,　4:1871
stereoblock copolymers,　4:1873
thermodynamics,　4:1863-1864
topology,　4:1804-1805,1873-1877
transition metal-catalyzed,　2:1004,4:1854-1855,1856-1860
transition metal complex-catalysts,　4:1803-1804
ATRA see atom transfer radical addition
(±)-atractyligenin, synthesis ketone reductions,　2:858
ATRC see atom transfer radical cyclization
ATRP see atom transfer radical polymerization
Au3+ ions, photochemical radical-mediated metal nanostructure synthesis,　4:2202,2203
AuCl4- ions, photochemical radical mediated metal nanostructure synthesis,　4:2202,2203
autoinitiation, industrial radical polymenzation,　4:1706
autoxidations
antioxidants,　3:1623
β-carotene,　3:1670-1671
chain reactions,　1:73-74
glucose,　3:1681
heme proteins, reactive oxygen species generation,　3:1264-1265,1266
lipid isomenzation,　3:1616
nitroxide-mediated, synthetic applications,　2:1123
organoboranes,　2:602
tris(trimethylsilyl)silane,　2:568-569
see also inhibited autoxidation
axanthate, radical arylations, organoboranes,　2:607
2-azabenzonorobornanes, synthesis, tris(trimethylsilyl)silane-mediated,　2:589-590
azabicyclic N-oxyl radicals, menthol oxidations, electrochemically initiated,　2:1203
azachrachtin, AB ring synthesis, stereoselective radical cascade,　2:730
6 azaindoles, synthesis, xanthates,　2:979,981
6-azaindolines, synthesis, xanthates,　2:979,981
azeotropic composition, copolymerization,　4:1715
azethoxyl nitroxides, spin labels and spin probes,　4:1967
azidations
aldehydes, iodine azide,　2:1035
alkyl radicals, pyrrolidinone synthesis,　2:804
benzyl ethers, iodine azule,　2:1034
carbon compounds, iodine azide,　2:1034-1035
cyclic acetals, iodine azide,　2:1034-1035
hydrocarbons, azidolodinanes,　2:1035-1036
azide-alkyne click reactions, nucleic acid spin labeling,　4:1971,1972
azides
cyclizations, acyl/alkyl radicals,　2:1021
inorganic,　2:1034-1036
nitrogen-centered radical formation,　2:767-771
organic,　2:1020-1034
as radical acceptors,　2:1019-1036
reductions, tris(trimethylsilyl)silane,　2:1026
α-azidoalkyl radicals, iminyl radical generation,　2:1032
azido groups, transfers, organic azides,　2:1028
azidolodinanes, azidatons, hydrocarbons,　2:1035-1036
azidonitriles cyclizations, dichlorindium bromide,　2:1026-1027
azidoselenations, exo-glycals, C-ketoside synthesis,　2:1141-1142
azidosulfonylations, 1,6-dienes/1-en-6-ynes, organic azides,　2:1030-1031
azido-transfers, organic azides, sulfonyl radicals,　2:1028
azindmes, opening, N-tosylamino radical formation,　2:778
azindinyl ketones aldol reactions, aldehydes, samarium diiodide-mediated,　2:888
azindinyl radicals,　2:773-774
azo(bisisobutyrate), fullerene reactions,　4:2179
azo(bisisobutyronitrile) radicals, fullerene inactions,　4:2179
azo compounds
free-radical sources, history,　1:25-26
initiators, industrial radical polymenzation,　4:1706-1707,1708
thermolysis,　1:39-40
azurin biomolecular rectifiers,　3:1495
backbiting, polymerization kinetics,　4:1779
backside mechanisms, intramolecular homolytic substitutions,　2:629-631
bacteria, lipid isomenzation,　3:1617-1619
Baldwin's rules of ring closure, radical chain cyclizations,　1:71,2:693
Barbier conditions, C-chsaccharide synthesis,　2:1140
Barbier reactions, samarium diiodide-mediated,　2:879-884
Barton carbonates, C-centered radical conversion,　2:611
Barton decarboxylations, radical chain reactions,　1:67-68
Barton esters,　1:110,113-114
decarboxylations, photochemical cleavage,　2:1235-1237
photochemical cleavage
disulfide trapping,　2:1236-1237
platensimycin synthesis,　2:1235-1236
preparation, tin hydride-mediated,　2:547
PTOC esters, radical chain reaction initiation,　1:110,113-114
PTOC thiol method,　1:112-113
radical chain reactions,　1:68,76-77
reductive decarboxylations, cyclopropanes, tin hydride-mediated,　2:547
Barton-McCombie deoxygenations
alcohols,　2:621
alkene formation, vicinal hydroxysulfones,　2:971
carbohydrate synthesis,　2:1158-1160
flow mtcroreactor experiments,　2:1244-1246
mechanism,　2:965-967
radical chain reactions,　1:67
synthetic variations,　2:970-972
tin-free modifications,　2:967-970
tributyltin hydride-mediated,　2:549-550
xanthates,　2:549-550,965-967
Barton-McCombie intermediates, xanthate derived, neophilic rearrangements,　2:971
Barton reactions
aldosterone synthesis, hydrogen atom migration,　1:131,132,133-134
nonchain reaction sequences,　1:109
"base off, his-on" mutases,　3:1506,1507-1508,1511-1514
"base on" eliminases,　3:1505-1506,1507,1509-1511
base-pair disruption, DNA hole transfer,　3:1409-1411
base stacking, DNA charge transfer effects,　3:1398
batch reactors, industrial radical polymerization,　4:1724-1725
batteries
conventional,　4:2163
flexible,　4:2163,2167,2169
polyrachcal,　4:2163-2170
radical polymers,　4:2164,2165-2168
charge transport and storage,　4:2165-2166
configuration,　4:2166-2168
rechargeable
conventional,　4:2163-2169
organic,　4:2163-2169
types and materials,　4:2163
BBDTA salts, ferromagnetism, crystal solvent evaporation,　4:2155-2156
BDE see bond dissociation energy
(BDTA)2[Co(mnt)2]
charge transfer phase transitions,　4:2152-2154
crystal structine,　4:2153
BDTA see 1,3,2-benzodithiazolyl
BDTDA, photoconductivity,　4:2159
BEBO see bond energy-bond order
bengamide E, total synthesis, nitroxide-mediated,　2:1114
Benson's group additivity scheme, enthalpies of formation estimation,　1:84,88
benzaldehydes, coupling samarium dnodide,　2:854-855
benzazepines, synthesis, electrochemically initiated,　2:1193
benzene, arylations, iron-catalyzed,　2:1013-1014
1,4-benzene chradical trapping, nitroxides, enediyne Bergman cyclizations,　2:1101-1102
benzeneselenol
polarity reversal catalysis, tin hydride mediated alkyl radical reductions,　2:542
radical mediator,　2:809-810
benzoates, synthesis, phenol conversions,　2:697
benzochazepinone synthesis, homolytic aromatic substitutions,　2:1066
1,3,2-benzochthiazolyl (BDTA),　4:2151-2152
benzoic acids, slime mediated reactions,　2:594-595
benzophenone-initiated photoadditions, branched chain sugar synthesis,　2:1142-1143
benzophenones, steroid remote functionalizations,　2:1229-1231
benzophenone triplet state (3BP), hydrogen abstraction,　1:48-49
benzoquinones synthesis, phenol oxidations, Fremy's salt,　2:1122
benzo[b]tellurophenes, synthesis,　2:638-639,643-644
benzothiazole, alkylations, alkyl bromides,　2:1007
benzylamine, photocatalytic oxygenation,　1:380
benzylations, alkyl halides,　2:1008-1009,1014
α-benzylations, aldehydes, SOMO catalysis,　2:682-683
N-benzyl-N-cyclopropylamine radical cations, mechanistic inhibitors in SET enzymes,　1:310
benzyl derivatives, activated, SRN1 reactions,　1:355-358
benzyl ethers, azidations, iodine azide,　2:1034
benzyl halides, activated, SRN1 reactions,　1:355-358
benzyl methacrylate, polymerizations, flow microreactor experiments,　2:1247,1249
1-benzyloxy-9,10-anthraquinones, photochemical isomerizations,　2:698
benzyl radicals
addition to fullerenes,　4:2172,2173
clocks,　1:114-115
matrix isolation spectroscopy,　1:222-223
stability,　1:454,458
synthesis, 10-exo-trig closures,　2:714-715
4-benzylseleno-β-lactams, intramolecular homolytic substitutions,　2:640
benzylsuccinate synthase, theoretical studies,　3:1566-1568
Bergman cyclizations
5-endo-dig cyclization terminations,　2:709
enediynes,　2:1101-1102
Bergman cycloaromatizations,　2:710-711
Bethe equations,　1:395-396
BGBC see bottom-gate bottom-contact
BGTC see bottom-gate top-contact
BHJ see bulk heterojunction
BHT see 2,6-di-tert-butyl-4-methylphenol
biaryls
synthesis
electrochemically initiated,　2:1184-1195
Mn(III)-assisted,　2:616
bicompetent systems
nitroxide-mediated polymerization,　4:1821-1822
persistent radical effect,　4:1816,1817
bicyclic ketones, cis-fused, synthesis,　2:787-788
bimolecular reactions, gas phase radicals,　1:479,495-497,498
bimolecular routes, photochemical radical-mediated metal nanostructure synthesis,　4:2200-2201
biofuels, combustion research,　1:478,479
biologically relevant radicals,　3:1502
biological samples
lipidomics, cis-trans isomerization,　3:1612-1615
lipid peroxidation products,　3:1583,1588-1589,1590
biological systems
electron transfer,　3:1475,1476-1477
lipid isomerization, environmental effects,　3:1615-1619
oxidants
defensive systems,　3:1425
interconversion,　3:1425-1426
proteins,　3:1426-1450
reaction rate constants,　3:1425-1426,1427
sources,　3:1425,1426
reactive oxygen species,　3:1259-1281
defence,　3:1277
generation,　3:1261-1266
oxidant sources,　3:1425,1426
properties,　3:1266-1273
protein damage,　3:1425-1457
targets,　3:1273-1277
repair/removal of damaged proteins,　3:1448-1450
see also membranes
biomacromolecular interactions, time resolved chemically induced dynamic nuclear polarization studies,　1:197-198
biomarkers
free-radical stress, trans-isomers of fatty acids,　3:1601,1613
oxidative stress, lipid peroxidation products,　3:1577-1578,1590-1593
biomedical applications, DNA hole transfer,　3:1411-1412
biomimetics
factors affecting lipid isomerization,　3:1615
liposomes, lipid isomerization,　3:1609-1610,1611,1619
S-containing amino acid damage, lipid isomerization,　3:1606
tandem desulfurization/isomerization,　3:1607
see also membrane models
biomolecular electronic devices,　3:1495-1497
DNA nanoscale electronic wiring,　3:1397,1412,1413
biomolecular reactions, matrix isolated radicals,　1:210,220
bioorganic molecule synthesis, radical thiol-X click chemistry,　4:2021-2033
biotechnological applications, radical enzymes,　3:1539-1540
biotin synthase, 5'-deoxyadenosine radical,　3:1501
Birch reduction, electron transfer, history,　1:19-20
BIRP see bismuthine-mediated living radical polymerization
Bi-S see thiobismuthine
bisadditions, nitroxides, ketene,　2:1104
bisallylic hydrogen abstraction, free-radical-mediated lipid peroxidation,　3:1581
bismuthine-mediated living radical polymerization (BIRP),　4:1932-1958,1960
bisnitroxides, nitroxide-mediated polymerization,　4:1828
bisphosphino ligands, P-chiral, Kolbe electrolysis synthesis,　2:1201-1202
bis(silyl) silicon-centered radicals
EPR,　4:2133
persistent and stable,　4:2132-2135
bis-sulfoxides, optically active, synthesis, nitroxide radical trapping,　2:1100-1101
(+)-bistramide, multistep synthesis, oxygen-centered radical remote functionalizations,　2:1233
bistriflimide anions, room-temperature ionic liquids,　1:434,442
bis(triphenylmethyl) peroxide
history,　1:2,3-4
rearrangements,　1:13
structure,　1:3-4
bis-xanthates, radical generation, tin hydride-mediated,　2:550-551
BlocBuilder[R] (Arkema), controlled reversible-deactivation radical polymerization,　4:1728-1729,1731
block copolymers
atom transfer radical polymerization,　4:1803,1804,1805,1871-1872,1878
controlled/living RP,　4:1787,1788,1794
controlled reversible-deactivation radical polymerization,　4:1726,1728,1729
industrial radical polymerization,　4:1714,1726,1728,1729
nitroxide-mediated polymerization,　4:1840,1843,1844
organoheteroatom-mediated radical living polymerization,　4:1945-1949,1958
radical thiol-X click chemistry,　4:2033,2041
reversible addition fragmentation chain transfer polymerization,　4:1805,1806,1807,1906-1916
convergent pathways,　4:1906,1912-1916
divergent pathways,　4:1906,1907-1912
thermosensitive micelles,　4:1958
blood plasma, lipid peroxidation products,　3:1583,1586,1589,1590-1593
Bohr magneton, EPR spectra,　1:148
bond dissociation energy (BDE),　1:81-106
ab initio values,　1:84
alkoxyamines, nitroxide-mediated polymerization,　4:1836
electron paramagnetic resonance,　1:169-170
experimental measurements,　1:84
Hess's Law,　1:81-82
literature values,　1:85-87
measurements,　1:82-83
phenolic antioxidant O-H bonds,　3:1641-1642
radical instability scales,　1:98-99
radical stability,　1:58-59,450,453
radical stability tables,　1:455-456,459-462,465,466-468,470
radical stabilization energies,　1:97-98
substituent effects,　1:102-103
thermolysis,　1:38
bond dissociation energy(B-H), radical stability tables,　1:470
bond dissociation energy(C-H), radical stability tables,　1:455-456,459-462,465
bond dissociation energy(N-H), radical stability tables,　1:468
bond dissociation energy(O-H), radical stability tables,　1:467
bond dissociation energy(S-H), radical stability tables,　1:466
bond energy-bond order (BEBO) method, hydrogen transfer kinetics,　1:100
bonding/antibonding energies, reaction rate prediction,　1:100
borane-catechol systems, synthetic strategies,　2:621-622
borinium cation (B(OH)2+), vertical neutralization to boryl radical, gas phase,　1:489-490
borohydride, reductive processes,　2:621
boron-containing radicals,　2:622-624
electron paramagnetic resonance,　1:161,162
stability measurement,　1:469-470,471
boron enolates, radical generation,　2:615
boron trichloride-mediated reactions, methanol synthesis, methane conversions,　2:620
borylations, arenes, synthetic strategies,　2:1086-1087
α-boryl radicals, generation,　2:624
bottom-gate bottom-contact(BGBC), organic-based field-effect transistors,　4:2058
bottom-gate top-contact (BGTC), organic-based field-effect transistors,　4:2058
3BP see benzophenone triplet state
branched-chain sugar synthesis
intermolecular carbon-carbon bond formation,　2:1142-1143
intramolecular carbon-carbon bond formation,　2:1146-1149
sequential radical cyclization-intermolecular trapping,　2:1146-1147
branched polymers
atom transfer radical polymerization,　4:1875,1878
thiol addition to unsaturated compounds,　4:2039,2041
C-2 branched pyranosides, synthesis, sequential additions,　2:1147-1148
"bremsstrahlung", charged particles interacting with matter,　1:395,396
bridged halides, SRN1 reactions,　1:349-351
bridging mechanism, coenzyme B12-dependent eliminases,　3:1509-1510
brominations
fullerenes,　4:2185-2186
photocatalytic,　1:383-386
photoinduced, cycloalkanes,　2:1253
sugars,　2:1165-1166
bromine, intramolecular homolytic substitutions,　2:630
bromine atom transfer
organoboranes,　2:605
radical additions,　2:952-954
radical cyclizations,　2:954
bromine-carbon bonds
formation, carbohydrate synthesis,　2:1165-1166
reductive cleavage, ruthenium-mediated photocatalysis,　2:1225-1226
bromoalkynes, cyclizations, triethylamine,　2:1252-1253
α-bromo esters, atom transfer radical additions, alkenes,　2:953
α-bromoketones, coupling, tetrakisdimethylaminoethene-mediated,　2:828
N-bromosuccinimide, free-radical bromination, history,　1:18-19
bromouracil (BrU), electron acceptor, DNA charge transfer,　3:1415-1416,1417,1418
Bronsted acid-mediated reactions, additions, enantioselective,　2:685
Brook rearrangements, alkoxy radicals,　2:785-787
Brown conjugate additions, trialkylboranes,　2:607-608
BrOx radicals
atmospheric,　1:507-509,510-511,512,517-518,525
stratosphere,　1:507-509,510-511,512,525
troposphere,　1:517-518
BrU (bromouracil), electron acceptor, DNA charge transfer,　3:1415-1416,1417,1418
brush copolymers
atom transfer radical polymerization,　4:1875
see also macromolecular bottle brush polymers
bulge DNA structures, hole transfer,　3:1409
bulk heterojunction (BHJ), polymer-based solar cells,　4:2059,2060,2067-2068
bulk polymerization
industrial processes,　4:1720
initiation stage, nitroxide-mediated polymerization,　4:1820-1821
methyl methacrylate, controlled/living radical polymerization,　4:1789-1791,1792,1793
butadienes, 2-phenylselenated, synthesis,　2:808
N-tert-butyl-N-2-methyl-1-phenylpropyl nitroxide (TIPNO), nitroxide-mediated polymerization,　4:1729,1827,1838
N-tert-butylsulfinyl imines, heteropinacol coupling, samarium diiodide,　2:869-870
butyrylCoA dehydrogenase, electron bifurcation,　3:1531,1532
C2'-oxidized abasic sites (C2-AP),　3:1361
C4'-oxidized abasic sites (C4-AP),
DNA lesions,　3:1354-1356
analytical detection/quantification,　3:1356
caged C4-AP in oligonucleotides,　3:1354-1355
repair,　3:1356
C60
additions, scandine,　2:1217-1218
C70 radical addition comparison,　4:2173
see also fullerenes; fullerite
caged electrons, reducing radicals, photochemical nanoparticle synthesis,　4:2200
cage effects
azoinitiators, industrial radical polymerization,　4:1706-1707
C4'-oxidized abasic sites, oligonucleotides,　3:1354-1355
history,　1:27
matrix isolation of radical pairs,　1:207
radical initiators in solution,　1:42
spin cages,　4:1999-2000
calixarenes, nitroxide spin labels,　4:1995-1998
calorimetry, bond dissociation enthalpy measurement,　1:83
calothrixin B, synthesis, radical cascade steps,　2:743-744
calothrixin derivatives, synthesis, homolytic aromatic substitutions,　2:1065
camptothecins
synthesis
hexamethylditin photochemical cleavage,　2:1238-1239
isonitrile annulations,　2:1043
CAN see cerium(IV) ammonium nitrate
captodative interactions, radical stability,　1:462
capture, high-energy neutral particles interacting with atomic nuclei,　1:395,396
carbamotelluroates, additions, acetylenes,　2:961
carbamoyl diethyldithiocarbamate, (-)-aphanophine synthesis,　2:1235
carbamoylmethyl radicals, γ-lactam synthesis, 5-endo-trig cyclizations,　2:703-704
α-carbamoyl radicals, Lewis acid-promoted cyclizations,　2:951
carbanion nucleophiles, SRN1 reaction,　1:336-338
carbapyranoses, synthesis,　2:1154
carbene-catalyzed oxidations, aldehyde conversions, carboxylic esters,　2:1105-1106
carboaminohydroxylations, olefins,　2:1081-1082
carboaminoxylations, alkenes, flow microreactor experiments,　2:1247,1249
carboazidations
lepadiformine total synthesis,　2:746
methylenecyclohexanes, sulfonyl azides,　2:1030-1031
carbocationic polymerization, controlled/living radical polymerization,　4:1786
carbocycles
synthesis
acylic sugar derivatives,　2:1149-1155
tris(trimethylsilyl)silane,　2:574-575
carbodiazenylations, olefins,　2:1081-1082
carbofuranoses, synthesis, acylic sugar derivatives,　2:1149-1153
carbohydrate-derived chiral auxiliaries, stereoselective reactions,　2:661-662
carbohydrates
alkoxyl radical fragmentations,　2:1165-1169
intermolecular carbon-carbon bond formation,　2:1131-1143
oxidations, 2,2,6,6-tetramethylpiperidine-N-oxyl, electrochemically initiated,　2:1202-1203
synthesis
Barton-McCombie deoxygenations,　2:1158-1160
carbon-hydrogen bond formation,　2:1155-1160
carbon-nitrogen bond formations,　2:1160-1162
carbon-oxygen bond formation,　2:1162-1164
carbon-phosphorus bond formation,　2:1162
carbon-selenium bond formation,　2:1164-1165
carbon-sulfur bond formation,　2:1164-1165
intramolecular carbon-carbon bond formation,　2:1143-1155
non-anomeric alcohol deoxygenations,　2:1158-1160
nonanomeric C-radical reductions,　2:1158-1160
radical thiol additions,　4:2022,2023,2024
stereoselective,　2:1156-1158
strategies and applications,　2:1131-1174
carbon-13 labelling, carboxylic acids, isonitriles,　2:1042-1043
carbonate radical anions
additions, 8-oxo-7,8-dihydroguanine radical cation,　3:1310-131.
DNA damage, one-electron oxidation,　3:1294-1295
guanine oxidation,　3:1294-1295
guanine radical reactions,　3:1307-1308
inflammatory response,　3:1288,1289-1290
carbonate radicals, methionine reactions,　3:1471-1472
carbon-bromine bonds
formation, carbohydrate synthesis,　2:1165-1166
reductive cleavage, ruthenium-mediated photocatalysis,　2:1225-1226
carbon-carbon bonds
carbon-centered radicals,　1:57,58
cleavage
fullerene dimers,　4:2172
fullerene reduction,　4:2190
photoinduced homolytic α-cleavage,　1:281-283
photoinduced mesolytic cleavage,　1:293-294
radical generation, tin-hydride mediated,　2:547
radical stabilization energy characterization,　1:451
thermolysis,　1:38,40
formation
fullerene additions,　4:2173,2189
intermolecular
branched-chain sugar synthesis,　2:1142-1143
C-disaccharide synthesis,　2:1139-1141
C-ketoside synthesis,　2:1141-1142
tris(trimethylsilyl)silane-mediated,　2:583-585
intramolecular
branched-chain sugar synthesis,　2:1146-1149
carbohydrate synthesis,　2:1143-1155
C-glycoside synthesis,　2:1143-1144
C-ketoside synthesis,　2:1144-1145
SAM radical enzymes,　3:1524
sequential, samarium diiodide-mediated,　2:890-895
SRN1 reactions,　1:333,336-338
intermolecular, carbohydrate synthesis,　2:1131-1143
photoinduced cleavage,　1:281-283,293-294
samarium diiodide-mediated sequential formation
anionic/anionic sequences,　2:895
anionic/radical sequences,　2:895
radical/anionic sequences,　2:891-894
radical/radical sequences,　2:890-891
thermolysis,　1:38,40
carbon-carbon coupling, polycyclic aromatic hydrocarbons/soot formation, combustion,　1:479
carbon=carbon double bonds
additions
primary amidyl radicals,　2:772
radical thiol mechanism,　4:2018-2019
carbon-centered radicals,　1:57,58
unsaturated fatty acids, lipid isomerization,　3:1599-1622
carbon-carbon multiple bonds
fluoroalkyl radical additions, tris(trimethylsilyl)silane-mediated,　2:585-586
radical thiol addition reactions
click chemistry,　4:2017,2021-2053
mechanisms,　4:2017,2018-2020
carbon≡carbon triple bonds
carbon-centered radicals,　1:57,58
radical thiol addition reaction mechanism,　4:2018,2019-2020
carbon-centered radicals
acceptors
organic azides,　2:1020-1023
sulfonyl azides,　2:1027-1031
addition to fullerenes,　4:2171-2180
arylations, synthetic strategies,　2:1059-1069,1074-1079
bent structures,　1:57,58
α-carbon radicals from proteins,　3:1428-1429
carbonylations, cascade reactions,　2:745-746
chain reactions,　1:57-79
clocks,　1:114-117,118
calibration methods,　1:112-114
conversions, Barton carbonate,　2:611
4-exo-trig cyclizations,　2:699
5-endo-dig cyclizations,　2:707-708
cysteine residue reactions,　3:1461-1464
direct trapping, nitroxides,　2:1095-1097
DNA sugar moieties,　3:1346-1366
double ligand/double bond structures,　1:57,58
electron paramagnetic resonance,　1:156-157
electrophilic, arylations,　2:1068-1069,1076-1079
enthalpies of formation,　1:88-91
ester interactions,　1:125-126
generation
alkylcatecholborane nitroxide additions,　2:1097
phenylselenium leaving groups,　2:805-806
photochemical processes,　1:275-300
tin hydride-mediated,　2:543-554
geometries at Cα, electron paramagnetic resonance,　1:156-157
homolytic substitutions, selenium-centered radicals,　2:806-807
linear structures, 1:57,　58
nitrophilic cyclizations,　2:719-722
nucleophilic, arylations,　2:1059-1067,1074-1076
organoboranes,　2:607-616
oxophilic reactions, cyclizations,　2:722-724
planar structures,　1:57,58
protein side chains,　3:1430
radical enzymes,　3:1502
single ligand/triple bond structures,　1:57,58
stability,　1:57-59,454-465
definitions,　1:449-453
di-/trisubstituted C-centered radicals,　1:457-463
monosubstituted radicals,　1:454-457
σ-type,　1:463-465
silyl substitution,　4:2117
value tables,　1:455-456,459-462,465
structures,　1:57,58,156-157
trapping, nitroxides,　2:1095-1102
trialkylborane reactivity,　2:602
triple ligand/single bond structures,　1:57,58
carbon-cobalt bonds
homolysis
coenzyme B12-dependent enzymes,　3:1549-1551
radical generation by enzymes,　3:1502,1506,1509
carbon compounds, azidations, iodine azide,　2:1034-1035
carbon filament synthesis, atom transfer radical polymerization,　4:1876,1877
carbon-halogen bonds
cleavage
photoinduced homolytic α-cleavage,　1:275-278
photoinduced mesolytic cleavage,　1:294-296
tin hydride-mediated radical generation,　2:543-546
carbon-heteroatom bonds
formation
carbohydrate synthesis,　2:1160-1165
SRN1 reactions,　1:333
tris(trimethylsilyl)silane,　2:566-568
carbon-hydrogen bonds
activation, silicon surfaces, functionalized monolayers,　4:2101-2104
carbonylations, flow microreactor experiments,　2:1254-1255
formation, carbohydrate synthesis,　2:1155-1160
functionalizations
indoles, ruthenium-mediated photocatalysis,　2:1226-1227
remote, hydrogen atom migration,　1:135,136
hydroxyalkylations,　2:619
photoinduced mesolytic cleavage,　1:291-292
carbon-metal bonds, thermolysis,　1:41
carbon monoxide (CO)
atmospheric reactions,　1:515,519-520
NOx, radical effects,　1:520
high gas pressure carbonylations, alkyl halides,　2:1246-1248
photochemically-induced extrusions, cyclic ketones,　2:1231
carbon nanotubes, thiol-ene functionalization,　4:2045,2047
carbon-nitrogen bonds
cleavage
nitrogen-centered radical formation,　2:778-779
photoinduced homolysis of azo compounds,　1:283
radical generation, tin-hydride mediated,　2:548-549
formation, carbohydrate synthesis,　2:1160-1162
carbon-ON bonds
bond dissociation energies, alkoxyamines, nitroxide-mediated polymerization,　4:1836
homolysis, alkoxyamines, nitroxide-mediated polymerization,　4:1829-1831
reformation, alkoxyamines, nitroxide-mediated polymerization,　4:1831-1833
carbon-oxygen bonds
cleavage
photoinduced homolysis of aromatic ethers/esters,　1:280-281
radical generation, tin-hydride mediated,　2:549-550
formation, carbohydrate synthesis,　2:1162-1164
carbon-phosphorus bonds
formation
carbohydrate synthesis,　2:1162
tris(trimethylsilyl)silane-mediated,　2:587-588
carbon-selenium bonds
cleavage
photoinduced mesolytic,　1:296
radical generation, tin-hydride mediated,　2:550-551
formation, carbohydrate synthesis,　2:1164-1165
carbon-silicon bonds
formation, tris(trimethylsilyl)silane,　2:566-568
photoinduced mesolytic cleavage,　1:292-293
self-assembled monolayers,　4:2081,2084-2089
carbon-skeleton rearrangements
class I mutases,　3:1548,1551-1552
coenzyme B12-dependent mutases,　3:1511-1513
carbon-sulfur bonds
cleavage
isocyanide triggered,　2:803
photoinduced homolysis of thioethers,　1:283
radical generation, fin-hydride mediated,　2:550-551
formation, carbohydrate synthesis,　2:1164-1165
carbon=X double bonds, reversible addition fragmentation chain transfer agents,　4:1896,1897,1905-1906
carbonyl-alkene coupling
heterocycle synthesis, samarium diiodide,　2:874-875
intermolecular, samarium diiodide,　2:871-872
intramolecular, samarium diiodide,　2:872-876
natural product synthesis, samarium diiodide,　2:874-875
samarium diiodide,　2:870-877
carbonyl-alkene cyclizations, samarium diiodide,　2:874-875
carbonyl-arene cyclizations, samarium diiodide,　2:875-876
carbonylations
alkanes, flow microreactor experiments,　2:1254-1255
cascade reactions, carbon-centered radicals,　2:745-746
high gas pressure, alkyl halides, carbon monoxide,　2:1246-1248
iodoalkanes, flow microreactor experiments,　2:1254
photoinduced, flow microreactor experiments,　2:1253-1256
carbonylative cyclizations, palladium-catalyzed,　2:1005
carbonyl compounds
pinacol coupling, samarium diiodide,　2:864-870
reductions, samarium diiodide, reaction mechanisms,　2:853-856
carbonyl groups
additions, N-stannylaminyl radicals,　2:768-769
cyclizations, stannylaminyl radicals,　2:1023-1024
reductive cyclizations, electrochemically initiated,　2:1206-1208
carbonyl reductions, electron transfer, history,　1:19
carbotellurations
alkynes,　2:958-959
isonitriles,　2:959
carboxylic acids
additions, alkenes, γ-lactone synthesis,　2:904-906
anodic oxidations, substrate substitution patterns,　2:1196
13C-labelling, isonitriles,　2:1042-1043
cyclizations, metal-dependent,　2:918-919
electrolysis, α-heteroatom effects,　2:1200
primary aliphatic, Kolbe dimerizations,　2:1199-1200
reductions, samarium diiodide, synthetic applications,　2:860
silicon surfaces, functionalized monolayers,　4:2104,2105
carboxyl radicals, 1,5-hydrogen atom abstractions,　1:136
carboxyl shift, acyloxy radical rearrangements,　1:126
β-carotene
antioxidant action,　3:1670-1672,1673
autoxidation,　3:1670,1671
pro-oxidant action,　3:1670,1671,1672
carrier doping for Mott phase, 1,3,5-trithia2,4,6-triazapentalenyl,　4:2156-2157
cascade reactions
addition-allylations, B-allcylcatecholboranes,　2:613
allylsilyloximes, haloesters,　2:741-742
carbonylations, carbon-centered radicals,　2:745-746
cerium complex-catalyzed,　2:757-758
chain radical synthetic strategies,　2:729-746
copper complex-catalyzed,　2:754-755
cyclization/aromatic homolytic substitutions
fortucine pentacycle core synthesis,　2:737
luotonin A synthesis,　2:737
7-exo/6-exo cyclizations, acyl radicals,　2:732
cyclizations,　1:72
with fragmentations,　2:732-735
with homolytic substitutions,　2:737-739
with translocations,　2:735-737
cycloadditions, SOMO catalysis,　2:683-684
five-membered ring synthesis,　2:739-742
fragmentations, with cyclizations,　2:732-735
haloesters, allylsilyloximes,　2:741-742
homolytic substitutions, with cyclizations,　2:737-739
hydrophosphinations, phosphorus-centered radicals,　2:794-795
intermolecular chain radical processes,　2:746
intramolecular chain radical processes,　2:729-739
iron complex-catalyzed,　2:752-754
manganese complex-catalyzed,　2:749-752
polycyclizations,　2:729-732
redox processes,　2:746-763
samarium complex-catalyzed,　2:759-760
silver complex-catalyzed,　2:756-757
six-membered ring synthesis,　2:742-745
titanium complex-catalyzed,　2:746-749
translocations, with cyclizations,　2:735-737
tris(trimethylsilyl)silane-mediated,　2:587-593
visible light-catalyzed,　2:761-763
zinc complex-catalyzed,　2:755-756
catalase, antioxidant action,　3:1626
catalyst regeneration
atom transfer radical addition/cyclization,　4:1880-1887
see also activators regenerated by electron transfer; initiators for continuous activator regeneration
catalysts
atom transfer radical addition/cyclization,　4:1851,1853-1854,1879-1880
atom transfer radical polymerization,　4:1854-1855,1856-1860,1862-1863
radical-catalyzed odd-oxygen destruction in stratosphere,　1:507-509
radical chain reactions,　1:75-76
catecholboranes, additions, nitroxides,　2:1097
catechols
antioxidant action,　3:1657-1659
coupling, anodic oxidations,　2:1205-1207
hydrogen abstractions, TEMPO-mediated,　2:1121-1122
catenanes, mechanical interlocking, 1:239,　241
cathodic processes, electrochemically initiated reactions,　2:1206-1212
cationic radicals
anion/neutral radical comparison,　1:301-333
deprotonations,　1:326-329
hydrogen atom transfer comparison,　1:329-330
kinetics,　1:327-329
thermodynamics,　1:326-327
electron transfer, history,　1:20-21
fragmentation, mesolytic cleavage,　1:291
fullerenes,　4:2186,2191
generation by LFP, electron transfer in peptides,　3:1480
guanine radicals, one-electron oxidation of DNA,　3:1300-1302
initiation, silicon surfaces, experimental models,　4:2099-2100
room-temperature ionic liquids,　1:433-434,436-437,438,444-446
sulfur-containing amino acids,　3:1467,1468,1469
trapping, tetrathiafulvalenes, synthetic applications,　2:820-824
see also DNA radicals
cationic ring-opening polymerization, controlled/living radical polymerization,　4:1786
cations, organic, room-temperature ionic liquids,　1:433,434
CCl3 radical
Kharasch reaction,　1:62-63
metal-catalyzed chain reactions,　1:75-76
CDs see cyclodextrins
ceiling temperature, monomers, radical polymerization,　4:1714
cellular processes
inflammation, DNA damage by reactive species,　3:1283-1312
phase-separated antioxidants,　3:1668-1669
reactive oxygen species generation,　3:1261-1266
see also membranes
cellular signaling
lipid peroxidation products,　3:1594
radical modification of enzymes,　3:1459
reactive oxygen species,　3:1262,1264,1274
(-)-cephalotaxine, synthesis, cascade cyclizations,　2:1081-1082
cerium(IV) ammonium nitrate (CAN)-mediated reactions
addition-cyclizations, aryl rings,　2:911-913
additions
aldehydes, ketones,　2:906-907
alkenes, β-dicarbonyl compounds,　2:907-918
glycals, malonates,　2:1142
aerobic oxidation of alcohols,　2:1113
α-arylations,　2:924-927
dihydrofuran synthesis,　2:907-910
dimerizations, enol ethers,　2:916
enantioselective allylations, aldehydes,　2:906-907
intermolecular arylations, β-dicarbonyl compounds,　2:910
organic electron donor activations,　2:834-837
ring opening,　2:932-935
α-thioketone synthesis,　2:916
cerium complex-catalyzed reaction cascades,　2:757-758
chain-breaking antioxidants,　3:1623,1627-1672
chain-breaking reactions, radical polymerization,　4:1785,1786
chain capping agents, controlled/living radical polymerization,　4:1788
chain end functionality (CEF)
nitroxide-mediated polymerization,　4:1840-1843
preservation
controlled/living radical polymerization,　4:1788-1797
chain length-dependent termination,　4:1793-1794
dead chain fraction,　4:1788-1793
minimal polymerization time,　4:1789
radical initiators,　4:1794-1797
chain-length-dependent termination (CLDT)
controlled/living radical polymerization,　4:1787,1793-1794
polymerization kinetics,　4:1740,1745-1748,1771-1775
chain-length distribution (CLD), polymerization kinetics,　4:1744,1745,1746
chain length effect, nitroxide-mediated polymerization,　4:1835
chain-length-independent propagation, polymerization kinetics,　4:1740
chain-length-independent termination (CLIT), polymerization kinetics,　4:1741,1743,1745-1746,1747,1753
chain length magnitude, SRN1 reactions,　1:334-335
chain propagation cycle, SRN1 reactions,　1:334-335
chain reactions
atmospheric CO/CH4 oxidation,　1:519-522
atom transfer processes,　1:65-66,75-76
autoxidations,　1:73-74
catalysts,　1:75-76
discrete processes,　1:59-63
group transfer processes,　1:65-66,76-78
halogenations,　1:74-75
initiation stage,　1:59,60,62,63,108,110
initiators,　1:40
intermolecular radical additions to multiple bonds,　1:69-71
intermolecular radical processes,　2:746
intramolecular radical processes,　2:729-739
introduction of functional groups,　1:73-75
iodine atom transfers,　2:617-619
iodoaldehydes, triethylborane,　2:617
Kharasch reaction,　1:62-63,66,75-76
lipid peroxidation,　3:1580,1581,1583-1584
non-reductive processes,　1:73-78
organoboranes,　2:616-620
propagation, self-assembled monolayers on silicon surfaces,　4:2084-2089
propagation stage,　1:59-63
protein oxidative damage,　3:1429
radical kinetics,　1:109-110
radical mediators,　1:63-65
lipid peroxidation,　3:1580,1581,1583-1584
reductive mediators,　1:66-73
radical processes,　1:57-79
reactive oxygen species,　3:1268
reductive dehalogenation of organohalides,　1:64
reductive removal of functional groups,　1:66-69
selectivity,　1:75-76
silane-mediated consecutive radical reactions,　2:574-595
silylated cyclohexadienes,　2:571,573
steps,　1:108
synthesis,　1:66-78
termination,　1:60,62
thiocarbonyl organosilanes,　2:571
thiol radical addition to unsaturated compounds,　4:2018-2020
tri(organo)tin hydride mediators,　1:63-65
versus nonchain reactions, radical kinetics,　1:108-110
xanthates,　2:619
see also cascade reactions
chain termination, industrial radical polymerization,　4:1717-1719
chain transfer agents (CTAs)
industrial radical polymerization,　4:1716
organoheteroatom-mediated radical living polymerization,　4:1933-1935,1937,1938
chain transfer reactions
degradative chain transfer, polymerization,　4:1738,1739,1779
enandoselective reactions,　2:666-667
iodoaldehydes, triethylborane,　2:617
organoboranes,　2:616-620
polymerization
industrial,　4:1715-1717
reversible addition fragmentation chain transfer,　4:1895-1929
radical polymerization,　4:1738
kinetics,　4:1739,1777-1778
radical thiol addition to unsaturated compounds,　4:2018,2019
reversible chain transfer-catalyzed polymerization,　4:1933-1937,1939-1944,1949,1960
via hydrogen atoms,　2:619-620
via iodine atoms,　2:617-619
via xanthates,　2:619
chain transfer to polymer (CTP), radical polymerization kinetics,　4:1779-1780
chalcogenations, B-alkylcatecholboranes,　2:613-616
chalcogens
intramolecular homolytic substitutions,　2:630-631
reductive cleavage, tris(trimethylsilyl)silane,　2:562-564
transfer reactions,　2:943-963
Chapman mechanism, stratospheric oxygen/ozone reactions,　1:506-507
charge delocalization, versus spin delocalization, radical anion ring opening,　1:305
charged particles, high-energy radiation interactions with matter,　1:395,396
charge separation, photocatalytic reactions of radical ions,　1:365-393
charge storage
radical polymers,　4:2165-2166
see also batteries
charge transfer
DNA,　3:1397-1424
isonitriles, electrophilic attack,　2:1040
peptides/proteins,　3:1489-1490
phase transitions, BDTACo,　4:2152-2154
radical polymers for batteries,　4:2164,2166,2169
room-temperature ionic liquids,　1:436,437,440
charge transport
radical polymers,　4:2165-2166
see also batteries
chelation
samarium(III),　2:873-874,883
transition metals,　3:1273
chemically induced dynamic electron polarization (CIDEP),　1:175,176,199-203
principles,　1:199-200
radical ions and follow-up products,　1:202-203
radical polymerization,　1:200-202
see also time-resolved electron paramagnetic resonance
chemically induced dynamic nuclear polarization (CIDNP),　1:175-199
cyclic reactions
degenerate electron exchange,　1:185-187
deprotonation,　1:187
kinetics,　1:185
examples,　1:187-198
field dependence,　1:198-199
hyperfine coupling constant,　1:177,184-185
kinetics,　1:180-182,185
phenomenological description,　1:177
photoinitiators,　1:189-190
radical pairs,　1:175-179
radical polymerization,　1:189-190
scope,　1:176-177
solid-state,　1:199
steady-state, organic radicals/radical ions,　1:187-188
see also photochemically induced dynamic nuclear polarization; time resolved chemically induced dynamic nuclear polarization
chemical methods, gas phase isolated radical generation,　1:485-486
chemical models, radical enzymes,　3:1547
chemical passivation, silicon-carbon bonds,　4:2084
chemical switching, molecular machines,　1:241-244
chemical tracers, atmospheric radicals,　1:515-516
chemiluminescence, photocatalytic oxygenation of tetraphenylethylene to 1,2-dioxetane,　1:372
chemoselective oxidations, alcohols, oxoammonium salts,　2:1108-1117
chimera bonds,　1:81,102
chiral allylsilanes, carboazidations, sulfonyl radicals,　2:1029-1030
chiral auxiliaries, stereoselective reactions,　2:659-662
P-chiral bisphosphino ligands synthesis, Kolbe electrolysis,　2:1201-1202
chiral Bronsted acid-mediated reactions, enantioselective additions,　2:685
chiral chain-transfer reagents, enantioselective reactions,　2:666-667
chirality transfer, aryl radical generation, tin hydride-mediated,　2:544-545
chiral Lewis acids
enantioselective reactions,　2:668-679
fragmentations,　2:676-678
halogen atom transfers, reactions,　2:670-672
hydrogen atom transfers,　2:668-670
quaternary centre synthesis,　2:677-678
reductive alkylations,　2:672-677
tandem conjugate addition-fragmentation reactions,　2:678-679
template effects, reductive alkylations,　2:673-674
chiral ligand-assisted asymmetric electron transfers, synthetic strategies,　2:686-689
chiral oxazolidinone auxiliaries, Lewis acid-mediated reactions,　2:664-665
chiral quaternary center synthesis,　2:677-678
chiral spiroketals, anodic coupling, triphenylene core synthesis,　2:1191-1192
chiral sulfoxides, ring-closures,　2:636
chiral tin hydrides, preparation,　2:536,538-540
chiral zinc complex-catalyzed cyclizations,　2:742-743
chlorinations
fullerenes,　4:2185
photoinduced,　2:1250-1252
chlorine atom transfer
intramolecular homolytic substitutions,　2:630
organoboranes,　2:605
radical additions,　2:954-956
radical cyclizations,　2:954-956
chlorine-centered radicals, atmospheric,　1:507-509,510-511,512-513,516-518,525
chlorine compounds, ClOOCl photolysis, stratospheric ozone depletion,　1:512-513
chlorine-hydrogen gas mixture, radiation-induced radicals in gaseous systems,　1:398
chloroaromatics, photoinduced electron transfer followed by mesolytic cleavage,　1:296
cholesterol, oxidation,　2:1116,3:1586-1588,1591,1592
chorismate synthase, ketyl radicals,　3:1533-1534
chronic inflammation, oxidative stress, DNA damage,　3:1283-1312
CIDEP see chemically induced dynamic electron polarization
CIDNP see chemically induced dynamic nuclear polarization
Cinetique de Reaction en Ecoulement Supersonique Uniforme (CRESU), low temperature gas-phase studies,　1:482,496-497
CIS see Criegee biradical intermediates
cis-fatty acids, natural biosynthesis,　3:1599
cis-fused bicyclic ketones, synthesis,　2:787-788
cis/trans fatty acids
lipid isomerization,　3:1599-1622
relative stability,　3:1599
cis-trans isomerase (Cti), bacteria,　3:1618-1619
13C-labelling, carboxylic acids, isonitriles,　2:1042-1043
(+)-cladantholide, synthesis, tin hydride reduction step,　2:541
classic hydrogen atom transfer,　1:323
class I mutases, coenzyme B12-dependent enzymes,　3:1548,1551-1552
class II eliminases, coenzyme B12-dependent enzymes,　3:1556-1561
class III aminomutases, coenzyme B12-dependent enzymes,　3:1561-1562
class I ribonucleotide reductases,　3:1503
class II ribonucleotide reductases,　3:1503
class III ribonucleotide reductases,　3:1503-1504
CLD see chain-length distribution
CLDT see chain-length-dependent termination
cleavage
allylic C-N bonds, thiol-mediated,　2:798
C-C bonds, radical generation, tin-hydride mediated,　2:547
C-halogen bonds, radical generation, tin-hydride mediated,　2:543-546
C-N bonds, radical generation, tin-hydride mediated,　2:548-549
C-O bonds, radical generation, tin-hydride mediated,　2:549-550
C-S bonds, radical generation, tin-hydride mediated,　2:550-551
C-Se bonds, radical generation, tin-hydride mediated,　2:550-551
electrochemically initiated, thioesters,　2:1209-1210
esters, silicon surfaces, functionalized monolayers,　4:2104-2106
isonitriles, tin-hydride mediated,　2:548
nickel-mediated, thioesters, electrochemically initiated,　2:1209-1210
olefins, sulfur-centered radicals,　2:801-802
photochemical
Barton esters, platensimycin synthesis,　2:1235-1236
carbamoyl diethyldithiocarbamate, (-)-aphanophine synthesis,　2:1235
photoinduced
hexamethylditin,　2:1238-1239
homolytic,　1:275-283
reductive
C-Br bonds, ruthenium-mediated photocatalysis,　2:1225-1226
chalcogens, tris(trimethylsilyl)silane,　2:562-564
thioesters, nickel-mediated, electrochemically initiated,　2:1209-1210
thiol-mediated, allylic C-N bonds,　2:798
α-cleavage (homolytic)
photoinduced
C-C bonds,　1:281-283
C-halogen bonds,　1:275-278
C-N bonds,　1:283
C-O bonds,　1:280-281
C-S bonds,　1:283
N-O bonds,　1:279-280
O-I bonds,　1:278-279
cleavage quantum yields, photolysis,　1:43,44-45
click chemistry
branched polymer synthesis,　4:2039,2041-2045
dendrimer synthesis,　4:2028,2030-2033
features,　4:2017
functionalized monolayers on silicon surfaces,　4:2111-2112,2113
functional polymer synthesis,　4:2033,2035-2039,2040
nucleic acid spin labeling,　4:1971,1972
radical thiol addition to unsaturated compounds,　4:2017-2056
applications,　4:2021-2053
colloidal particles,　4:2045-2048
dendrimer synthesis,　4:2028,2030-2033
functional polymer synthesis,　4:2033,2035-2039,2040
macromolecular chemistry,　4:2033-2045
mechanisms,　4:2018-2020
organic chemistry applications,　4:2021-2033
surface chemistry,　4:2045,2048-2052
reversible addition fragmentation chain transfer polymerization,　4:1905,1913,1916
CLIT see chain-length-independent termination
ClOOCl photolysis, stratospheric ozone depletion,　1:512-513
clouds
atmospheric condensed phase processes,　1:503-504
see also polar stratospheric cloud
ClOx radicals
atmospheric,　1:507-509,510-511,512-513,516-518,525
stratosphere,　1:507-509,510-511,512-513,525
troposphere,　1:516-518
clustered DNA oxidative damage, adjacent nucleobases,　3:1335
CMC see critical micelle concentration
CO see carbon monoxide
coatings, UV-curing, industrial radical polymerization,　4:1711-1712
cobalamins, radical enzymes,　3:1504
cobalt60, radiolysis source,　1:396
cobalt-carbon bonds, homolysis, coenzyme B12-dependent enzymes,　3:1549-1551
cobalt-carbon σ bonds, homolytic fission, radical generation by enzymes,　3:1502,1506,1509
cobalt-mediated reactions
alkylations, styrene,　2:1010-1011
arylations, alkyl halides,　2:1009
arylative cyclizations,　2:1008-1009
cross-coupling allylations, alkyl halides,　2:1008-1009
cross-coupling benzylations, alkyl halides,　2:1008-1009
cyclopropyl benzene synthesis, electrochemically initiated,　2:1210-1211
electrochemically initiated, cyclopropyl benzene synthesis,　2:1210-1211
Mizoroki-Heck reactions,　2:1010-1011
oxidative additions,　2:1008-1012
ring expansions, cyclopentane-1,3-diones,　2:1210-1211
tandem radical cyclization/cross-coupling arylations, 6-halo-1-hexene derivatives,　2:1008-1009
tetrahydrofuran synthesis,　2:789
cocatalysts, organoheteroatom-mediated radical living polymerization,　4:1935-1937,1956-1958
coefficient of transfer (C1r), RAFT polymerization,　4:1899,1900
coenzyme B12
ribonucleotide reductases,　3:1504-1505
SAM comparison,　3:1502
structure,　3:1504,1549
coenzyme B12-dependent enzymes,　3:1505-1514
aminomutases,　3:1513-1514
"base-on"versus"base-off, his-on",　3:1505-1506,1507-1508
biotechnological applications,　3:1539
carbon-skeleton mutases,　3:1511-1513
class I mutases,　3:1548,1551-1552
class II eliminases,　3:1548,1556-1561
class III aminomutases,　3:1561-1562
eliminases,　3:1505-1506,1507,1509-1511
mechanisms,　3:1501,1502,1506,1508-1509
mutases,　3:1506,1507-1508,1511-1514
reactivases,　3:1514
theoretical studies,　3:1548-1562
co-inhibited autoxidation studies, antioxidants in homogenous media,　3:1667-1668
colloidal nanoparticles, spontaneous self assembly, radical-mediated photochemical method,　4:2197-2210
colloidal particles, radical thiol addition click chemistry,　4:2045-2048
colored radicals, history,　1:1,2
color of polymers, industrial radical polymerization,　4:1731
comb copolymers, atom transfer radical polymerization,　4:1874-1875
combination reactions
polymerization,　4:1738
kinetics,　4:1739-1740,1776-1777
combustion research, gas phase radicals,　1:478-480
commercial applications
conducting polymers,　4:2075-2077
see also industrial radical polymerization
Commonwealth Scientific and Research Organization (CSIRO), reversible addition fragmentation chain transfer,　4:1895
compartmentalization
emulsion polymerization,　4:1722
phase-separated antioxidants,　3:1668-1669
reactive oxygen species,　3:1275-1277
compensation effect, hydrogen transfer kinetics,　1:102
competition kinetics
kinetic expressions,　1:111-112
overview,　1:110-111
radical clocks,　1:107-108,110-114
competitive q method, redox potential determination,　1:253-255
complementary circuits, polymer-based field-effect transistors,　4:2075-2076
complex I (NADH-ubiquinone oxidoreductase), reactive oxygen species generation,　3:1261-1262
complexing ligands, copper-catalyzed atom transfer radical polymerization,　4:1856-1857,1858
Compton effect
DNA ionization,　3:1374
electromagnetic radiation,　1:395,396
computational methods
DNA radical molecular orbital calculations,　3:1371
phenolic antioxidant mechanistic considerations,　3:1653-1654
computational methods (continued)
phenolic antioxidant thermodynamics,　3:1644-1645
radical enzyme modeling,　3:1547,1548,1550-1551,1555,1557-1558
redox potential determination,　1:258
CO-N bonds
bond dissociation energies, alkoxyamines, nitroxide-mediated polymerization,　4:1836
homolysis, alkoxyamines, nitroxide-mediated polymerization,　4:1833
concentration effects, radical polymerization,　4:1785
concentration measurements, kinetic EPR spectroscopy,　1:165-167
concerted steps, radical chain reactions,　1:60
condensed phase processes, atmospheric radical chemistry,　1:503-504,519
conducting polymers,　4:2057-2080
commercial applications,　4:2075-2077
polymer-based field-effect transistors,　4:2058-2059,2061-2067,2075-2076
polymer-based light emitting diodes,　4:2057
polymer-based solar cells,　4:2059-2061,2067-2075,2076-2077
δ-coneceine, synthesis, Hofmann-Loffler-Freytag reaction,　1:131
conformational analysis
electron paramagnetic resonance,　1:157-159
stable silyl radicals in solution,　4:2131-2132
conformational energies, DNA radicals,　3:1381-1383
confusarin synthesis, intramolecular homolytic aromatic substitutions,　2:1061
conjugate additions
B-alkylcatecholboranes,　2:610-612
5-endo-trig cyclizations,　2:703-705
diastereoselective, chiral oxazolidinone auxiliaries,　2:664-665
trialkylboranes,　2:607-609
conjugated acyclic triynes, cascade reactions, polycycle synthesis,　2:743-744
conjugated enones, endocyclic, benzophenone-initiated photoadditions, methanol,　2:1142-1143
conjugated polymers, conducting electricity,　4:2057
conjugate reduction/aldol cyclizations, samarium diiodide-mediated,　2:888-889
conjugation effects, imidoyl radicals,　2:1041
conjugation protocols, block copolymers, reversible addition fragmentation chain transfer polymerization,　4:1908,1912-1916
consecutive radical reactions
silane-mediated,　2:574-595
see also chain reactions
contact-molding lithography, radical thiol-ene process,　4:2048,2049
continuous reactors, industrial radical polymerization,　4:1725
continuous wave (CW) EPR,　1:147-148,150
controlled/living radical polymerization (CRP),　4:1785-1812
atom transfer radical polymerization,　4:1854-1855
chain end functionality,　4:1788-1797
chain length-dependent termination,　4:1787,1793-1794
conventional radical polymerization comparison,　4:1786,1787-1788
conversion, dead chain fraction effects,　4:1789-1790
dead chain fraction,　4:1788-1795
degenerative transfer processes,　4:1786,1787,1794-1795,1805-1806,1807
fullerenes,　4:2180,2181
history,　4:1725
industrial processes,　4:1727-1731
initial monomer concentration,　4:1791-1792
mechanisms,　4:1786-1787,1931,1932,1953-1956
minimal polymerization time,　4:1789,1792-1793
organoheteroatom-mediated,　4:1931-1963
persistent radical effect,　4:1786-1787,1797-1799
reaction rates,　4:1787,1788-1797
reversible addition fragmentation chain transfer,　4:1895,1896
techniques,　4:1726-1727
use of terms,　4:1725,1786
see also atom transfer radical polymerization; living radical polymerization; nitroxide-mediated polymerization; organometallic radical polymerization; reversible addition fragmentation chain transfer polymerization; stable free radical polymerization
controlled molecular weight radical polymerization, reversible addition fragmentation chain transfer,　4:1896,1901-1903
controlled reversible-deactivation radical polymerization (CRDRP)
concepts,　4:1786-1787
history,　4:1725
industrial applications,　4:1727-1731
techniques,　4:1726-1727
use of terms,　4:1725,1786
see also controlled/living radical polymerization
conventional radical polymerization
controlled/living radical polymerization comparison,　4:1786,1787-1788
industrial processes,　4:1704-1725,1731
limitations,　4:1785
convergent synthesis, block copolymers, reversible addition fragmentation chain transfer polymerization,　4:1906,1912-1916
conversions
alcohols, thiols, Barton-McCombie deoxygenations,　2:971-972
controlled/living radical polymerization, dead chain fraction effects,　4:1789-1790
iodides, lactames, homolytic aromatic substitutions,　2:1062
coordination polymers, TITA.Cu(hfac)2,　4:2154-2155
Cape-type eliminations, nitroxide-mediated polymerization,　4:1818,1825,1833-1834
copolymerizations
conventional versus controlled/living radical polymerization,　4:1786,1788
industrial radical polymerization,　4:1714-1715
kinetics,　4:1749-1752,1766-1770,1775-1776
nitroxide-mediated polymerization,　4:1826-1827,1840,1843,1844
parameters,　4:1715
propagation
kinetics,　4:1766-1770
monomer reactivity ratios,　4:1766-1768
radical reactivity ratios,　4:1768-1770
copolymers
alternating, organoheteroatom-mediated radical living polymerization,　4:1943,1944-1945,1949
atom transfer radical polymerization,　4:1854-1855,1870-1873
applications,　4:1878-1879
industrial emulsion polymerization,　4:1723
organoheteroatom-mediated radical living polymerization,　4:1943-1949
polymer-based field-effect transistors,　4:2063,2065,2066,2067
polymer-based solar cells,　4:2068-2070,2073,2074
random, organoheteroatom-mediated radical living polymerization,　4:1943-1944
synthesis, radical thiol-X click chemistry,　4:2033,2036,2037,2041
see also alternating copolymers; block copolymers; brush copolymers; comb copolymers; gradient copolymers; graft copolymers
copper(II) acetate monohydrate-mediated radical reactions, fullerenes,　4:2177-2178
copper-catalyzed reactions
aerobic oxidations, alcohols, nitroxide-mediated,　2:1119-1121
atom transfer radical additions,　2:955-956,4:1853-1854,1880
atom transfer radical cyclizations,　2:955-956
atom transfer radical polymerization,　4:1854-1855,1856-1857,1858
copper complex-catalyzed reactions, cascades,　2:754-755
copper(I)-mediated reactions, amidyl/arninyl radical formation,　2:774
copper nanoparticles, radical-mediated photochemical synthesis,　4:2198,2202,2205,2206
copper reagents, organic electron donor activations,　2:840-841
coptodative radicals, carbon-centered radicals,　1:58
coriolin, synthesis, carbon-carbon bond sequential formation, samarium diiodide-mediated,　2:890
corrinoids, structure,　3:1504
costs, commercial applications, conducting polymers,　4:2075-2077
connterion influence, radical-mediated metal nanostructure synthesis,　4:2205
coupling
acetophenones, samarium diiodide,　2:854-855
anisole-veratrol, triphenylene core synthesis,　2:1191-1192
aromatic thiols, anodic oxidations,　2:1205-1207
arylethers, electrochemically initiated,　2:1191-1192
benzaldehydes, samarium diiodide,　2:854-855
α-bromoketones, tetrakisdimethylaminoethene-mediated,　2:828
carbonyl-alkene, samarium diiodide, synthetic applications,　2:870-877
carbonyl compounds, samarium diiodide, synthetic applications,　2:864-870
cerium(IV) ammonium nitrate-mediated,　2:917-918
2,6-di-tert-buty/phenol, electrochemically initiated,　2:1188
2,6-dihalogenated phenols, electrochemically initiated,　2:1190-1191
electrochemically initiated,
anisole-veratrol,　2:1191-1192
arylethers,　2:1191-1192
chiral spiroketals,　2:1191-1192
ketone reductions,　2:1211-1212
veratrol-anisole,　2:1191-1192
with electrophiles, following reduction, photoinduced electron-transfer,　1:289
enolates,　2:924,926
Grignard reagents, nitroxide-mediated,　2:1105
iron(III) salt-mediated,　2:917-918,924
manganese(III) acetate-mediated,　2:917-918
metal-dependent,　2:917-918,924,926
4-methylguaiacol, electrochemically initiated,　2:1188-1189
with nucleophiles, following oxidation, photoinduced electron-transfer,　1:288-289
phenoxides,　2:926
pinacols, samarium diiodide, synthetic applications,　2:864-870
radical chain reaction termination,　1:60,62
reductive, imines, samarium diiodide,　2:876
three-component, tris(trimethylsilyl)silane-mediated,　2:588-589
veratrol-anisole,　2:1191-1192
COX see cyclooxygenase
CPR see controlled/living radical polymerization
CRDRP see controlled reversible-deactivation radical polymerization
CRESU see Cinetique de Reaction en Ecoulement Supersonique Uniforme
Criegee biradical intermediates (CIs), ozone/isoprene reactions in troposphere,　1:525
critical micelle concentration (CMC), emulsion polymerization,　4:1721
cross-coupling
alkyl halides,　2:1006-1008
cobalt-catalyzed, allylations/benzylations,　2:1008-1009
electrochemically initiated,　2:1184-1195
iron-catalyzed,　2:1012-1013
nickel-catalyzed,　2:1006-1008
palladium-catalyzed,　2:1004-1005
crossed-beam techniques, bimolecular reactions, gas phase radicals,　1:497
cross-experiments, ketene dithioacetal cyclizations, electrochemically initiated,　2:1179
cross linking, UV-curing of coatings/inks/adhesives,　4:1711-1712
cross-links
DNA-protein, oxidation damage,　3:1338
interstrand DNA lesions, oxidation damage,　3:1335-1336
intrastrand DNA lesions, oxidation damage,　3:1292-1293,1335-1336
crown-ethers, nitroxide spin labels,　4:1990,1991
cryogenics, matrix isolation,　1:207-228
cryostats, matrix isolation,　1:208,210
cryptands, nitroxide spin labels,　4:1990,1991
crystal solvent evaporation, BBDTA salts, ferromagnetism,　4:2155-2156
CSIRO see Commonwealth Scientific and Research Organization CTAs see chain transfer agents
CTP see chain transfer to polymer
cucurbiturils
encapsulation, radical stabilization,　1:236-237
nitroxide spin labels,　4:1998-1999
paramagnetic rotaxanes,　1:244
cumulative molar masses, polymerization kinetics,　4:1748
cumyl radicals, persistent radical effect,　4:1816
curcumin, antioxidant action,　3:1625
curing, polymerizable coatings/inks/adhesives,　4:1711-1712
CV see cyclic voltammetry
CW see continuous wave
cyanamides, additions, N-stannylaminyl radicals,　2:768
cyanations
B-alkylcatecholboranes,　2:614
isonitriles,　2:1042
tris(trimethylsilyl)silane-mediated,　2:584-585
cyanocobalamin, structure,　3:1504
cyano groups, cyclizations, stannylaminyl radicals,　2:1024
cyclic acetals, azidations,　2:1034-1035
cyclic alkoxysilanes, synthesis,　2:646
cyclic amines, synthesis, tris(trimethylsilyl)silane,　2:576-577
cyclic aminyl radical generation,　2:769
cyclic diols, synthesis,　2:623
cyclic ethers, synthesis, tris(trimethylsilyl)silane,　2:575,577
cyclic ketene acetals, nitroxide-mediated polymerization,　4:1839
cyclic ketones
photochemically-induced extrusions,　2:1231
synthesis, tris(trimethylsilyl)silane-mediated tandem reactions,　2:588-589
cyclic monomers, radical ring opening, industrial radical polymerization,　4:1713
cyclic nitrones, spin trapping,　4:2002,2004-2005
cyclic nitroxides, nitroxide-mediated polymerization,　4:1727-1728,1827,1838
cyclic oligopeptides, synthesis, radical thiol additions,　4:2025,2028,2029
cyclic polymers, atom transfer radical polymerization,　4:1876
cyclic radicals, stereoselective reactions,　2:658-661
cyclic reactions
chemically induced dynamic nuclear polarization,　1:185-187
degenerate electron exchange,　1:185-187
deprotonation,　1:187
kinetics,　1:185
cyclic selenocarbonates, synthesis,　2:642
cyclic transition states
acyloxy rearrangements,　1:126,127
hydrogen atom migration,　1:130,133
cyclic voltammetry (CV), redox potential determination,　1:250-253
cyclindricines, synthesis, cascade endo-cyclizations,　2:731-732
cyclization-rearrangements, Ugi products, metal-dependent,　2:912
exo versus endo cyclizations, Δ-5-hexenyl radical,　1:317-318
exo cyclizations, radical chain reactions,　1:71-72
3-exo cyclizations
titanocene-mediated
aldehydes,　2:995-997
ketones,　2:995-997
3-exo-tet cyclizations,　2:698
3-exo-trig cyclizations
alkoxy radicals,　2:717-718
aromatic rings,　2:697
exothermic β-scission trapping,　2:696-697
kinetics,　2:694-698
4-exo cyclizations
titanocene-mediated
aldehydes,　2:995-997
ketones,　2:995-997
4-exo-trig cyclizations
alkene substitutions,　2:699-700
kinetics,　2:698-702
nitrogen substituent effects,　2:701
olefin substituent effects,　2:701
regioselectivity,　2:698-702
5-endo-dig cyclizations
Bergman cycloaromatizations,　2:709
carbon-centered radicals, kinetics,　2:707-708
cascades,　2:730
dynamics,　2:706-709
phosphorous ylide flash vacuum pyrolysis,　2:706-707
5-endo-trig cyclizations
aryl radicals,　2:705-706
1,5-H atom transfers,　2:703-704
cascades,　2:730-731
kinetics/thermodynamics,　2:704
radical conjugate additions,　2:703-705
silylmethyl radicals,　2:705-706
stereoelectronics,　2:703-706
tertiary carbon radicals,　2:705
5-exo/6-endo cyclizations
cascades,　2:730-731
manganese complex-catalyzed reactions,　2:749
5-exo/6-exo cyclizations, then SRN1 reaction,　1:344
5-exo cyclizations
allyl iodoacetate,　2:950
carbofuranose synthesis,　2:1149-1153
diastereoselectivity,　2:658-659
titanocene-mediated, epoxide ring opening,　2:997-998
5-exo-trig cyclizations
cascades,　2:730
cyclobutylcarbinyl radical trapping, strained systems,　2:699-700
iminyl radicals,　2:717-718
Kolbe electrolysis,　2:1199
with nitroxide radical trapping, synthetic applications,　2:1100-1101
6-endo cyclizations
cascades,　2:730-731
titanocene-mediated, epoxide ring opening,　2:998-999
6-endo-trig cyclizations, cascades,　2:731
6-exo-cyclizations, diastereoselectivity,　2:658,660
6-exo-trig cyclizations
carbapyranose synthesis,　2:1153-1154
cascades,　2:732
isodasycarpidone synthesis,　2:806
7-endo-trig cyclizations, cascades,　2:731
7-exo-trig cyclizations
cascades,　2:732
unusual pathways,　2:714-715
cyclizations,　1:65,66,71-72,77
acyl radicals
aliphatic azides,　2:1022
electrophilic nitrogen effects,　2:713
aldehydes, metal-dependent,　2:919
aldimines
aryl radicals,　2:721
vinyl radicals,　2:720-721
alkyl halides, tris(trimethylsilyl)silane-mediated, polyimide film microreactors,　2:1244-1246
alkyl radicals, aliphatic azides,　2:1021
alkynyl isonitriles, indole synthesis,　2:1045-1046
amide bond distortions,　2:712
aminyl radicals, sp-hybridized carbons,　2:717-718
aromatic azides, dichlorindium bromide,　2:1026-1027
arylativecobalt-catalyzed,　2:1008-1009
aryl radicals
organic azides,　2:1020
synthetic strategies,　2:1082-1086
tris(trimethylsilyl)silane,　2:579
at germanium,　2:650-653
at oxygen,　2:644-645
at selenium,　2:637-644
at silicon,　2:645-650
at sulfur,　2:635-637
at tellurium,　2:637-641
at tin,　2:650-653
azidonitriles, dichlorindium bromide,　2:1026-1027
carbapyranose synthesis,　2:1154
carbofuranose synthesis,　2:1149-1153
carbon-centered radicals
nitrophilic reactions,　2:719-722
oxophilic reactions,　2:722-724
carbonylative, palladium-catalyzed, 5-iodo-1-pentene derivatives,　2:1005
carbonyl groups, stannylaminyl radicals,　2:1023-1024
carboxylic acids, metal-dependent,　2:918-919
cascade reactions
with aromatic homolytic substitutions,　2:737
with β-eliminations, fused polycyclic cyclopropane synthesis,　2:735
five-membered ring synthesis,　2:739-742
with fragmentations,　2:732-735
with homolytic substitutions, synthetic strategies,　2:737-739
six-membered ring synthesis,　2:742-745
with translocations, synthetic strategies,　2:735-737
chiral Lewis acid-mediated, enantioselective,　2:671-672
chiral zinc complex-catalyzed,　2:742-743
cyano groups, stannylaminyl radicals,　2:1024
cyclic diol synthesis,　2:623
cycloaromatizations,　2:709-711
5-cyclodecynone, oxygen-centered radicals,　2:788
cyclopentane derivative synthesis,　2:1149-1153
dichlorindium bromide
aromatic azides,　2:1026-1027
azidonitriles,　2:1026-1027
dienes, silylated cyclohexadienes,　2:594
β-diketones, manganese(III) acetate-mediated,　2:924
dithiocarbonyl radicals, organic azides,　2:1020-1021
electrochemically initiated
carbonyl groups,　2:1206-1208
enol-ether anisole derivatives,　2:1183
enol-ether furan derivatives,　2:1181-1182
ketene dithioacetals,　2:1178
methoxylated phenanthrene synthesis,　2:1192-1193
enantioselective, chiral Lewis acid-mediated,　2:671-672
energetics,　1:89
enol-ether anisole derivatives,　2:1183
enol-ether furan derivatives,　2:1181-1182
entropy,　2:711-712
epoxides, titanocene-catalyzed/mediated,　2:995-999
epoxypolyenes, titanocene-mediated,　2:998-999
five-membered rings
stereoelectronically disfavoured,　2:703-709
unusual synthesis pathways,　2:709-711
followed by SRN1 reaction,　1:344
α-haloamides, tin hydride-mediated,　2:545
Δ-5-hexenyl radicals,　1:317-323
history,　1:5,8,9,14,29
iminyl radicals, unusual bond formation,　2:717-718
intramolecular,　2:1176
intramolecular homolytic substitutions,　2:645-653
2β-iodo glucopyranosides, branched-chain sugar synthesis,　2:1147-1148
iron(III) salt-mediated, malonates,　2:922-923
ketene dithioacetals,　2:1179
o-ketenimino-substituted benzylic radicals,　2:1052
α-ketenyl alkyl radicals,　2:1052
ketimines
aryl radicals,　2:721
vinyl radicals,　2:720-721
β-ketoesters, metal-dependent,　2:919-921
ketones, metal-dependent,　2:919
Kolbe electrolysis,　2:1198-1199
leaving groups,　2:634-635
Lewis acid-catalyzed, α-carbamoyl radicals,　2:951
Lewis acid-promoted, α-ester radicals,　2:950
malonates, metal-dependent,　2:921-924
manganese(III) acetate-mediated
β-diketones,　2:924
β-ketoesters,　2:919-921
malonates,　2:921-924
memory of chirality,　2:668
metal-dependent,　2:918-932
aldehydes,　2:919
carboxylic acids,　2:918-919
higher order,　2:928-932
β-ketoesters,　2:919-921
ketones,　2:919
silyl enol ethers,　2:928-929
methyl-substituted silyl enol ethers, stannylaminyl radicals,　2:1025
nitrogen-centered radicals, unusual bond formation,　2:716-717
with nitroxide carbon radical trapping,　2:1099-1101
oxidations, cyclopropane synthesis,　2:903-904
oxygen-centered radicals, unusual bond formation,　2:717-719
oxyl radicals, tin hydride-mediated,　2:556
palladium-catalyzed, 6-iodo-1-hexene derivatives,　2:1005-1006
phenyl-substituted silyl enol ethers, stannylaminyl radicals,　2:1025
photoinduced, bromoalkynes, triethylamine,　2:1252-1253
polyfunctionalized cyclohexane analog synthesis,　2:1154
radical
at germanium,　2:650-653
at oxygen,　2:644-645
at selenium,　2:637-644
at silicon,　2:645-650
at sulfur,　2:635-637
at tellurium,　2:637-641
at tin,　2:650-653
cyclic diol synthesis,　2:623
leaving groups,　2:634-635
radical chain reactions,　1:71-73
atom transfer radical cyclizations,　1:65,66
radical clocks,　1:89,111,113,114,116-117
reductive
iron-catalyzed, 6-halo-1-hexene,　2:1012
silanes,　2:602
regioselectivity
aryl radicals,　2:721
ring size effects,　2:712
selenoesters, isodasycarpidone synthesis,　2:806
sequential bond formation, carbon-carbon bonds, samarium diiodide-mediated,　2:890-894
silyl enol ethers
metal-dependent,　2:928-929
stannylaminyl radicals,　2:1024-1025
silylheptadienes,　2:739-740
six-membered ring synthesis, unusual pathways,　2:709-711
small cycle synthesis,　2:694-702
spirocyclic azidocyclohexadienyl radical formation, aromatic azides,　2:1032-1033
stannylaminyl radicals
carbonyl groups,　2:1023-1024
cyano groups,　2:1024
methyl-substituted silyl enol ethers,　2:1025
phenyl-substituted silyl enol ethers,　2:1025
silyl enol ethers,　2:1024-1025
stereoelectronics,　2:693
stereoselective, vinyl iodides, Lewis acid effects,　2:665-666
stereoselective reactions,　2:657-659
tandem, tris(trimethylsilyl)silane-mediated,　2:590-592
tetrahydrofuran synthesis,　2:644-645
tetrathiafulvalene electron donation, diazonium salts,　2:819-820,825
thermodynamics,　2:693
thiol-mediated, natural product synthesis,　2:798-799
thionocarbonates,　2:970
three-membered ring synthesis,　2:694-698
tin hydride-mediated, oxyl radicals,　2:556
titanocene-catalyzed, epoxypolyenes,　2:748-749
tris(trimethylsilyl)silane-mediated, alkyl halides, polyimide film microreactors,　2:1244-1246
unusual,　2:693-728
bond formations,　2:715-724
cyclizations (continued)
five-membered rings,　2:703-709
four-membered rings,　2:698-702
iminyl radicals,　2:717-718
nitrogen-centered radicals,　2:716-717
oxygen-centered radicals,　2:717-719
small cycle synthesis,　2:694-702
vinyl iodides, Lewis acid effects,　2:665-666
vinyl radicals
at silicon,　2:648
organic azides,　2:1022
xanthate transfers,　2:976-981
[2+2] cycloadditions
alkenes, ruthenium-mediated photocatalysis,　2:1223-1224
enones, ruthenium-mediated photocatalysis,　2:1221-1222
ruthenium-mediated photocatalysis,　2:1221-1222,1223-1224
cycloadditions
cascades, SOMO catalysis,　2:683-684
fullerenes with 3,4-fused pyrroleo-3-sulfolenes,　4:2180
cycloalkanes
photoinduced brominations, flow microreactor experiments,　2:1253
photoinduced chlorinations, flow microreactor experiments,　2:1250-1252
cycloalkylacyl radicals, conformation, EPR,　1:158,159
cycloalkyl halides, SRN1 reactions,　1:348-349
cycloalkylmethyl radicals, conformation, EPR,　1:158,159
cycloaromatizations
concepts,　2:709-711
5-endo-dig cyclization terminations,　2:709
five/six membered ring synthesis,　2:709-711
cyclobutanes, synthesis, Knoevenaget adduct paired electrolysis,　2:1184
cyclobutanols, synthesis, titanocene-mediated,　2:996-997
cyclobutanones, synthesis, titanocene-mediated,　2:996-997
cyclobutylcarbinyl radical trapping, strained system, 5-exo-trig cyclizations,　2:699-700
5-cyclodecynone, oxidative cyclizations, oxygen-centered radicals,　2:788
(5'S)-5',8-cyclo-2'-cleoxyadenosine, synthesis, tris(trimethylsilyl)silane,　2:580-581
cyclodextrins (CDs)
nitroxide inclusion,　4:1991-1995
paramagnetic rotaxanes,　1:244
radical complexes, EPR studies,　1:233-234,235-236
cyclohexadieniminyl radicals, formation, aromatic azides,　2:1033-1034
cyclohexadienyl radical derivatives, matrix isolation spectroscopy,　1:222
cyclohexadienyl radicals
aromatizations, isonitriles,　2:1044
homolytic aromatic substitutions, synthetic applications,　2:1067
cyclohexane derivatives, synthesis,　2:1153-1154
cyclohexanes, synthesis, titanocene-mediated 6-endo cyclizations,　2:998-999
cyclohexannone, allylations, SOMO catalysis,　2:684
cycloketones, one-carbon ring expansions, tris(trimethylsilyl)silane,　2:581-582
5',8-cyclonucleosides, DNA oxidation,　3:1338,1340
cyclonucleosides, synthesis, tris(trimethylsilyl)silane-mediated,　2:590
cyclooxygenase (COX), lipid peroxidation,　3:1578,1579-1580
cyclopentanes
synthesis
enol ether oxidations, electrochemically initiated,　2:1176-1177
ketene dithioacetal oxidations, electrochemically initiated,　2:1179
polyfunctionalized analogs, acylic sugar derivatives,　2:1149-1153
cyclopropanations, haloalkenes, electrochemically initiated,　2:1209
cyclopropane
radical cation/anion comparison,　1:301-317
ring opening
N-cyclopropylaniline radical cations,　1:311-312
cyclopropylarene radical cations,　1:313-316
radical anions,　1:303-304
radical cation,　1:307-308
synthesis,　2:903-904
cyclopropane substituted radicals
cations, ring opening,　1:307-316
neutral/cation/anion trends comparison,　1:316-317
cyclopropanols
β-scission, alkoxy radicals,　2:785
synthesis, titanocene-mediated,　2:996-997
cyclopropanol silyl ethers, ring opening, metal-dependent,　2:934
cyclopropylacyl radicals,　2:976-977
cyclopropylamine radical cation, ring opening,　1:309
N-cyclopropylaniline radical cations,　1:311-312
cyclopropylarene radical cations, cyclopropane ring opening in chemical systems,　1:313-316
cyclopropyl benzene, synthesis, cobalt-mediated styrene transformations,　2:1210-1211
N-cyclopropylbenzylamine radical cation, ring opening, SET,　1:310
cyclopropylcarbinyl→homoallyl-type rearrangements,　1:301-307
aliphatic ketyl radical anions,　1:303-306
probes/clocks,　1:301
radical anions from aliphatic ketones,　1:303-306
radical anions from aromatic ketones,　1:302-303,305
structure/reactivity trends, neutral radicals versus radical anions from ketones,　1:305-307
unimolecular rearrangement,　1:301
cyclopropylcarbonyl radical fragmentation, rate constants,　1:122
cyclopropyl radicals, matrix isolation spectroscopy,　1:218,219
5',8-cyclopurines
C5' sugar radical, anaerobic conditions,　3:1348-1351
DNA lesions, repair and mutagenicity studies,　3:1351-1352
ribonucleosides,　3:1352
cyclo[8]pyrrole, synthesis, electrochemically initiated,　2:1194-1195
cyclorearomatizations, concepts,　2:711
cyclotetrasilenyl sily radicals, persistent and stable,　4:2125-2126
cylopropanes, vinyl/siloxy substituted, ring opening,　1:309-310
N-cylopropyl ring opening, arylcyclopropane ring expansions,　1:308-309
cysteine (Cys)
carbon-centered radical reactions,　3:1461-1464
cellular function,　3:1459
ionization,　3:1460
model, relay stations in electron transfer,　3:1487
NO/NO2 radical reactions,　3:1465
oxidant reaction rates,　3:1426,1427
proteins, radical reactions,　3:1467
radical reactions,　3:1460-1467
relay stations in electron transfer,　3:1484-1485
residues, spin labeling, MTSL,　4:1967,1969,1970
structure,　3:1461
superoxide radical reactions,　3:1464-1465
thiyl radicals
enzymatic processes,　3:1460
formation and properties,　3:1460-1461
molecular oxygen reactions,　3:1466
tyrosyl radical reactions,　3:1465-1466
cytochrome P450s, inhibition, N-benzyl-N-cyclopropylamine radical cations,　1:310
cytoprotective effects, lipid peroxidation products,　3:1578,1593-1594
cytosine (C)
hydroxyl radical reactions,　3:1292
one-electron oxidation, thermodynamics,　3:1293-1294
one-electron oxidized G:C, intra-base pair proton transfer,　3:1385-1386
oxidation
adducts arising from C4' radicals,　3:1338,1339
hydroxyl radicals,　3:1324-1326
one-electron transfer,　3:1330
reduction, DNA charge transfer,　3:1398
see also 5-hydroxycytosine; 5-methylcytosine
cytotoxic effects, lipid peroxidation products,　3:1578,1593-1594
D-A see donor-acceptor dyads
DADTFs see dithiadiazafulvalenes
DBNO see di-tert-butyl-N-oxyl
DCF see dead chain fraction
DDH see diol dehydratase
DEA see dissociative electron attachment
deactivation/activation mechanisms, persistent radical effect, controlled/living radical polymerization,　4:1786-1787,1953-1956
deactivation of polymer-end radicals, cocatalysts, organoheteroatom-mediated radical living polymerization,　4:1956,1957-1958
deactivation rate constants, atom transfer radical polymerization,　4:1865-1866
dead chain fraction (DCF), controlled/living radical polymerization,　4:1788-1795
dead chains
conventional versus controlled/living radical polymerization,　4:1786,1787
instantaneous molar mass distributions, polymerization kinetics,　4:1743-1744
dead-end polymerization, kinetics,　4:1742
deaminations
disaccharides, tin-hydride mediated,　2:548
isonitriles,　2:1042
dearomatizations, iodobenzene, meso-tetraol synthesis,　2:810-811
decarbonylations, acyl derivatives, tris(trimethylsilyl)silane,　2:563-565
decarboxylations
Barton esters, photochemical cleavage,　2:1235-1237
radical chain reactions,　1:67-68
tin-hydride mediated, radical generation,　2:547
decatungstate catalysis, fullerene radical reactions,　4:2173-2174,2175
decomposition rate coefficients, initiation, polymerization kinetics,　4:1756-1757
decomposition rates, thermolysis,　1:38,39
defunctionalizations
electrochemically initiated,　2:1212
silicon hydrides,　2:571-572
degenerate electron exchange, cyclic reactions, chemically induced dynamic nuclear polarization,　1:185-187
degenerate-transfer radical polymerization (DTRP), industrial processes,　4:1726,1727,1730-1731
degenerative transfer (DT) processes
controlled/living radical polymerization,　4:1786,1787,1805-1806
advantages and limitations,　4:1807
organoheteroatom-mediated,　4:1953-1956
radical initiators, chain end functionality,　4:1794-1795
xanthates,　2:972-983
mechanisms,　2:972-974
see also reversible addition fragmentation chain transfer
degradable ("green") polymers, industrial radical polymerization,　4:1731
degradative chain transfer
polymerization,　4:1738
kinetics,　4:1739,1779
degradative processes, sulfur-containing compounds, lipid isomerization,　3:1605
degree of polymerization (DP)
controlled/living radical polymerization,　4:1791
conventional radical polymerization,　4:1785
reversible addition fragmentation chain transfer polymerization,　4:1900,1901
see also targeted degree of polymerization
degree of pyramidality
silyl radicals,　4:2121
bis(silyl) silicon-centered radicals,　4:2132,2133,2134
tris(silyl) substituted silyl radicals,　4:2123,2126,2127
dehalogenations, tris(trimethylsilyl)silane,　2:562-563
dehydrogenases, 2-oxoacids, pseudo radical enzymes,　3:1538
demethyl calamenene, synthesis, organic electron donors,　2:837
dendrimer investigation
nitroxide spin probes,　4:1988-1991
covelent/non-covelent approaches,　4:1988
dendrimer synthesis, radical thiol additions,　4:2028,2030-2033,2034
dendritic structures, atom transfer radical polymerization,　4:1875-1876
denitrations, tetracyclic nitro compounds, tin-hydride mediated,　2:548-549
density functional theory (DFT)
benzylsuccinate synthase,　3:1567
coenzyme B12-dependent enzymes,　3:1548,1550,1551
DNA radicals,　3:1376,1380-1381
methyl-coenzyme M reductase,　3:1573
radical stability determination,　1:453-454
ribonucleotide reductase,　3:1568
see also time dependent density functional theory
deoligomerizations, allyl iodoacetate,　2:952
(5'S)-5,8-cyclo-2'-deoxyadenosine, synthesis, tris(trimethylsilyl)silane,　2:580-581
5'-deoxyadenosylcobalamin (AdoCb1) see coenzyme B12
5'-deoxyadenosyl radicals
radical enzyme mechanisms,　3:1501,1502
SAM radical enzymes,　3:1501,1514
structure,　3:1504
2-deoxy-α-D-arabino-hexopyranosyl chloride, C-glycoside synthesis,　2:1137
deoxygenations
Barton-McCombie-type
synthetic variations,　2:970-972
tin-free modifications,　2:967-970
tributyltin hydride-mediated,　2:549-550
xanthates,　2:549-550,965-967
epoxides, titanocene-mediated,　2:989-990
deoxygenations (continued)
β-hydroxyepoxides, allylic alcohol synthesis,　2:989-990
non-anomeric alcohols, carbohydrate synthesis,　2:1158-1160
radical chain reactions,　1:67
titanocene-mediated, epoxides,　2:989-990
2-deoxy glycosyl phosphate, rearrangement of phosphate esters,　1:128-129,130
2'-deoxyguanosine, oxidation,　3:1320-1321,1333
2'-deoxynucleotides, conversion from ribonucleotides, ribonucleotide reductase mechanism,　3:1568-1570
2-deoxypentos-4-ulose lesion, C4' DNA sugar radicals,　3:1353-1354
2-deoxyribonolactone (L) lesion
biochemical studies,　3:1364-1365
generation in duplex DNA,　3:1362-1364
generation in oligonucleotides,　3:1364
2'-deoxyribonucleotides, generation, ribonucleotide reductases,　3:1503-1505
2-deoxyribose sugar moiety
hydrogen abstraction,　3:1345-1346
oxidation,　3:1338,1345-1370
radicals,　3:1345-1370,1372
C1',　3:1362-1365,1367
C2',　3:1359-1362,1367
C3',　3:1357-1359,1366
C4',　3:1352-1356,1366
C5',　3:1346-1352,1366
(±)-13-deoxyserratine, synthesis, tin hydride-mediated,　2:555
2-deoxy sugars
preparation
acyloxy shift,　1:128,129
1,2-ester rearrangements,　2:1158
deprotonations
cyclic reactions, chemically induced dynamic nuclear polarization,　1:187
hydrogen atom transfer comparison,　1:329-330
radical cations,　1:326-329
kinetics,　1:327-329
thermodynamics,　1:326-327
radical dications, ionization of ionic liquids,　1:436,437
DEs see destabilization energies
"design concept", supramolecular systems,　4:1987
destabilization energies (DEs), radical instability scales,　1:98-99
desulfurated sequences, peptides/proteins,　3:1606-1607
desulfurizations
phosphine sulfides, tris(trimethylsilyl)silane,　2:565-566
proteins, lipid isomerization combination, radical damage,　3:1607-1609
thiols, alkyl radical generation,　2:1047
desymmetrization, oxoammonium salt-mediated, synthetic applications,　2:1117-1118
DET see dissociative electron transfer
DFT see density functional theory
DFT, quantum mechanical models, isotropic electron paramagnetic resonance parameters,　1:155-156
diabetes type-2,　3:1679,1680-1684
diabetic complications
free radicals,　3:1692-1694
lipid peroxidation,　3:1693-1694
reactive oxygen species,　3:1693
diacetoxyiodobenzene, oxygen-centered radical remote functionalizations,　2:1233-1234
diacetyl peroxide, Kharasch reaction initiation,　1:62,63
diacylperoxides
history,　1:16
matrix isolation,　1:208
dialkylanilines, electrochemical conversions,　2:1193
dialkyldiazenes, azoinitiators, industrial radical polymerization,　4:1706
N,N-dialkyl-1,7-dibromo-3,4,9,10-perylene diimide and dithienothiophene copolymer (P(PDI2OD-DD)),　4:2066-2067
dialkyl nitroxides, main reactions,　2:1096
dialkyl phosphites, oxidative phosphonations,　2:1086
diamagnetic behavior, thiazyl radicals,　4:2149,2150,2151
diamagnetic dimers, fullerenyl radicals,　4:2171-2172
diastereoselective reactions,　2:655-666
[3+2] annulations,　2:658,660
5-exo-cyclizations,　2:658-659
6-exo-cyclizations,　2:658,660
hydrogen quenching, anomeric radicals,　2:1156-1157
Lewis acid-mediated,　2:662-666
tetrahydrofuran synthesis,　2:1180
diazenes, free-radical sources, history,　1:25-26
diazonamide A, synthesis, heteropinacol coupling,　2:868
diazonium salts
monolayer generation on silicon surfaces,　4:2092-2093
oxidations, tetrathiafulvalenes, synthetic applications,　2:819-826
dibenzothiophenes, synthesis, homolytic substitutions at sulfur,　2:804
diblock copolymers
nitroxide-mediated polymerization,　4:1843
thermosensitive micelles, organoheteroatom-mediated radical living polymerization,　4:1958
diboron radical traps,　2:624
2,6-di-tert-butyl-4-methylphenol (BHT), antioxidant activity,　3:1628
di-tert-butyl-N-oxyl (DBNO) radical
nitroxide-mediated polymerization,　4:1827,1838
structure,　4:1814
2,6-di-tert-butylphenol, anodic oxidations,　2:1188
1,4-dicarbonyl compounds, synthesis, SOMO catalysis,　2:681-682
β-dicarbonyl compounds
additions
alkenes,　2:907-918
enamines, pyrrole synthesis,　2:915
dicarboxylic acids, protected, anodic oxidations,　2:1197
dichlorindium bromide, organic azide reductions,　2:1026
dicyanamide anions, room-temperature ionic liquids,　1:434
1,5-dienes, hydroxysulfenations, endoperoxide synthesis,　2:800-801
1,6-dienes, azidosulfonylations, organic azides,　2:1030-1031
dienes
azidosulfonylation/5-exo-trig cyclizations,　2:739-740
cyclizations, silylated cyclohexadienes,　2:594
hydrosilylations, silylated cyclohexadienes,　2:594
nitroxide-mediated polymerization,　4:1838
1,3-diesters, reductions, samarium diiodide,　2:860
dietary antioxidants
effectiveness,　3:1277
radical formation,　3:1266
supplements,　3:1672,1673
diethylthiophosphite, alkene additions,　2:604
differential oxygen uptake apparatus, inhibited autoxidation kinetic studies,　3:1630-1631
diffusion, reactive oxygen species,　3:1275-1277
diffusion distances, reactive oxygen species,　3:1276-1277
2,6-dihalogenated phenols, electrochemical coupling,　2:1190-1191
diheteroatom compounds, cocatalysts, organoheteroatom-mediated radical living polymerization,　4:1935-1937,1956-1958
dihydrobenzo[b]tellurophenes, synthesis,　2:638-639
dihydrodeoxyepiallocernuine, synthesis, photochemical Hofmann-LOffler-Freytag reactions,　2:1234
dihydrofurans(DHF)
additions, α-xanthate-α-fluoroacetate,　2:606
synthesis,　2:907-910
dihydro-imidazopyrimidinoes, synthesis, xanthate radical cyclizations,　2:979,982
dihydronaphthalenes, synthesis, addition-rearrangement-cyclizations,　2:912-913
2,3-dihydroselenolo[2,3-b]pyridines, synthesis,　2:640
1,2-dihydroxyalkyl radicals, water/ammonia elimination reactions, possible bridging mechanism, 3:1509,　1510
1,22-dihydroxynitiane nitiol analogs, A ring construction, Norrish reactions,　2:1228
diisobutyryl peroxide, photolysis, matrix isolation,　1:213,214
1,3-diketones, alkenyl substituted, reductive cyclizations,　2:1207-1208
α-diketones, synthesis, 1,2-dial oxidations, oxoammonium salts,　2:1111
β-diketones, cyclizations, manganese(III) acetate-mediated,　2:924
dilauroyl peroxide (DLP)
branched-chain sugar synthesis,　2:1142
homolytic aromatic substitutions,　2:1066
neophyl-type rearrangements,　2:1070-1071
dimerizations
alkyl substituted arenes,　2:1184-1195
cerium(IV) ammonium nitrate-mediated,　2:916
electrochemically initiated,　2:1184-1195
enol ethers, metal-dependent,　2:916
radicals, combustion,　1:478,479
tris(silyl)-substituted silyl radicals,　4:2127-2130
vindoline,　2:1194
9,10-dimethylanthracene (DMA)
photocatalytic dimerization,　1:388,389
photocatalytic oxygenation,　1:371
dimethyl azo(bisisobutyrate) (DMAIB), fullerene reactions,　4:2179
dimethyllepidopterene, photocatalytic formation,　1:388,389
5,5-dimethyl-oxazolidine-N-oxyl nitroxides, spin labels and spin probes,　4:1967
4,6-dimethylphenol, anodic oxidations, spirolactone synthesis,　2:1189
2,5-dimethylpyrroline carboxamide, stereoselective reactions,　2:660-661
dimethylsulflde (DMS), atmospheric,　1:518,519
dimethylzinc-mediated reactions, polar crossovers,　2:657-658
diol dehydratases (DDHs),　3:1506,1507
active-site structure,　3:1558
mechanism,　3:1509-1510,1511
RNR comparison,　3:1505
theoretical studies,　3:1556-1558
dioleoyl phosphatidyl chane (DOPC), liposome formation,　3:1609
1,2-diols
oxidations, a-diketone formation,　2:1111
reductions by tris(trimethylsilyBsilane,　2:563-564
synthesis
epoxide ring opening,　2:991-992
vinylsilane epoxide-olefin additions,　2:995
1,2-dioxetane, photocatalytic oxygenation of tetraphenylethylene,　1:372-374
1,3-dioxolanes, ferric perchlorate-mediated fullerene fusion,　4:2182
dipeptides (His-Tyr/Tyr-His), intramolecular electron transfer,　1:195-196
diphenylacelylene (DPA), DNA conjugation, excess electron transfer,　3:1420-1421
diphenyl diselenide, O-trityl oximes closure,　2:809-810
2,2-diphenyl-3-phenylimino-2,3-dihydroindo1-1-yloxyl (DPAIO) radical
nitroxide-mediated polymerization,　4:1827-1828
structure,　4:1814
2,2-dipheny1-1-picrylhydrazyl radical (DPPH)
free-radical inhibition, history,　1:27-28
phenolic antioxidant kinetic measurements,　3:1640-1641
dipolar hyperfine interactions, DNA radicals,　3:1376-1377
dipole moments, electron transfer in peptides/proteins,　3:1487-1489
diradicals
aliphatic rearrangements,　1:7-8
history,　1:7-8,11-12
silyl radicals,　4:2139,2144
direct effects of ionizing radiation
DNA radical formation,　3:1371-1372
on solvents,　1:396,401-402
direct (type 1) photo-oxidation, proteins,　3:1444-1445
direct radical substitutions, radical chain reactions,　1:60-61
direct trapping, carbon radicals, nitroxides,　2:1095-1097
disaccharides
deaminations, tin-hydride mediated,　2:548
synthesis, radical thiol additions,　4:2022
C-disaccharides
synthesis
Barbier conditions,　2:1140
intermolecular carbon-carbon bond formation,　2:1139-1141
intermolecular samariations,　2:1139-1141
samarium diiodide reductions,　2:1140
discovery of free radicals, history,　1:1-19
disease
lipid peroxidation,　3:1577
the metabolic syndrome,　3:1679-1700
diselenide radical anions, amino acids,　3:1467
disilenes, stable anion radicals,　4:2135-2136
disilynes, stable anion radicals,　4:2136-2137
dispersion polymerization.
industrial processes,　4:1703,1722-1723,1724
reversible addition fragmentation chain transfer,　4:1923
dispersion spectrum, electron paramagnetic resonance,　1:149
dispersity, polymerization kinetics,　4:1747-1748
disproportionation reactions
epoxides, hydrogen atom abstractions,　2:989-990
polymerization,　4:1738,1739-1740
disproportionation-to-combination ratio, polymerization kinetics,　4:1776-1777
dissociative electron attachment (DEA), room-temperature ionic liquids,　1:441,442,446
dissociative electron transfer (DET), radical anion ring opening,　1:307
dissociative photoionization, gas phase radicals,　1:490-491
distance dependence, single-step electron transfer,　3:1477,1478
distance measurements in the nanometer range (1:5-8nm), spin labels and spin probes,　4:1971
disubstituted alkyl radicals, stability,　1:457-463,464
α,β-disubstituted enoyls, reductive alkylations, chiral Lewis acid-mediated,　2:674-675
1,2-disubstituted epoxides, reductive opening,　2:991-992
2,3-disubstituted indoles, synthesis, allylic O-stannylketyl radicals, tin hydride-mediated,　2:553-554
disubstituted ketones, synthesis, ring opening,　2:934
disubstitutions, SRN1 reactions,　1:335,336-337,339,361
disulfide radical anions, amino acids,　3:1460,1461,1467
disulfides, thermolysis,　1:41
dithiadiazafulvalenes (DADTFs), spontaneous electron transfers,　2:826-831
dithienothiophene and N,N-dialkyl-1,7-dibromo-3,4,9,10-perylene diimide copolymer,　4:2066-2067
dithiocarbamates, sequential cyclization/group transfers,　2:741-742
dithiocarbonates
Barton-McCombie deoxygenations,　2:965-967
as precursors,　2:965-987
tin-free modifications,　2:967-970
see also xanthates
dithiocarbonyl radicals, cyclizations, organic azides,　2:1020-1021
dithioesters, reversible addition fragmentation chain transfer polymerization agents,　4:1896,1902,1903,1904,1913-1914,1918
dityrosine-class natural products, synthesis, 2,6-dihalogenated phenol electrochemical coupling,　2:1190-1191
divergent synthesis, block copolymers, reversible addition fragmentation chain transfer polymerization,　4:1906,1907-1912
DLP see dilauroyl peroxide
DMA see 9,10-dimethylanthracene
DMAIB see dimethyl azo(bisisobutyrate)
DMS see dimethylsulfide
DNA
artificial nanostructures, charge transfer,　3:1397-1398,1407-1411,1412-1413
charge transfer,　3:1397-1424
damage and repair,　3:1401,1411-1412
excess electron transfer,　3:1413-1422
hole transfer,　3:1399-1413
cleavage, photocatalytic oxygenation,　1:380-383
electrical conduction,　3:1397,1399
electron transfer hopping,　3:1414-1416,1478-1479
excess electron transfer,　3:1413-1422
hopping mechanism,　3:1414-1416
injection,　3:1416-1421
tunneling mechanism,　3:1414
higher order structures, hole transfer,　3:1407-1411
hole transfer,　3:1399-1413
applications,　3:1411-1413
hopping mechanism,　3:1403-1407
tunneling mechanism,　3:1399-1403
unusual structures,　3:1407-1411
intercalation, electron donors/acceptors, hole tunneling study,　3:1399-1401
intrastrand pyrimidine-purine cross-links,　3:1292-1293,1335-1336
mismatched base pairs, hole transfer effects,　3:1409-1411,1412
nanoscale electronic wiring,　3:1397,1412,1413
oxidation,　3:1319-1344
complex lesions,　3:1338-1340
hydroperoxyl radicals,　3:1336-1338
hydroxyl radicals,　3:1319,1321-1328,1336,1337
interstrand cross-links,　3:1338
intrastrand cross-links,　3:1335-1336
long range hole transfer,　3:1401,1411-1412
nucleobase modifications,　3:1319-1344
one-electron transfer,　3:1293-1300,1319-1320,1328-1333
photocatalytic oxygenation,　1:380-383
secondary lesions,　3:1333-1335
single-base damage,　3:1320-1335
sugar radical formation,　3:1345-1370
C1' position,　3:1362-1365,1367
tandem base lesions,　3:1335-1338
oxidation and reduction,　3:1397,1398-1399
photocatalytic oxygenation,　1:380-383
profluorescent spin labels and spin probes,　4:1987
sequence, oxidation potential effects,　3:1398
small reactive species, reaction kinetics,　3:1290-1311
spin labels and spin probes,　4:1970-1971,1987
sugar moieties
hydrogen abstraction,　3:1345-1346
oxidative radical formation,　3:1345-1370,1372
DNA damage,　3:1345,1397
C4-AP lesions,　3:1354-1356
charge transfer,　3:1401,1411-1412
chronic inflammation,　3:1283-1312
complex lesions,　3:1338-1340
5',8-cyclopurine lesions, repair and mutagenicity studies,　3:1351-1352
2-deoxyribonolactone lesion,　3:1362-1365
DNA radicals, ESR/theoretical studies,　3:1371-1396
double strand breaks,　3:1371,1390
guanine lesions
aromatic radical cations,　3:1295-1297
base-sequence effects,　3:1294
carbonate radicals,　3:1294-1295
effects of oxidant charge and solvent exposure,　3:1297-1298
hydroxyl radicals
products,　3:1291-1292
reaction kinetics,　3:1290-1291
tandem lesions,　3:1292-1293
inflammatory response,　3:1283-1312
intrastrand pyrimidine-purine cross-links,　3:1292-1293,1335-1336
lipid peroxidation products,　3:1577,1588
low-energy electrons
ESR studies,　3:1390-1392
theoretical studies,　3:1392-1393
one-electron oxidation,　3:1293-1300
aromatic radical cations,　3:1295-1297
base-sequence effects,　3:1294
carbonate radical reaction kinetics,　3:1294-1295
end products of guanine reactions,　3:1300-1311
thermodynamics,　3:1293-1294
oxidation,　3:1319-1344
oxidative, long range hole transfer,　3:1401,1411-1412
photocatalytic oxygenation,　1:380-383
single-base lesions,　3:1320-1335
single strand breaks,　3:1373,1390-1391
small reactive species reactions,　3:1283-1317
sugar radical formation,　3:1345-1370
tandem base lesions,　3:1335-1338
tandem lesions, hydroxyl radicals,　3:1292-1293
DNA hairpins
excess electron transfer,　3:1415,1417,1418,1420-1421
hole transfer,　3:1401,1402,1404-1406
DNA photocleaver, synthesis, Pschorr reactions,　2:1060
DNA photolase
electron transfer,　3:1482,1483
ketyl radicals,　3:1531-1533
DNA-protein cross-links, oxidative lesions,　3:1338
DNA radicals
anions
ionizing radiation formation,　3:1371-1372
low-energy electron effects,　3:1390
salvation effects,　3:1383
anisotropic hyperfine interactions,　3:1375,1376-1381
cations
hole transfer,　3:1389-1390
intra-base pair proton transport,　3:1385
ionizing radiation formation,　3:1371-1372
low-energy electron formation,　3:1390
solvation effects,　3:1383
electron spin resonance spectroscopy,　3:1371,1373-1374,1375-1380,1381-1392
ESR study/theoretical understanding,　3:1371-1396
formation,　3:1371-1375
ground state properties,　3:1381-1388
conformation,　3:1381-1383
intra-base pair proton transfer in one-electron oxidized G:C,　3:1385-1386
protonation states of one-electron oxidized guanine monomers,　3:1384-1385
solvation/hydration effects,　3:1383-1384
hyperfine coupling constant,　3:1375-1376,1380-1381
hyperfine interactions, ESR/theory,　3:1375-1376
ionizing radiation formation pathway,　3:1371-1374
neutral, formation,　3:1372,1375,1388
oxidative (electron-loss) formation pathway,　3:1373,1374-1375
reductive (electron-loss) formation pathway,　3:1373,1375
structures,　3:1372
sugar radicals,　3:1345-1370
electron spin resonance spectroscopy,　3:1374
formation,　3:1345-1370,1372
oxidation of C1' position,　3:1362-1365,1367
oxidation of C2' position,　3:1359-1362,1367
oxidation of C3' position,　3:1357-1359,1366
oxidation of C4' position,　3:1352-1356,1366
oxidation of C5' position,　3:1346-1352,1366
theoretical prediction of properties,　3:1371,1380-1381
DNA repair
C4-AP lesions,　3:1356
complex oxidative lesions,　3:1338
5',8-cyclopurine lesions,　3:1351-1352
non-enzymatic, time resolved chemically induced dynamic nuclear polarization studies,　1:196-197
DNA studies, spin labels and spin probes,　4:1970-1971,1987
DNP see dynamic nuclear polarization
domino reactions, tris(trimethylsilyl)silane-mediated,　2:592-593
donor-acceptor dyads (D-A)
electron transfer reactions of charge separated state,　1:365-366
9-mesityl-10-methylacridinium ion, photocatalytic charge separation,　1:366-370
donor-acceptor interactions, radical stability,　1:458,462
"doped" polymers, conducting electricity,　4:2057
Doppler spectroscopy, unimolecular reactions, gas phase radicals,　1:494
dormant radical species
controlled/living radical polymerization,　4:1786-1787,1931,1932
activation/deactivation mechanisms,　4:1953-1956,1957-1958
nitroxide-mediated polymerization,　4:1813,1816
double alkylations, titanium-catalyzed, styrene,　2:1014-1015
double bonds
electron-rich, intramolecular anodic coupling, nucleophiles,　2:1176
reversible addition fragmentation chain transfer agents,　4:1896,1897,1905-1906
unsaturated fatty acids, lipid isomerization,　3:1599-1622
see also carbon=carbon double bonds
double chalcogenations, isonitriles,　2:1047-1048
double melting, thiazyl radicals,　4:2152
double quantum coherence EPR, nanometer distance measurements, spin labels,　4:1971
double strand breaks (DSBs), DNA damage,　3:1371,1390
double-stranded DNA (dsDNA), oxidative lesions,　3:1323,1325,1332-1333,1335-1338
doubly charged radicals, ionization of ions, room-temperature ionic liquids,　1:436-437
doxyl nitroxides, spin labels and spin probes,　4:1967
DP see degree of polymerization
DPAIO see 2,2-dipheny1-3-phenylimino-2,3-dihydroindo1-1-yloxyl
DPPH see 2,2-diphenyl-l-picrylhydrazyl radical
DPT see targeted degree of polymerization
driving force, electron transfer rate,　3:1475,1477
drugs/xenobiotics, reactive oxygen species generation,　3:1265-1266
dry electrons, radiolysis of ionic liquids,　1:418-419
dry products, industrial emulsion polymerization,　4:1723
DS see stilbene diether
DSBs see double strand breaks
DT see degenerative transfer processes
DTRP see degenerate-transfer radical polymerization
dynamic equilibrium, propagating radical/dormant species, controlled/living radical polymerization,　4:1786
dynamic nuclear polarization (DNP), spin probes,　4:1974-1975
dynamics, 5-endo-dig cyclizations,　2:706-709
EAL see ethanolamine ammonia lyase
early evolution
radical enzymes,　3:1540
reactive oxygen species,　3:1261
E.Coll (Escherichia coli), ribonucleotide reductases,　3:1503,1504,1505
EDEad see adiabatic electron detachment energies
EDTA see ethylenediaminetetraacetic acid
EET see epoxyeicosatrienoic acid
egg lecithin liposomes, lipid isomerization,　3:1610-1611
eicosanoids, enzymatic lipid peroxidation products,　3:1579
eight-membered carbocycles, synthesis,　2:1154-1155
elastic collisions/scattering, high-energy charged particles interacting with matter,　1:395,396
electrical discharge methods, gas phase isolated radical generation,　1:485
electrically excited oxygen (O('D)), atmospheric photolysis of oxygen species,　1:506,514
electrical transport, nonlinear, thiazyl radicals,　4:2157-2159
electrochemical evaluation techniques, redox potentials,　1:249,250-255
electrochemically initiated reactions
aminoxyl radical-mediated,　2:1202-1203
anodic processes,　2:1176-1206
biaryl compound synthesis,　2:1184-1195
cathodic processes,　2:1206-1212
coupling, biaryl compound synthesis,　2:1184-1195
cyclizations
amine-bearing thioenol ethers,　2:1177-1178
four-membered ring synthesis,　2:1183-1184
ketene dithioacetals,　2:1178
defunctionalizations,　2:1212
functionalizations,　2:1203-1205
halide-mediated,　2:1203
Hofer-Moest reactions,　2:1195-1196
Kolbe-type,　2:1195-1202
nickel-mediated,　2:1206-1211
electrochemically initiated reactions (continued)
oxidations
amine-bearing electron-rich olefins,　2:1177-1178
electron-rich aromatic rings,　2:1180-1183
enol ethers,　2:1176-1177
ketene dithioacetals,　2:1177-1180
radical generation, room-temperature ionic liquids,　1:433,434,437,444,445
radical initiation,　1:51
reductive cyclizations,　2:1206-1211
SRN1 reactions,　1:335
synthetic strategies,　2:1175-1215
electrochemical switching, molecular machines,　1:241,242
electrochemistry
computational,　1:258
fundamentals,　1:250
see also redox…
electrolysis, 2,6-dihalogenated phenols,　2:1190-1191
electromagnetic radiation
DNA radiolysis,　3:1414
high-energy interactions with matter,　1:395,396
see also light...; photo…
electron affinities
definition,　1:249
photoionization of gas phase radicals,　1:489-490
electron bifurcation, ketyl radicals, radical enzymes,　3:1531,1532
electron-deficient alkenes, reductions, samarium diiodide,　2:863
electron detachment energies, anions, room-temperature ionic liquids,　1:441
electron donors/acceptors
DNA excess electron transfer study,　3:1415-1416,1420-1421
DNA hole tunneling study,　3:1399-1401
see also organic electron donors
electronegativity equation, radical stabilization energies,　1:99-100
electronic applications
biomolecular devices,　3:1495-1497
conducting polymers,　4:2057-2079
electronic characteristics, thiazyl radicals,　4:2147-2161
electronic coupling matrix element, electron transfer rate,　3:1475,1477
electronic effects, thermodynamic stabilization of silyl radicals,　4:2118-2120
electronic stabilization, carbon-centered radicals,　1:57,58
electron paramagnetic resonance (EPR) spectroscopy,　1:147-174
basic concepts,　1:147-148
biological systems, spin labels and spin probes,　4:1966-1987
carbon-centered radical geometry,　1:156-157
exchange broadening,　1:159-160
heteroatom-centered radicals,　1:160-165
host-guest complex study,　1:233-237
internal motions,　1:159-160
interpretation of complex spectra,　1:151-153
isonitrile radical adducts,　2:1038-1041
isotropic g-factors,　1:148,150-151,156,162,163
isotropic hyperfine splittings,　1:148,151,152,153-156
kinetic EPR spectroscopy,　1:165-169
line shapes,　1:148-150
matrix isolation spectroscopy,　1:208,209-210,211-212
nanometer distance measurements,　4:1971,1973
phenolic antioxidant study
kinetics,　3:1633,1640-1641
thermodynamics,　3:1642-1644
polymerization kinetics,　4:1752-1753,1771,1772,1779
pulse electron double resonance, nanometer distance measurements,　4:1971,1973
quantum mechanical models,　1:155-156
radical conformations,　1:157-159
radical equilibrium study,　3:1642-1644
radicals in inert environments,　1:175
radical study,　1:175
relaxation phenomena,　1:148-150
room-temperature ionic liquids,　1:434,440,441,442
silyl radicals,　4:2126-2127,2128,2131
alkali-metal-/mercury-substituted silyl radicals,　4:2139,2140,2141
bis(silyl) silicon-centered radicals,　4:2133,2134
transition metal-substituted silyl radicals,　4:2142,2143
tris(silyI)-substituted silyl radicals,　4:2127,2128,2131
spin labels and spin probes,　4:1965-2015
biological systems,　4:1966-1987
supramolecular systems,　4:1987-2004
supramolecular radical chemistry,　1:229-230
supramolecular systems, spin labels and spin probes,　4:1987-2004
temperature-dependent linewidths,　1:159
thermodynamic parameter determination,　1:169-170
see also chemically induced dynamic electron polarization
electron paramagnetic resonance imaging (EPRI), spin probes,　4:1973
electron paramagnetic resonance/spin trapping (EPR/ST),　4:1966,2002,2003,2004-2005
electron-rich aromatic rings, oxidations, electrochemically initiated,　2:1180-1183
electron-rich double bonds, intramolecular anodic coupling, nucleophiles,　2:1176
electron-rich olefin (carbene/symmetric dimer), muonium attachment, ionic liquids,　1:434-435
electrons
dry, radiation-induced radical reactions,　1:418-419
hydrated, radiation-induced radical reactions,　1:401,403,407-408
ionizing radiation-induced production,　1:395,396
solvated, radiation-induced radical reactions,　1:410,418-419
water radiolysis,　1:401,403,407-408
electron self-exchange reactions, radical polymer batteries,　4:2166,2169
electron spin resonance (ESR) spectroscopy
DNA excess electron transfer,　3:1414
DNA radicals,　3:1371,1373-1374
anisotropic hyperfine interactions,　3:1379-1380
excited state properties,　3:1388-1392
ground state properties,　3:1381-1388
fullerenyl radicals,　4:2171-2172
electron transfer (ET)
amino acids,　3:1459,1472
asymmetric, chiral ligand-assisted,　2:686-689
biomolecular electronic devices,　3:1495-1497
cysteine radical reactions,　3:1465,1466,1467
DNA,　3:1413-1422,1478-1479
followed by proton transfer, hydrogen atom transfer mode,　1:323-324
from guanine by aromatic radicals,　3:1295-1297
history,　1:19-21
hole migration,　3:1299-1300
hopping,　3:1478-1481
9-mesityl-10-methylacridinium ion donor-acceptor linked dyad,　1:366-389
nucleophilic substitutions,　1:333
one- and two-electron reductions, fullerenes,　4:2190
peptides/proteins,　3:1475-1499
amide bond stepping stones,　3:1490-1493
amino acids,　3:1459
aromatic amino acids,　3:1481-1484
backbone influences,　3:1487-1493
charges,　3:1489-1490
dipole moments,　3:1487-1489
pathway investigation,　3:1479-1481
peptide assays,　3:1479-1481,1482
radiation-induced radicals in aqueous solutions,　1:409
relay amino acids,　3:1480-1487
ribonucleotide reductase,　3:1475,14-77,1493-1495
sulfur-containing amino acids,　3:1484-1487
photocatalytic oxygenation, 9-mesityl-10-methylacridinium ion,　1:370-383
photoinduced,　1:288-297
synthetic strategies,　2:1217-1221
prolonged lifetime charge separated state,　1:365,366-389
radical chain reactions,　1:62
rates
parameters,　3:1475,1477
peptide backbone influences,　3:1487-1493
redox properties of radicals,　1:249-273
single-step process,　3:1475,1477-1478
SRN1 reactions,　1:333,334-335
theory, DNA study,　3:1398
thioethers,　3:1467,1471
time resolved chemically induced dynamic nuclear polarization studies,　1:194-197
see also activators generated by electron transfer; excess electron transfer; one-electron oxidation
electron transferring flavoprotein (Ed), ketyl radicals, radical enzymes,　3:1530,1531,1532
electron transport, mitochondrial reactive oxygen species generation,　3:1261-1262
electron-withdrawing groups (EWGs)
Kolbe electrolysis,　2:1196,1198-1199
Meerwein arylations,　2:1080
SRN1 reactions,　1:333,354-361
electron Zeeman interactions, EPR spectra,　1:148
electrophilic carbon-centered radicals, arylations, synthetic strategies,　2:1068-1069,1076-1079
electrophilic coupling
following oxidation,　1:288-289
intramolecular anodic,　2:1176
electrophilic radicals, in vivo, reactions with proteins,　3:1428
eliminases
coenzyme B12-dependent enzymes,　3:1505-1506,1507,1509-1511
ribonucleotide reductases,　3:1505,1507
β-eliminations
cascade reactions, with cyclizations, fused polycyclic cyclopropane synthesis,　2:735
phosphorus-centered radical generation,　2:795-796
radical chain reactions,　1:60,61,62,63
sulfur-centered radicals,　2:803-804
tris(trimethylsilyl)silane-mediated,　2:584-585
ellipticine
synthesis
homolytic aromatic substitutions,　2:1064-1065
selenium-centered radicals,　2:806-807
empirical estimation schemes, enthalpies of formation,　1:84,88
empirical valence bond (EVB) calculations, Co-C homolysis,　3:1551
emulsion polymerization (EP)
ab initio, RAFT,　4:1920-1921
industrial formulations,　4:1723
industrial processes,　4:1721-1724
industrial products,　4:1722-1723
inverse,　4:1722
nitroxide-mediated polymerization,　4:1821,1822,1840
reversible addition fragmentation chain transfer,　4:1920-1925
seeded. RAFT,　4:1921-1922
see also microemulsion polymerization; miniemulsion polymerization
enamines
additions, β-dicarbonyl compounds, pyrrole synthesis,　2:915
α-oxyaminations, nitroxide carbon radical trapping,　2:1097-1099
enantioselective reactions,　2:666-689
additions, N-acyl hydrazones, organoboranes,　2:618
allylations
cerium(IV) ammonium nitrate-mediated,　2:906-907
SOMO catalysis,　2:680-681
α-arylations, SOMO catalysis,　2:680-681
cascades, bromine atom transfers, organoboranes,　2:605
chiral Bronsted acid-mediated,　2:685
chiral chain-transfer reagents,　2:666-667
chiral ligand-assisted asymmetric electron transfers,　2:686-689
conjugate addition-radical alkoxyaminations, B-alkylcatecholboranes,　2:615
cyclizations
chiral Lewis acid-mediated,　2:671-672
chiral zinc complex-catalyzed,　2:742-743
5-exo cyclizations, Sharpless epoxide ring opening,　2:997-998
halogen atom transfers, chiral Lewis acids,　2:670-672
hexylsilanes,　2:595-596
hydroborations, rhodium-catalyzed,　2:612
hydrogen atom transfers, chiral Lewis acids,　2:668-670
hydrogen bonding-mediated,　2:685-686
lipid peroxidation,　3:1579-1580
organocatalysis,　2:679-686
α-oxyaminations, aldehydes,　2:680-681
phenylselenium transfers, organoboranes,　2:605-606
radical transfer additions, iodine atoms,　2:952
reductive alkylations, chiral Lewis acids,　2:672-676
SOMO catalysis,　2:680-684
tandem conjugate addition-fragmentation reactions, chiral Lewis acid-mediated,　2:678-679
tris(trimethylsilyl)silane-mediated,　2:583-584
see also stereosective reactions
encapsulation, by cucurbiturils, radical cation stabilization,　1:236
end-functionalized polymers
atom transfer radical polymerization,　4:1877-1878,1879
organoheteroatom-mediated radical living polymerization,　4:1949-1953
synthesis, radical thiol-X click chemistry,　4:2037-2039,2040
end-group chemistry
organoheteroatom-mediated radical living polymerization,　4:1949-1953
reversible addition fragmentation chain transfer polymerization,　4:1916-1919
endocyclic closure, aryl radicals,　2:713-714
endocyclic conjugated enones, benzophenone-initiated photoadditions, methanol, branched-chain sugar synthesis,　2:1142-1143
endo cyclization see cyclizations
endogenous oxidant sources,　3:1425,1426
endoperoxides, synthesis, 1,5-diene hydroxysulfenations,　2:800-801
endoplasmic reticulum (ER), flavoprotein oxidases, reactive oxygen species generation,　3:1264,1265
endoplasmic reticulum oxidoreductin I (ERO1), reactive oxygen species generation,　3:1264,1265
endo-tet reaction pathways,　2:694
enediynes, Bergman cyclizations, 1,4-benzene diradical trapping,　2:1101-1102
engines, combustion research,　1:478-479
enolate ions of aliphatic ketones, SRN1 reactions,　1:336
enolates
coupling, iron(III) salt-mediated,　2:924
oxidative coupling, metal-dependent,　2:926
enol ethers
anisole derivatives, cyclizations, electrochemically initiated,　2:1183
dimerizations, metal-dependent,　2:916
furan derivatives, cyclizations, electrochemically initiated,　2:1181-1182
oxidation, electrochemically initiated,　2:1176-1177
enones
additions, organoboranes,　2:611
[2+2] cycloadditions, ruthenium-mediated photocatalysis,　2:1221-1222
reductive alkylations, chiral Lewis acid-mediated,　2:676-677
enoxy radical, stability measurement,　1:452-453
enthalpies of formation (Δ-fH°),　1:82-84
ab initio values,　1:84
alcohols/alkoxy radicals,　1:91-93
amines/nitrogen-centered radicals,　1:95-97
bond dissociation enthalpy measurement,　1:83-84
electron paramagnetic resonance,　1:169
empirical estimation schemes,　1:84,88
experimental measurements,　1:84
group additivity based estimates,　1:84,88
Hess's Law,　1:82
hydrocarbons/carbon-centered radicals,　1:88-91
hydroperoxides/hydroperoxyl radicals,　1:93-95
literature values,　1:85-87,90,92
regularities,　1:84,88
enthalpies of reactions, Hess's Law,　1:81-82
entrainment, SRN1 reactions,　1:334,341,349
entropy, cyclizations,　2:711-712
environmental impact, radical batteries,　4:2163,2168,2169
1-en-6-ynes, azidosulfonylations, organic azides,　2:1030-1031
enynes, azidosulfonylation/5-exo-trig cyclizations,　2:739-740
enzymes
antioxidants
indirect,　3:1626-1627
preventive,　3:1625-1626
electron transfer,　3:1475,1477,1482,1485,1493-1494
lipid peroxidation,　3:1578,1579-1580
cholesterol oxidation,　3:1587-1588
see also radical enzymes
EP see emulsion polymerization
epoxide radicals, intermolecular additions, alkenes,　2:993-995
epoxides
aldehydes,　2:995-997
cyclizations, titanocene-catalyzed/mediated,　2:995-999
deoxygenations,　2:989-990
disproportionations,　2:989-990
intramolecular homolytic substitutions,　2:644-645
ketones,　2:995-997
lipid peroxidation products,　3:1585
reductive opening, alcohol formation,　2:990-993
styrene alkylations, cobalt-catalyzed,　2:1010-1011
sustainable hydrogen atom donors,　2:993
titanocene-catalyzed/mediated reactions,　2:989-1001
β-titanoxy radical synthesis,　2:989-990
epoxyeicosatrienoic acid (EET), lipid peroxidation product,　3:1580,1585
α,β-epoxy ketones, opening, titanocene-mediated,　2:991-992
epoxypolyenes
cyclizations, titanocene-mediated,　2:998-999
titanocene-catalyzed cyclizations,　2:748-749
EPR see electron paramagnetic resonance
EPRI see electron paramagnetic resonance imaging
EPR/ST see electron paramagnetic resonance/spin trapping
equilibrium constants
atom transfer radical polymerization,　4:1864,1866-1868
redox potential correlation,　4:1866-1868
ER see endoplasmic reticulum
EROI see endoplasmic reticulum oxidoreductinl
erythrocytes, lipid peroxidation,　3:1583,1589
(-)-erythrodine, synthesis, sulfur-centered radicals,　2:799
Escherichia coil (E.Coli), ribonucleotide reductases,　3:1503,1504,1505
ESR see electron spin resonance
ester carbonyl-alkene cyclizations, samarium diiodide,　2:876-877
α-ester radicals, cyclizations, Lewis acid-promoted,　2:950
1,2-esters, rearrangements, 2-deoxy sugar synthesis,　2:1158
esters
activation, silicon surfaces, functionalized monolayers,　4:2106-2109
benzoic acid-derivatives, silane-mediated synthesis,　2:594-595
fragmentations, tin hydride-mediated,　2:553
functionalized, synthesis, flow microreactor experiments,　2:1254-1255
hydrolysis/reduction/cleavage, silicon surfaces, functionalized monolayers,　4:2104-2106
nitrite, photoinduced remote functionalizations, oxygen-centered radicals,　2:1231-1233
reductions, samarium diiodide, synthetic applications,　2:860
1,2-shift, radical rearrangements,　1:125-129,2:1158
β-ester substituted alkyl radicals, rearrangements,　1:127,128
ester-substituted radicals, rearrangements,　1:125-129
ET see electron transfer
ethane, atmospheric reactions,　1:522-523
ethanolamine ammonia lyase (EAL)
mechanism,　3:1506,1507,1510
theoretical studies,　3:1559-1561
ethyl 2-(benzenesulfonylamino)acrylate, reductive coupling, alkenes,　2:613
ethylene, hydroxyl radical reactions, radiation-induced radicals in gaseous systems,　1:398-399
ethylenediaminetetraacetic acid (EDTA), metal chelating preventive antioxidant,　3:1623,1624
ethyl pyruvate, alkylations,　2:613
ethyl radicals, matrix isolation spectroscopy,　1:212-213
ethynyl benzenes, 5-endo-dig cyclizations, kinetics,　2:707
ethynyl radicals, matrix isolation spectroscopy,　1:214-215
eudesmanolide, semisynthesis, germacrane,　2:998-999
EVB see empirical valence bond
evolution
radical enzymes,　3:1540-1541
reactive oxygen species,　3:1261
EWGs see electron-withdrawing groups
excess electron transfer
DNA,　3:1413-1422
see also electron transfer
exchange broadening, electron paramagnetic resonance,　1:159-160
exchanges, functional groups, electrochemically initiated,　2:1203-1205
excitation of molecules, ionizing radiation,　1:395,396
excited electronic states, unimolecular reactions, gas phase radicals,　1:493
excited state processes, DNA radicals,　3:1388-1393
exciton-mediated initiation, monolayer generation on silicon surfaces,　4:2093-2096
exobiology (astrobiology), atmospheric chemistry,　1:480
exocyclic closure, transition state electronics,　2:714-715
exo cyclization see cyclizations
exogenous oxidant sources,　3:1425,1426
exothermic β-scissions, 3-exo-trig cyclizations,　2:696-697
experimental modeling studies, monolayer generation on silicon surfaces,　4:2096-2100
FAD see flavin adenine dinucleotide
fatty acids
free radicals, the metabolic syndrome,　3:1685-1690
lipid isomerization,　3:1599-1622
structures,　3:1599,1600
see also free fatty acids; monounsaturated fatty acids; polyunsaturated fatty acids
FCF see Frank-Condon factors
Fe(III) see iron(III)
Fenton chemistry
history,　1:15
preventive antioxidants,　3:1624,1625
reactive oxygen species,　3:1272-1273
ferric perchlorate (Fe(ClO4)3)-mediated radical reactions, fullerenes,　4:2174,2176-2177
ferromagnetism
BBDTA salts, crystal solvent evaporation,　4:2155-2156
coupling/ordering, thiazyl radicals,　4:2154-2156
FFAs see free fatty acids
field dependence, chemically induced dynamic nuclear polarization studies,　1:198-199
field-effect mobility, polymer-based field-effect transistors,　4:2059,2061
field-effect transistors (FETs)
organic,　4:2058-2059
see also polymer-based field-effect transistors
Fischer's phase diagrams, nitroxide-mediated polymerization,　4:1819,1824
Fisher-Ingold persistent radical effect, hydrogen abstractions,　1:131
five-membered heterocycles, synthesis, sulfanyl—isonitrile radical additions,　2:1045
five-membered rings
cyclic nitrones, spin trapping,　4:2002,2004-2005
synthesis
cascade reactions,　2:739-742
stereoelectronically disfavoured,　2:703-709
unusual pathways,　2:709-711
flash laser photolysis (FLP), DNA charge transfer studies,　3:1404,1406,1421
flash photolysis
characterization of radicals,　1:297-298
see also laser flash photolysis
flash vacuum pyrolysis (FVP)
matrix isolation of radicals,　1:207,208,210
phosphorous ylides, 5-ends-dig cyclizations,　2:706-707
flat silicon surfaces, self-assembled monolayers,　4:2082
flavin adenine dinucleotide (FAD), SAM-dependent enzymes,　3:1503,1529-1534,1538
flavin cofactors, DNA photolase,　3:1482,1483
flavin serniquinone, radical enzymes,　3:1503,1529-1534,1538,1539
flavoprotein oxidases, reactive oxygen species generation,　3:1264,1265
flexible batteries,　4:2163,2167,2169
flow microreactor experiments
atom transfer radical polymerizations,　2:1248-1250
carbonylations,　2:1246-1248
free radical polymerizations,　2:1247
gas-liquid biphasic reactions,　2:1246-1248
halogenations,　2:1250-1253
photo-carbonylations,　2:1253-1256
photoinduced reactions,　2:1250-1253
polymerizations,　2:1248-1250
synthetic strategies,　2:1243-1258
thermally-induced reactions,　2:1243-1250
fluoranthene, oxidations, perylene derivative synthesis,　2:1186-1187
fluorescence quenching
DNA mismatched base pair detection,　3:1412
spin labels and spin probes for living system study,　4:1986
fluoride-catalyzed attachment, monolayer generation on silicon surfaces,　4:2096
fluorinations, fullerenes,　4:2185
fluoroalkyl radicals
additions
to fullerenes,　4:2178-2179
tris(trimethylsilyl)silane-mediated,　2:585-586
fluorocarbon radical clocks,　1:117
α-fluoro-α-iodo-β-arylated ketones, synthesis, Meerwein arylations,　2:1081
fluorous tin hydrides, preparation,　2:534-537
follow-up homogeneous kinetics, redox potential determination,　1:252-253
fomitellic acids, AB ring synthesis, titanium complex-catalyzed,　2:749
food spoilage, lipid peroxidation,　3:1577
formylamine, 8-oxo-7,8-dihydroguanine lesion,　3:1336
formylations, B-alkylcatecholboranes,　2:614
fortucine, pentacycle core synthesis, cyclization/aromatic homolytic substitutions,　2:738
Fourier transform-nuclear magnetic resonance (FT-NMR), chemically induced dynamic nuclear polarization,　1:176
four-membered rings
synthesis
carbocycles,　2:1154-1155
electrochemically initiated,　2:1183-1184
unusual cyclizations,　2:698-702
FOx radicals, atmospheric,　1:510-511
F/R see fragmentation-recombination
fragmentation/recombination (F/R) mechanism
acyloxy rearrangements,　1:126,127
coenzyme B12-dependent enzymes,　3:1552-1553,1555
fragmentations
alkoxy radicals, hydroazulenone synthesis,　2:734-735
aryl esters, samarium diiodide,　2:860
cascade reactions, with cyclizations,　2:732-735
chiral Lewis acid-mediated, enantioselective,　2:676-678
esters, tin hydride-mediated,　2:553
ionization of ionic liquids,　1:436,438,440,441,442-441
ketones, samarium diiodide, synthetic applications,　2:859-860
radical clocks,　1:114,117-118,122
fragmentations (continued)
sulfur-centered radicals,　2:803-804
tin hydride-mediated, esters,　2:553
α-fragmentations, imidoyl radicals, isonitrile formation,　2:1038
β-fragmentations
alkoxyl radical-promoted, carbohydrates,　2:1165-1169
B-alkylcatecholboranes,　2:612-613
trialkylboranes,　2:609-610
Frank-Condon factors (FCFs), photoionization of gas phase radicals,　1:488-490
free fatty acids (FFAs)
the metabolic syndrome,　3:1685-1687
etiology of increased circulating levels,　3:1685-1686
insulin biosynthesis impairment,　3:1680
mitochondria effects,　3:1686
NADPH oxidase-mediated superoxide radical generation,　3:1687
obesity,　3:1691
peroxisome effects,　3:1686-1687
free-jet spectroscopy, isolated radicals,　1:482
free-radical chain oxidation,　3:1623
see also autoxidation; lipid peroxidation
free-radical independent lipid peroxidation,　3:1578,1579
free-radical-mediated lipid peroxidation,　3:1577,1578,1580-1588
free radicals
the metabolic syndrome,　3:1679-1700
self-assembly,　4:1999,2000-2004
use of term,　3:1501
free-radical stress,　3:1599,1601,1605,1607-1609,1612-1615,1619
Fremy's salt
amino acid oxidations, α-keto add synthesis,　2:1123
phenol oxidations, benzoquinone synthesis,　2:1122
unsaturations, synthetic strategies,　2:1103-1104
frontside mechanisms, intramolecular homolytic substitutions,　2:629-632
I.-fucos-1-y1 radicals, additions, α,β-unsaturated esters,　2:1133
fullerenes,　4:2171-2195
additions, scandine,　2:1217-1218
C60/C70 radical addition comparison,　4:2173
carbon-centered radicals,　4:2171-2180
derivatives, polymer-based solar cells,　4:2068
halogenations,　4:2185-2186
hydrogen atom additions,　4:2184-2185
metal-centered radicals,　4:2183-2184
oxygen-centered radicals,　4:2180-2182
[6,6]-phenyl-C61-butyric acid methyl ester,　4:2060,2068,2070,2071-2075
phosphorus-centered radicals,　4:2182
photocatalytic oligomerization via charge separation,　1:386-388
polymer-based solar cells,　4:2068,2070,2071-2072
radiation-induced radical reactions,　1:411-412
radical ions,　4:2186-2192
RC60 radicals, pyracylene unit, atom numbering,　4:2172
silicon-centered radicals,　4:2183
sulfur-centered radicals,　4:2180-2181
thiol-ene functionalization,　4:2045,2047
fullerenyl radical dimers,　4:2171-2172
fullerite (C60/C70 mixture), hydrogenation,　4:2185
functional group exchanges, electrochemically initiated,　2:1203-1205
functional group transformations, tin hydride-mediated,　2:540-556
functionalizations
electrochemically initiated,　2:1203-1205
isonitriles,　2:1042
α-this carbamates,　2:1205
functionalized amino acids/peptides, radical thiol additions,　4:2022,2024-2025,2026,2027,2028
functionalized esters, synthesis, flow microreactor experiments,　2:1254-1255
functionalized monolayers
silicon surfaces,　4:2101-2112
acid fluoride monolayers,　4:2109-2110
active esters,　4:2106-2109
carbon-hydrogen bond activation,　4:2101-2104
carboxylic acids,　4:2104,2105
click chemistry,　4:2111-2112,2113
ester activation,　4:2106-2109
ester hydrolysis/reduction/cleavage,　4:2104-2106
functionalized monomers, organoheteroatom-mediated radical living polymerization,　4:1940,1943
functionalized polymers
atom transfer radical polymerization,　4:1877-1878,1879
end group transformation, organoheteroatom-mediated radical living polymerization,　4:1949-1953
organotellurium-mediated radical living polymerization,　4:1958-1960
synthesis, radical thiol-X click chemistry,　4:2033,2035-2039,2040
functionalized vegetable oils, radical thiol additions,　4:2022
furans
enol-ether derivatives, cyclizations,　2:1181-1182
synthesis, tris(trimethylsilyl)silane,　2:575-576
fused bicyclic piperidinones, synthesis, radical cascade transfers,　2:618
fused polycyclic cyclopropanes, synthesis, cyclization/β-elimination cascades,　2:735
3,4-fused pyrroleo-3-sulfolenes, cycloadditions with fullerenes,　4:2180
FVP see flash vacuum pyrolysis
G3(MP2)-RAD, coenzyme Biz-dependent enzymes,　3:1548,1556
GA see group additivity
gain of function changes, protein oxidation,　3:1448
galvinoxyl radicals
inhibition/scavenging, history,　1:27-28
redox reactions,　4:2164-2165
γ-rays
DNA radiolysis,　3:1414
interactions with matter,　1:395,396
gas-liquid biphasic reactions, flow microreactor experiments,　2:1246-1248
gas phase oxidants, troposphere,　1:514-518
gas phase radicals
absolute photoionization cross-section,　1:491
bimolecular reactions,　1:479,495-498
chemical reactions,　1:477-502
combustion research,　1:478-480
dissociative photoionization,　1:490-491
extraterrestrial atmospheres,　1:480
Frank-Condon factors,　1:488-490
generation,　1:482-487
interstellar chemistry,　1:481-482
ionization energy,　1:488-490
isolated radical generation,　1:482-487
photoionization,　1:487-492
plasma chemistry,　1:480-481
radiation-induced radicals,　1:397-400
signatures,　1:487-488
study methods,　1:482
unimolecular reactions,　1:479,492-495,498
see also atmospheric chemistry
Gaussian lineshapes, electron paramagnetic resonance,　1:150
GDH see glycerol dehydratase
gel effect, polymerization kinetics,　4:1742-1743
gels
hydrogel synthesis, thiol addition to unsaturated compounds,　4:2044-2045
microgels, atom transfer radical polymerization,　4:1876
organotellurium-mediated radical living polymerization,　4:1959
geminate chemically induced dynamic nuclear polarization, hyperfine coupling constant,　1:184-185
geminate dynamics, neutral radicals, ionization of ionic liquids,　1:437
genetically encoded unnatural amino acids, orthogonal spin labeling,　4:1967,1970
geometric dependency, homolytic halogen translocations,　2:630
germacrane, eudesmanolide semisynthesis,　2:998-999
germanium, intramolecular homolytic substitutions,　2:650-653
germanium-centered radicals, electron paramagnetic resonance,　1:161-162
germylenol ethers, ketone perfluoroalkylations,　2:606
1,n-germyl translocations, intramolecular homolytic substitutions,　2:651
g-factors, electron paramagnetic resonance,　1:148,150-151,156,162,163
GGG, DNA hole hopping, 3:1403-1404,　1405-1406
Gh see guanidinodihydantoin
Giese-type additions, vinylpinacolborane,　2:623
glass effect
monolayer generation on silicon surfaces,　4:2091-2092
polymerization kinetics,　4:1742,1743
glucose autoxidation,　3:1681
glucose-derived free radicals, type-2 diabetes,　3:1680-1684
glucotoxicity, pancreatic β-cells,　3:1680
D-gluco-1-y1 radicals, generation,　2:1133
glutamate mutase (GM)
active-site structure,　3:1555
Co-C bond homolysis,　3:1550,1551
mechanism,　3:1508,1511-1513
theoretical studies,　3:1555-1556
glutathione peroxidase (GPx), antioxidant action,　3:1625-1626
glutathione (reduced) (GSH)
cellular function,　3:1459
ionization,　3:1460
radical scavenging,　3:1270,1271,1276,1277
structure,　3:1461
thiol-specific nitroxide spin labels,　4:1984,1985,1986
glycal epoxides, radical formation,　2:994
glycals, cerium(IV) ammonium nitrate-mediated additions to malonates, branched-chain sugar synthesis,　2:1142
exo-glycals, azidoselenations, C-ketoside synthesis,　2:1141-1142
glycation, advanced glycation end products,　3:1681,1682,1684-1685
glycerol dehydratase (GDH)
biotechnological applications,　3:1539
glycyl-radical enzyme,　3:1518,1519
mechanism,　3:1507,1509-1510,1511,1514
theoretical studies,　3:1558-1559
glycine esters, fullerene photochemical reactions,　4:2187
glycoclusters, synthesis, radical thiol additions,　4:2022,2023,2024
glycopeptides, synthesis, radical thiol additions,　4:2025,2026,2027,2035-2036
α-C-glycosides, synthesis,　2:1137-1139
β-C-glycosides, stereoselective synthesis,　2:1156-1158
C-glycosides
synthesis
enol ether oxidations, electrochemically initiated,　2:1176-1177
hexamethylditin photochemical cleavage,　2:1238-1239
intermolecular carbon-carbon bond formation,　2:1132-1139
intramolecular carbon-carbon bond formation,　2:1143-1144
transition metal-catalyzed,　2:1136
β-O-glycosides, stereoselective synthesis,　2:1156-1158
glycosylations, phosphate ester rearrangement to 2-deoxy glycosyl phosphate,　1:128-129,130
glycosyl pyridyl sulfones,　2:1137,1140
glycos-1-y1 radicals,　2:1131-1132,1133-1135,1144
glycylglycine, photoreactions, time resolved chemically induced dynamic nuclear polarization,　1:191-193
glycyl radical enzymes,　3:1502
irreversible SAM radical enzymes,　3:1517-1520
mechanisms,　3:1501,1502
theoretical studies,　3:1562-1568
see also glycerol dehydratase
GM see glutamate mutase
gold nanoclusters, 9-mesityl-10-methylacridinium ion, photocatalytic charge separation,　1:368,369
gold nanoparticles
radical-mediated photochemical synthesis,　4:2198,2202,2205
self-assembly monolayer protection,　1:237-239
Gomberg, M., triphenylmethyl radical discovery,　1:2-3
Gomberg-Buchmann reaction, history,　1:29
GPx see glutathione peroxidase
gradient copolymers
atom transfer radical polymerization,　4:1871
industrial radical polymerization,　4:1714
graft copolymers
atom transfer radical polymerization,　4:1874-1875,1878
industrial radical polymerization,　4:1714
grafting, molecular hybrids, atom transfer radical polymerization,　4:1876
gram-scale synthesis, methylene tetrahydrofurans,　2:1243-1244
Grignard reactions
free-radical formation, history,　1:26
samarium diiodide-mediated, synthetic applications,　2:879-884
Grignard reagents, homocoupling, nitroxide-mediated,　2:1105
ground-state oxygen (O(3P)), O2 photolysis in stratosphere,　1:506
group additivity (GA), enthalpies of formation estimation,　1:84,88
group transfer processes, radical chain reactions,　1:65-66,76-78
GSH see glutathione
g-tensor, anisotropic hyperfine interactions, DNA radicals,　3:1377-1378
guanacastepenes, synthesis, electrochemical transformations,　2:1183
guanidinodihydantoin (Gh), 8-oxoG oxidation,　3:1307,1309-1310,1311,1312
guanine (G)
DNA hole transfer,　3:1401,1402,1403-1407
hydroxyl radical reactions,　3:1292
one-electron oxidation,　3:1293-1300
aromatic radical cations,　3:1295-1297
base-sequence effects,　3:1294
carbonate radicals,　3:1294-1295
end products,　3:1300-1311
oxidant charge effects,　3:1297-1298
solvent exposure,　3:1297-1298
thermodynamics,　3:1293-1294
guanine (G) (continued)
one-electron oxidized G:C, intra-base pair proton transfer,　3:1385-1386
oxidation
5',8-cyclonucleosides,　3:1338,1340
DNA charge transfer,　3:1398
hydroxyl radicals,　3:1326-1328
one-electron transfer,　3:1331-1333
8-oxo-7,8-dihydro derivative,　3:1333-1334
singlet oxygen,　3:1320-1321
oxidative lesions, biological implications,　3:1311-1312
8-oxo-7,8-dihydroguanine lesions, biological implications,　3:1311-1312
8-oxo-7,8-dihydroguanine radical cation
nucleophilic additions,　3:1309
one-electron oxidation,　3:1308-1311
protonation states of one-electron oxidized guanine monomers,　3:1384-1385
radical cation, DNA hole hopping,　3:1403-1407
guanine radicals
cation/neutral forms, one-electron oxidation,　3:1300-1302
nucleophilic addition reactions,　3:1302-1305
one-electron oxidation,　3:1300-1311
radical reactions,　3:1305-1308
guanosyl radicals, electron transfer from amino acids, non-enzymatic DNA repair, time resolved chemically induced dynamic nuclear polarization studies,　1:196-197
guest inclusion, supramolecular systems,　4:1987,1988
guest spin probes, supramolecular systems,　4:1987
halide-mediated reactions, electrochemically initiated,　2:1203
halides
reductions
organoboranes,　2:602-603
samarium diiodide,　2:852-853
SRN1 reactions,　1:333,348-354,360-361
2-haloacrylate, ketyl radicals,　3:1533-1534
haloalkanes, C-halogen bond, photoinduced homolytic α-cleavage,　1:275-278
haloalkenes
carbon-halogen bonds, photoinduced homolytic α-cleavage,　1:278
cyclopropanations, electrochemically initiated,　2:1209
α-haloamides, cyclizations, tin hydride-mediated,　2:545
N-haloamines, pyrrolidine synthesis, hydrogen atom migration in acidic media,　1:129-131
haloarenes, carbon-halogen bonds, photoinduced homolytic α-cleavage,　1:278
α-halo carbonyl compounds, allylations, zirconium-catalyzed,　2:1015-1016
haloesters, cascade reactions, allylsilyloximes,　2:741-742
halogen anions, room-temperature ionic liquids,　1:434,438-439
halogenated hydrocarbons, radiolysis,　1:399,415-417
halogenations
B-alkylcatecholboranes,　2:613-616
chain reactions,　1:74-75
flow microreactor experiments,　2:1250-1253
fullerenes,　4:2185-2186
halogen atom transfers
agents, atom transfer radical addition,　4:1853
intramolecular homolytic substitutions,　2:630
Lewis acid-mediated, stereoselective reactions,　2:670-672
reactions,　2:943-963
halogen bonding, effects on free radicals,　1:232-233
halogen impurities, monolayer generation on silicon surfaces,　4:2088-2089
halogen radicals
atmospheric
F/Cl/Bra comparisons,　1:510-511,516-519
organic compound reactions,　1:516-517
ozone destruction,　1:508-509,510-511,512-513,517-518
stratosphere,　1:507-509,510-511,512-513
troposphere,　1:516-519
history,　1:16-19
ionization, room-temperature ionic liquids,　1:438-439
6-halo-l-hexenes
reductive radical cyclizations, iron-catalyzed,　2:1012
tandem radical cyclization/cross-coupling arylations, cobalt-catalyzed,　2:1008-1009
Hantzsch 1,4-dihydropyridines, photochemical aromatizations, nitroxide-mediated,　2:1105-1106
harmonic oscillators, electron transfer,　3:1477
HAT see hydrogen atom transfer
HBA see hydrogen-bond accepting
HDL see high density lipoprotein
head-to-head monomer addition, industrial radical polymerization,　4:1712-1713
head-to-tail (HT) regioregularity, polythiophenes, polymer-based field-effect transistors,　4:2061-2062
heat, see also thermolysis
heat of polymerization, industrial processes,　4:1719-1720
HEBA see 4-hydroxyethoxybenzoic acid
α-helical peptides, electron transfer,　3:1487-1488,1492,1495-1496
helicene compounds, synthesis, diiodide double arylations,　2:1064
heme-oxygenases (HOs), antioxidant action,　3:1626-1627
heme proteins, reactive oxygen species generation,　3:1264-1265,1266
hemicolfigation (radical reactions with nonradicals), ionized ionic liquids,　1:437
6-hepten-l-one radical anion, cyclizations,　1:320-322
6-heptenyl radicals, cyclizations, carbapyranose synthesis,　2:1154
Hess's Law, thermochemistry,　1:81-82
HETE see hydroxyeicosatetraenoic acid
heteroaromatic compounds, synthesis, xanthates,　2:978-981
heteroatom-centered radicals
acceptors, azides,　2:1023-1031
electron paramagnetic resonance,　1:160:165
generation, tin hydride-mediated,　2:554-556
history,　1:13-19
trialkylborane reactivity,　2:602
α-heteroatoms, carboxylic acids, electrolysis effects,　2:1200
α-heteroatom-stabilized radicals, atom transfer radical additions,　2:957
α-heteroatom-substituted carbonyl group reductions, samarium diiodide,　2:860-862
α-heteroatom-substituted radicals, phenylseleno transfers,　2:957
heterocoupling, metal-dependent,　2:917-918
heterocumulenes, radical acceptors,　2:1048-1052
heterocycles
benzyl analog substrates, SRN1 reactions,　1:358-360
carbonyl-alkene coupling, samarium diiodide,　2:874-875
five-membered, synthesis, sulfanyl-isonitrile radical additions,　2:1045
nitrogen, synthesis, tris(trimethylsilyl)silane,　2:578
thiazyl radicals, conductive and magnetic materials,　4:2147-2161
N-heterocyclic carbenes, organoborane complexes,　2:620-621
heterogeneous chemistry, stratosphere, ozone depletion mechanisms,　1:511-513
heterogeneous kinetics, redox potential determination,　1:251-252
heterogeneous media, antioxidant synergism and cooperativity,　3:1668-1669
heterogeneous nucleation, emulsion polymerization,　4:1721
heterogeneous polymerizations
reversible addition fragmentation chain transfer,　4:1919,1920-1925
see also emulsion polymerization; microemulsion polymerization; mini emulsion polymerization; suspension polymerization
heterolytic bond cleavage, thermochemistry,　1:83
heterophosphinations, phosphorus-centered radicals,　2:792-794
heteropinacol coupling
N-t-butylsulfinyl imines, samarium diiodide,　2:869-870
diazonamide A synthesis,　2:868
natural product synthesis,　2:868
nitrones, samarium diiodide,　2:868-869
hexaarylethanes, history,　1:4-5
hexabutyltin, radical chain reactions, initiator,　1:66
hexamethylditin
photochemical cleavage
camptothecin synthesis,　2:1238-1239
C-glycoside synthesis,　2:1238-1239
hexamethylphosphoramide (HMPA), samarium diiodide reactions, synthetic applications,　2:850-900
hexaphenylethanes, history,　1:4
Δ-hexenyl radicals
cyclizations,　1:317-323
radical anions,　1:317,322-323
regioselectivity,　1:318
solvent effects,　1:319-320
stereo-/regiochemical trends,　1:322-323
stereoselectivity,　1:318-319
hexylsilanes, enantioselective reactions,　2:595-596
hfs see hyperfine splittings
high density lipoprotein (HDL), oxidation,　3:1577
high density lipoprotein (HDL)-cholesterol concentration, the metabolic syndrome,　3:1685
high-energy radiation
radical production,　1:395-397
see also ionizing radiation
high gas pressure carbonylations, carbon monoxide, alkyl halides,　2:1246-1248
high-level ab initio methods, radical enzymes, theoretical studies,　3:1548,1552
high molecular weight polymers, reversible addition fragmentation chain transfer agents,　4:1901-1902
high performance liquid chromatography with electrochemical detection (HPLC-EC), DNA oxidation products,　3:1325
high performance liquid chromatography-tandem mass spectrometry (HPLC-MS/MS), DNA oxidation products,　3:1320,1322,1340
high-spin molecules, history,　1:11
hirsutene, synthesis, iron(III) salt-mediated,　2:924
histidine
protonated, hydrogen bonded to TolSQ,　1:229-230
relay amino acids in electron transfer,　3:1481,1484
history,　1:1-35
aliphatic radicals,　1:6-9
controlled/living radical polymerization,　4:1725
delocalized radical discovery,　1:9-12
electron transfer processes,　1:19-21
heteroatom-centered radicals,　1:13-19
plastics industry,　4:1701-1702
pre1900　1:1-1:2
radical processes,　1:25-30
reactive oxygen species,　3:1260-1261
triarylmethyl radicals, 1:2-6,　21-25
triphenylmethyl radical discovery,　1:1-6
HMPA see hexamethylphosphoramide
5-HMU see 5-hydroxy-4-methyluracil
HOCl see hypochlorous acid
HODE see hydroxyoctadecadienoic acid
Hofer-Moest reactions,　2:1195-1196
Hofmann-Loffier-Freytag reactions
dihydrodeoxyepiallocemuine synthesis,　2:1234
hydrogen atom migration,　1:129-131
hole injection, DNA,　3:1399-1403
hole migration
DNA,　3:1399,1403
guanine lesions in DNA,　3:1298-1300
irradiated zeolites,　1:421
hole transfer
DNA,　3:1399-1413
applications,　3:1411-1413
hopping mechanism,　3:1403-1407
sugar radical formation,　3:1388-1390
tunneling mechanism,　3:1399-1403
unusual structures,　3:1407-1411
hollow polystyrene spheres, reversible addition fragmentation chain transfer polymerization,　4:1925
homocoupling
Grignard reagents, nitroxide-mediated,　2:1105
metal-dependent,　2:917-918
4-methylguaiacol,　2:1188-1189
homocysteine (Heys)
carbon-centered radical reactions,　3:1462,1463
cellular function,　3:1459-1460
ionization,　3:1460
structure,　3:1461
homogeneous kinetics, follow-up, redox potential determination,　1:252-253
homogeneous media, antioxidant synergism and cooperativity,　3:1667-1668
homogeneous nucleation, emulsion polymerization,　4:1721
homogeneous polymerization, reversible addition fragmentation chain transfer,　4:1919-1920
homogeneous redox catalysis, competitive q method,　1:253-255
homogenization, mini-/microemulsion polymerization,　4:1724
homolytic cleavage
radical initiation,　1:37-49
alkoxyamines, nitroxide-mediated polymerization,　4:1829-1831
chain reactions,　1:60,61,62
photochemical cleavage,　1:43-49
photo-induced,　1:275-287
radiolysis,　1:52
thermal decomposition,　1:37-42
homolytic α-cleavage
photoinduced
carbon-C bonds,　1:281-283
carbon-halogen bonds,　1:275-278
carbon-N bonds,　1:283
carbon-O bonds,　1:280-281
carbon-S bonds,　1:283
N-O bonds,　1:279-280
O-I bonds,　1:278-279
homolytic halogen translocations, geometry dependency,　2:630
homolytic substitutions
aromatic
carbon-centered radicals,　2:1059-1069,1074-1079
cyclohexadienyl radicals,　2:1067
iminyl radicals,　2:1067
intermolecular,　2:1074-1079
intramolecular,　2:1059-1074
radical aryl migrations,　2:1069-1074
reaction mechanisms,　2:1062
synthetic strategies,　2:1059-1080
tris(trimethylsilyl)silane-mediated,　2:586-587
see also arylations; Pschorr reactions
carbon-centered radicals, selenium-centered radicals,　2:806-807
cascade reactions
with cyclizations,　2:737-739
ortho-substituted benzoyl rings,　2:738-739
intramolecular,　2:629-654
aromatic,　2:1059-1074
at germanium,　2:650-653
at oxygen,　2:644-645
at selenium,　2:637-644
at silicon,　2:645-650
at sulfur,　2:635-637
at tellurium,　2:637-641
at tin,　2:650-653
chiral sulfoxides,　2:636
kinetics,　2:632-635
β-lactams,　2:640-641
leaving groups,　2:634-635
phosphorus-centered radical generation,　2:796
radical chain reactions,　1:61
selenium-centered radicals,　2:805-808
carbon-centered radicals,　2:806-807
synthetic strategies,　2:804
tandem radical reactions, at selenium,　2:641-644
homopolymers
atom transfer radical polymerization,　4:1869-1870
functionalization, radical thiol-X click chemistry,　4:2033
nitroxide-mediated polymerization,　4:1838-1839
hopping mechanisms, charge transfer,　3:1403-1407,1414-1416,1478-1481
Horsfiline, synthesis, phosphorus-centered radicals,　2:792-793
HOs see heme-oxygenases
HOSCN see hypothiocyanous acid
host-guest complexes
electron paramagnetic resonance,　1:233-237
macrocyclic hosts,　1:233,234
nitroxide radicals,　1:233-234
supramolecular radical chemistry,　1:233-237
host-guest interactions, supramolecular systems,　4:1987,1988,1995,1999-2000
host spin probes, supramolecular systems,　4:1987
HOx radicals
stratosphere,　1:507-509
troposphere,　1:514-516
CO/CH4 oxidation chain reaction,　1:519-522
interconversions,　1:514-515
ozone/isoprene reactions,　1:525
see also hydroxyl radicals
10 hour half-life temperature, thermolysis,　1:38,39
3-HP see 3-hydroxypropionate
HPETE see hydro(pero)xyeicosatetraenoic acid
HPLC-ED see high performance liquid chromatography with electrochemical detection
HPLC-MS/MS see high performance liquid chromatography-tandem mass spectrometry
HPODE see hydro(pero)xyoctadecadienoic acid
HT see head-to-tail
human studies, physiological lipid peroxidation products,　3:1590-1593
hyacinthacine A, total synthesis, sulfonyl radicals,　2:1029-1030
2-hydoxyacyl-CoA dehydratases, ketyl radicals,　3:1526-1529
2-hydoxybutyryl-CoA dehydratase, ketyl radicals,　3:1529-1530
hydrated electrons, radiation-induced radical reactions,　1:401,403,407-408
hydration effects, DNA radical properties,　3:1383-1384
hydrazine derivatives, thermolysis,　1:40
hydrazines, nitrogen-centered radical generation,　2:771
hydrazones, reductive coupling, ketones,　2:1211-1212
hydroazulenone, synthesis, alkoxy radical fragmentations,　2:734-735
hydroborations, rhodium-catalyzed, enantioselectivity control,　2:612
hydrocarbons
autoxidation inhibition, phenolic antioxidants,　3:1627-1661
azidations, azidoiodinanes,　2:1035-1036
cracking models,　1:480
enthalpies of formation,　1:88-91
GA based estimation,　1:88-89
standard values of precursors,　1:90
radiolysis,　1:417-418
hydrogel synthesis, thiol addition to unsaturated compounds,　4:2044-2045
hydrogenations, Co radicals,　4:2184-2185
1,4-hydrogen atom abstractions,　1:140,141,142
1,5-hydrogen atom abstractions
alkoxy radicals,　1:131-134
aryl radicals,　1:137
carboxyl radicals,　1:136
naphthalene-1,3-diyl,　1:142-143
protecting-radical-translocating groups,　1:137-139
sulfonamidyl/amidyl radicals,　1:131,132
vinyl radicals,　1:137
1,6-hydrogen atom abstractions
benzylideneacetal,　1:139
radical inversion of anomeric center,　1:140,141
hydrogen atom abstractions
alcohols, metal-catalyzed, nitroxide-mediated,　2:1119-1121
catechols, TEMPO-mediated,　2:1121-1122
coenzyme B12-dependent enzymes,　3:1509
2-deoxyribose, radical formation,　3:1345-1346
electron-poor nitroxides,　2:1122-1123
epoxide disproportionations,　2:989-990
free-radical-mediated lipid peroxidation,　3:1581,1583,1584
ketones, photoinduced radicals,　1:283-286
nitroxide-mediated, synthetic applications,　2:1119-1123
phenols, TEMPO-mediated,　2:1121-1122
photochemically activated radical initiators,　1:48-49
photoexcited ketones,　1:135
quinones, photoinduced radicals,　1:286-287
radical chain mediators,　1:64
radical stability,　1:463
substituent effects,　1:102-103
tris(silyl)-substituted silyl radical generation,　4:2122
tris(trimethylsilyl)silane,　2:561-562
hydrogen atom donors
photochemical radical-mediated metal nanostructure synthesis,　4:2203,2204
sustainable, epoxide reductive openings,　2:993
hydrogen atom migration,　1:129-143
coenzyme B12-dependent enzymes,　3:1548,1549
N-haloamines in acidic media, pyrrolidine synthesis,　1:129-131
Hofmann-Loffier-Freytag reactions,　1:129-131
radical rearrangements,　1:129-143
1,2-hydrogen atom shift, alkoxyalkyl radicals, ketyl radical generation,　1:134
1,5-hydrogen atom transfer
5-endo-trig cyclizations,　2:703-704
germyl group translocation competition,　2:652
hydrogen atom transfer (HAT),　1:323-330
alkoxy radicals,　2:782-783
amino acids, 3:1459,　1472
carbon-nitrogen bond formation, carbohydrate synthesis,　2:1160-1162
carbon-oxygen bond formation, carbohydrate synthesis,　2:1162-1164
chain reactions,　2:619-620
classic mode,　1:323
deprotonation comparison,　1:329-330
electron transfer followed by proton transfer,　1:323-324
fullerene additions,　4:2184-2185
β-glycoside synthesis,　2:1157-1158
hydrogen bonding role in mode determination,　1:325-326
C-ketoside synthesis,　2:1144-1145
kinetics,　1:100-102
radical clocks,　1:119-121
Lewis acid-mediated, stereoselective reactions,　2:668-670
mechanisms,　1:323-330
memory of chirality,　2:667-668
modes,　1:323-326
nitroxide-mediated polymerization,　4:1833-1834
phenolic antioxidants,　3:1651-1653
proton-coupled electron transfer,　1:325
radical stabilization energy,　1:449-450,451-452,453,463-464
sequential proton loss electron transfer,　1:324-325
substituent effects,　1:102-103
sulfides, intramolecular homolytic substitution competition,　2:635
termination of nitroxide-mediated polymerization,　4:1818,1825,1826
thiols and selenols,　3:1460,1461-1464
tin hydride donors,　2:541-542
versus single electron transfer, tertiary amine oxidation,　1:310
see also proton transfer reactions
hydrogen-bond accepting (HBA) solvents, phenoxyl radicals,　1:230-231
hydrogen bonding
C-allylation stereocontrol,　2:657
effects on free radicals,　1:229-232
hydrogen atom transfer mode determination,　1:325-326
organocatalysis, enantioselective,　2:685-686
radical stability,　1:451
hydrogen gas, radiation-induced radicals in gaseous systems,　1:397-398
hydrogen peroxide
biological systems,　3:1271-1272
decomposition, antioxidants,　3:1625-1626
DNA reactions,　3:1319,1322,1325
enthalpies of formation,　1:93-95
flavoprotein oxidases,　3:1264,1265
inflammatory response,　3:1283,1285,1286-1288
NADPH oxidases,　3:1262-1264
reactivity relative to other two-electron oxidants,　3:1271
superoxide dismutase catalyzed formation,　3:1270
thiol protein reactions,　3:1274-1275
see also hydroperoxyl radicals
hydrogen quenching, diastereoselective, anomeric radicals,　2:1156-1157
hydrogen radicals, water radiolysis,　1:398,401,402,403,406-407
hydrogen-substituted bis(silyl) silicon-centered radicals,　4:2132
hydrogen terminated Si(100)/Si(111) surfaces
oxidation,　4:2083-2084
preparation,　4:2082-2083
self-assembled monolayer growth,　4:2084-2089
hydrolysis, esters, silicon surfaces, functionalized monolayers,　4:2104-2106
hydroperoxide see hydrogen peroxide
hydroperoxyeicosatetraenoic acid (HPETE), lipid peroxidation product,　3:1578,1579,1582-1583
hydroperoxyl radicals
cleavage, combustion,　1:478
enthalpies of formation,　1:93-95
OH radical interconversion, atmosphere,　1:507,508-509,514-515
hydroperoxyoctadecadienoic acid (HPODE), lipid peroxidation product,　3:1578,1579,1580,1581,1582,1584
hydrophobes, mini-emulsion polymerization,　4:1724
hydrophosphinations
phosphorus-centered radicals,　2:792-795
single electron oxidations, phosphorus-centered radicals,　2:795
hydroquinones, antioxidant action,　3:1657-1659
hydrosilylations
alkenes, tris(trimethylsilyl)silane,　2:566-568
alkynes, tris(trimethylsilyl)silane,　2:567-568,570-571
dienes, silylated cyclohexadienes,　2:594
4-hydroxyalkenals, lipid peroxidation, the metabolic syndrome,　3:1687-1694
hydroxyalkylations
C-H bonds,　2:619
radical, C-H bonds,　2:619
α-hydroxy-alkyl radicals, decatungstate catalyzed addition to fullerenes,　4:2174
hydroxy-assisted 1,2-hydrogen atom migration, in alcoholic or aqueous solutions,　1:134
5-hydroxycytosine
formation,　3:1325
secondary oxidation,　3:1334-1335
hydroxyeicosatetraenoic acid (HETE), lipid peroxidation product,　3:1578,1580,1583
β-hydroxyepoxides, deoxygenations, allylic alcohol synthesis,　2:989-990
4-hydroxyethoxybenzoic acid (HEBA), photochemical radical-mediated metal nanostructure synthesis,　4:2201,2205
hydroxy groups, installation, TEMPO carbon radical trapping,　2:1096-1097
hydroxy lactols, synthesis, 5-exo cyclizations,　2:997-998
hydroxylamines, antioxidant action,　3:1663-1664
hydroxyl radicals
adenine oxidation,　3:1328
cytosine oxidation,　3:1324-1326
DNA damage,　3:1372-1373
kinetics,　3:1290-1291
products,　3:1291-1292
DNA oxidation,　3:1319,1321-1328
Fenton reaction, history,　1:15
guanine oxidation,　3:1326-1328
hydrogen abstraction from DNA sugar moieties,　3:1345-1346
hydroperoxyl radical interconversion, atmosphere,　1:507,508-509,514-515
hydroxyl radicals (continued)
inflammatory response,　3:1283,1288-1289
methionine reactions,　3:1467-1471
5-methylcytosine oxidation,　3:1324-1326
oxidative damage in vivo,　3:1425,1428
reaction rate constants with biological molecules,　3:1425,1426,1428
stability,　1:449,450
thymine oxidation,　3:1321-1323
troposphere,　1:514-516
carbon monoxide oxidation,　1:515,519-520
interconversion reactions,　1:514-515
isoprene oxidation,　1:524
measurements/tracers,　1:515-516
methane oxidation,　1:515,519-522
water radiolysis
gas phase,　1:398-399
liquid phase,　1:401-403,404-406
hydroxymethylations
alkyl iodides, organoboranes,　2:621
fluorous tin hydride-mediated,　2:535
5-hydroxy-4-methyluracil (5-HMU), antioxidant action,　3:1670
hydroxyoctadecadienoic acid (HODE), lipid peroxidation product,　3:1578,1589,1591,1592
2-hydroxyphenoxyl radical, matrix isolation spectroscopy,　1:224-225
3-hydroxypropionate (3-HP), production, biotechnological applications of radical enzymes,　3:1539-1540
N-hydroxypyridine-2thione esters, thermolysis,　1:41
5-hydroxypyrimidines
formation,　3:1325
secondary oxidation,　3:1334-1335
hydroxysulfenations, 1,5-dienes, endoperoxide synthesis,　2:800-801
hydroxytetralones, synthesis, xanthate radical cyclizations,　2:978,980
5-hydroxyuracil
formation,　3:1325
secondary oxidation,　3:1334-1335
hyperbranched polymers
atom transfer radical polymerization,　4:1875
thiol addition to unsaturated compounds,　4:2041
hyperconjugative stabilization
aliphatic amine radical cations,　1:308
carbon-centered radicals,　1:454,457
hyperfine coupling constant (HFCC)
chemically induced dynamic nuclear polarization,　1:177,184-185
DNA radicals,　3:1375-1376
ESR spectroscopy,　3:1375-1376
theoretical calculation,　3:1380-1381
hyperfine splittings (hfs)
electron paramagnetic resonance,　1:148,151,152,153-156
carbon-centered radicals,　1:157
deduction,　1:152
nuclei two or more bonds from UPE,　1:153-155
origins,　1:153
quantum chemical computation,　1:155-156
hyperglycemia,　3:1679-1685
AGE-RAGE-induced free radicals,　3:1684-1685
glucose-derived free radicals,　3:1680-1684
lipid interactions,　3:1690,1693
hyperlipidemia, the metabolic syndrome,　3:1679,1680,1684,1685-1692
hypertriglyceridemia, the metabolic syndrome,　3:1685
hypervalent intermediates, intramolecular homolytic substitutions,　2:629-630
hypervalent iodine reagents, organic electron donor activations,　2:844
hypnophilin, synthesis, carbon—carbon bond sequential formation, samarium diiodide-mediated,　2:890
hypobromide, lipid oxidation,　3:1579
hypobromous acid (HOBr), protein oxidation,　3:1441-1443
hypochlorite, lipid oxidation,　3:1578,1579
hypochlorous acid (HOCI)
DNA damage,　3:1288
inflammatory response,　3:1283,1284,1285,1287-1288
protein oxidation,　3:1441-1443
hypohalides, lipid oxidation,　3:1579
hypohalous acids
in biological systems,　3:1272
generation, inflammatory response,　3:1284
hypophosphorus acid, tin-free Barton-McCombie deoxygenations,　2:969
hypothiocyanous acid (HOSCN), protein oxidation,　3:1441-1443
Ialibinone A, synthesis,　2:932
Ialibinone B, synthesis,　2:932
ICAR see initiators for continuous activator regeneration
IE see ionization energy
ILs see ionic liquids
imidazolidine-N-oxyl nitroxides, spin labels and spin probes,　4:1967
imidazoline-N-oxyl nitroxides, spin labels and spin probes,　4:1967
imidazolium cations, ionic liquids,　1:433-435
imidoyl radicals
conjugation effects,　2:1041
formation, isonitrile additions,　2:1037-1038
α-fragmentations, isonitrile formation,　2:1038
resonance stabilization,　2:1038-1039
imine derivatives, additions, nitrogen-centered radical formation,　2:780-781
imine equivalents, intramolecular Barbier additions, samarium diiodide-mediated,　2:884
imines
additions, trialkylboranes,　2:609
pinacol coupling, samarium diiodide, synthetic applications,　2:868-870
reductive coupling, samarium diiodide,　2:876
iminyl radicals
[4+1] annotations, isonitriles,　2:1043-1044
cyclizations, unusual bond formation,　2:717-718
generation,　2:770,776-777
α-azidoalkyl radicals,　2:1032
tin hydride-mediated,　2:554-556
xanthate Barton-McCombie deoxygenations,　2:971-972
homolytic aromatic substitutions,　2:1067
trapping, xanthate Barton-McCombie deoxygenations,　2:971-972
indirect antioxidants,　3:1623,1626-1627
indirect effects of ionizing radiation, molecules in solution,　1:396,402-403
indium-aminyl radicals,　2:769
indoles
additions, ketyl radicals, radical/anionic sequences,　2:893-894
ketone-bearing derivatives, reductive cyclizations,　2:1206-1207
malonylations, photocatalytic,　2:1077
photocatalytic C-H functionalizations, ruthenium-mediated,　2:1226-1227
synthesis
alkynyl isonitrile cyclizations,　2:1045-1046
Meerwein arylations,　2:1080
α-stannoimidoyl radicals, tin hydride-mediated,　2:552-556
xanthate radical cyclizations, 2:978,　980
indole tetramers, electrochemical generation,　2:1194-1195
indolizidine alkaloids, synthesis, Barton ester photochemical cleavage,　2:1236-1237
indolizidines, synthesis, arnidyl radical cascade reactions,　2:730-731
inducible nitric oxide synthase (iNOS), inflammation,　3:1284
1,n-inductions, stereoselective reactions,　2:656-657
1,2-inductions, acyclic, substrate controlled,　2:655-656
1,3-inductions, stereoselective reactions,　2:656-657
industrial radical polymerization,　4:1701-1736
controlled reversible-deactivation processes,　4:1725-1731
importance,　4:1703
mechanistic aspects,　4:1704-1719
processes,　4:1719-1725
process types,　4:1720-1724
reactor types,　4:1724-1725
inelastic collisions, charged particles interacting with matter,　1:395,396
inelastic scattering, neutral particles interacting with matter,　1:395,396
inert gases, matrix isolation,　1:207-228
inflammation
obese adipose tissue,　3:1691,1692
oxidative stress,　3:1283,1288,1302,1311
small reactive species
DNA damage,　3:1283,1290-1312
generation,　3:1283-1290
infrared (IR) spectroscopy, matrix isolation,　1:208,209-210,211
Ingold-Fisher effects see persistent radical effect
inhibited autoxidation
phenolic antioxidants,　3:1627-1629
kinetics,　3:1630-1635
inhibition rate constant, phenolic antioxidants,　3:1629
inhibitors, industrial radical polymerization,　4:1717-1718
iniferters, controlled reversible-deactivation radical polymerization,　4:1725
initialization (pre-equilibrium) stage, reversible addition fragmentation chain transfer polymerization,　4:1897,1898
initial monomer concentration; controlled/living radical polymerization,　4:1791-1792
initiation of radicals see radical initiation; radical initiators
initiation stage
polymerization,　4:1737
atom transfer radical polymerization,　4:1860-1861
decomposition rate coefficients,　4:1756-1757
industrial radical polymerization, 4:1706,　1711-1712
initiator efficiency,　4:1739,1743,1755,1757-1761
kinetics,　4:1739,1755-1762
nitroxide-mediated polymerization,　4:1818,1819,1820-1822
photoinitiation,　4:1711-1712,1761-1762
reversible addition fragmentation chain transfer,　4:1897
thermal autoinitiation,　4:1706
radical chain reactions,　1:59,60,62,63,108,110
SRN1 reactions,　1:334
initiation-termination balance, radical polymerization,　4:1785,1786,1787
initiator efficiency, polymerization kinetics,　4:1739,1743,1755,1757-1761
initiators
polymerization
atom transfer radical polymerization,　4:1856
industrial processes,　4:1706-1712
radical chain reactions, 1:62,　63
initiators for continuous activator regeneration (ICAR)
atom transfer radical addition/cyclization,　4:1879-1880
atom transfer radical polymerization,　4:1863
chain end functionality,　4:1794-1797
industrial processes,　4:1729-1730
injection mechanisms, DNA charge transfer,　3:1399-1403,1416-1421
inks, UV-curing, industrial radical polymerization,　4:1711
inner-sphere electron transfer (ISET), atom transfer radical polymerization,　4:1803,1869
inorganic anions, room-temperature ionic liquids,　1:438-440
inorganic azides, as radical acceptors,　2:1034-1036
inorganic bases-organic group anions, room-temperature ionic liquids,　1:440
inorganic material-polymer hybrids, atom transfer radical polymerization,　4:1876-1877,1879
inorganic salts, SRN1 reaction initiation,　1:335
iNOS see inducible nitric oxide synthase
insaturations, selenium-centered radical additions,　2:808-809
in situ nitroxide-mediated polymerization, industrial processes,　4:1727
in situ stabilization, metal nanoparticles,　4:2206
instability scales, radicals,　1:98-99
instantaneous copolymer composition, polymerization kinetics,　4:1749-1750
instantaneous dispersity, polymerization kinetics,　4:1747-1748
instantaneous molar mass distributions, polymerization kinetics,　4:1743-1748
instantaneous number-average degree of polymerization,　4:1746-1747
insulin, type-2 diabetes,　3:1680
insulin receptor substrate proteins (IRSs),　3:1680
integrated rate laws, polymerization,　4:1741-1742
intercalation, electron donors/acceptors, DNA hole tunneling study,　3:1399-1401
interchain transfer constant reversible addition fragmentation chain transfer polymerization,　4:1900,1901
intermediate radicals, reversible addition fragmentation chain transfer polymerization,　4:1897
intermolecular additions, alkenes, epoxide radicals,　2:993-995
intermolecular aldol-type reactions, samarium diiodide-mediated,　2:887-888
intermolecular arylations, β-dicarbonyl compounds,　2:910
intermolecular α-arylations, SOMO catalysis, enantioselective,　2:680-681
intermolecular Barbier reactions, samarium diiodide-mediated, synthetic applications,　2:881-882
intermolecular carbon-carbon bond formation
branched-chain sugar synthesis,　2:1142-1143
carbohydrate synthesis,　2:1131-1143
C-disaccharide synthesis,　2:1139-1141
C-glycoside synthesis,　2:1132-1139
C-ketoside synthesis,　2:1141-1142
intermolecular carbonyl-alkene coupling, samarium diiodide,　2:871-872
intermolecular chain radical processes, synthetic strategies,　2:739-746
intermolecular electron transfer, time resolved chemically induced dynamic nuclear polarization studies,　1:194-197
intermolecular Grignard reactions, samarium diiodide-mediated, synthetic applications,　2:881-882
intermolecular homolytic aromatic substitutions, synthetic strategies,　2:1074-1079
intermolecular pinacol coupling, samarium diiodide,　2:865-866
intermolecular radical additions to multiple bonds, chain reactions,　1:69-71
intermolecular reactions, tris(trimethylsilyOsilane-mediated,　2:583-587
intermolecular Reformatsky reactions, samarium diiodide-mediated, synthetic applications,　2:885-886
intermolecular samariations, C-disaccharide synthesis,　2:1139-1141
internal homolytic substitutions, tris(trimethylsilyl)silane,　2:582
internal motions, electron paramagnetic resonance,　1:159-160
interstellar chemistry (astrochemistry),　1:481-482,496-497
interstrand pyrimidine-purine cross-links, DNA oxidation,　3:1338
intra-base pair proton transfer in one-electron oxidized G:C, DNA radicals,　3:1385-1386
intra-inter-intra domino processes, oxygen-centered radicals,　2:790-791
intramolecular addition, Δ-5-hexenyl radicals, 5-exo-trig versus 6-endo-trig pathway,　1:317,318
intramolecular aldol-type reactions, samarium diiodide-mediated, synthetic applications,　2:888
intramolecular anodic coupling, electron-rich double bonds, nucleophiles,　2:1176
intramolecular α-arylations, SOMO catalysis, enantioselective,　2:680-681
intramolecular aryl migrations, tin to carbon,　2:948
intramolecular Barbier reactions, samarium diiodide-mediated,　2:882-884
intramolecular carbon-carbon bond formation
branched-chain sugar synthesis,　2:1146-1149
carbohydrate synthesis,　2:1143-1155
C-glycoside synthesis,　2:1143-1144
C-ketoside synthesis,　2:1144-1145
intramolecular carbonyl-alkene coupling
chelation control, samarium diiodide,　2:873-874
samarium diiodide, synthetic applications,　2:872-876
intramolecular chain radical processes, synthetic strategies,　2:729-746
intramolecular coupling
anodic, nucleophiles,　2:1176
carbonyl-alkene, samarium diiodide,　2:873-874
electrochemically initiated,　2:1193
methoxylated diphenylalkanes,　2:1193
pinacol, samarium diiodide,　2:866-868
intramolecular cyclizations
electrochemically initiated,　2:1176
C-glycoside synthesis,　2:1143-1144
Δ-5-hexenyl radicals,　1:317-318
methoxylated phenanthrene synthesis,　2:1192-1193
intramolecular electron transfer, TR-CIDNP,　1:194-197
intramolecular Grignard reactions, samarium diiodide-mediated,　2:882-884
intramolecular homolytic substitutions,　2:629-654
aromatic,　2:1059-1074
at germanium,　2:650-653
at oxygen,　2:644-645
at selenium,　2:637-644
at silicon,　2:645-650
at sulfur,　2:635-637
at tellurium,　2:637-641
at tin,　2:650-653
chalcogens,　2:630-631
chiral sulfoxides,　2:636
1,n-germyl translocations,　2:651
halogens,　2:630
kinetics,　2:632-635
β-lactams,　2:640-641
leaving groups,　2:634-635
radical chain reactions,　1:61
1,n-silyl translocations,　2:650
1,4-stannyl migrations,　2:649
1,n-stannyl translocations,　2:651
sulfides, hydrogen transfer competition,　2:635
tandem,　2:641-644
intramolecular hydrogen atom abstractions,　1:141-142
intramolecular hydrogen transfer reactions, termination of nitroxide-mediated polymerization, 4:1818,　1825
intramolecular long range electron transfer, radiation-induced radicals in aqueous solutions,　1:409
intramolecular pinacol coupling, samarium diiodide, synthetic applications,　2:866-868
intramolecular reactions, silane-mediated,　2:574-582
intramolecular Reformatsky reactions, samarium diiodide-mediated,　2:886-887
intramolecular SRN1 reactions, ring closure,　1:344-347
intrastrand G-T cross-links, hydroxyl radicals,　3:1292-1293
intrastrand pyrimidine-purine cross-links, DNA oxidation,　3:1335-1336
inverse emulsion polymerization,　4:1722
inverted spin trapping,　4:2003,2005
in vivo electron transfer,　3:1475,1476-1477
in vivo oxidants
formation,　3:1425,1426
lipid peroxidation,　3:1577-1578
protein reactions,　3:1426-1450
iodanes, photoinduced homolytic α-cleavage, O-I bonds,　1:278-279
iodides, conversion to lactames, homolytic aromatic substitutions,　2:1062
iodine, see also organoiodine
iodine atom transfer,　2:945-952
ATRA,　2:945-947
ATRC,　2:947-952
enantioselective additions,　2:952
intramolecular homolytic substitutions,　2:630
organoboranes,　2:604-605
iodine azide, azidations, carbon compounds,　2:1034-1035
iodine-mediated radical living polymerization (IRP),　4:1932-1944,1949,1953-1956
iodine radicals, IOx, atmospheric,　1:510-511,518-519
1-iodoadamantane, reductions, fluorous tin hydride-mediated,　2:536
iodoaldehydes, chain transfers, triethylborane,　2:617
iodoalkanes, atom transfer carbonylations, flow microreactor experiments,　2:1254
α-iodo-fi-alkoxyesters, reductions, Lewis acid-mediated,　2:662-663
iodobenzene, dearomatizations, meso-tetraol synthesis,　2:810-811
2-iodobenzyl protected aliphatic amines, iron-catalyzed arylations,　2:1013
α-iodo causes, photoinduced mesolytic cleavage,　1:296
α-iodoesters
additions, allylboron derivatives,　2:622
atom transfer radical cyclizations,　2:949
radical phenylations, organoboranes,　2:607
2β-iodo glucopyranosides, tandem cyclizations, branched-chain sugar synthesis,　2:1147-1148
6-iodo-l-hexene derivatives, cyclizations, palladium-catalyzed,　2:1005-1006
iodomethylaziridine derivatives, annulations, pyrrolidine derivative synthesis,　2:604
5-iodo-1-pentene derivatives, carbonylative cyclizations, palladium-catalyzed,　2:1005
2-iodoxybenzoic acid (IBX), anilinamide oxidations,　2:779
ionic conjugate additions, polar crossover reactions,　2:657,659
ionic liquids (ILs)
aromatic anions,　1:442-441
cations,　1:444-446
constituents,　1:433,434
ionization of ions,　1:436-438
nonaromatic anions,　1:438-442
radiation-induced radical reactions,　1:418-420
room-temperature,　1:433-448
ionic polymerization, radical polymerization comparison,　4:1785
ionic radicals
DAN, ionizing radiation formation,　3:1371-1372
fullerene reactions,　4:2186-2192
versus neutral radicals,　1:301-332
ionization..., see also photoionization
ionization cross-sections, photoionization of gas phase radicals,　1:488,491
ionization energy (IE), photoionization of gas phase radicals,　1:488-490
ionization of ions, room-temperature ionic liquids,　1:436-438
ionization potentials
definition,　1:249
redox potential determination,　1:258
tris(silyl)-substituted silyl radicals,　4:2130
ionizing radiation
DNA radical formation,　3:1371-1374
direct effects,　3:1371-1372
direct-type effects,　3:1372
indirect effects,　3:1372
quasi-direct effects,　3:1371-1372
radical reactions,　1:395-432
aqueous solutions,　1:400-410
gas phase,　1:397-400
ionic liquids,　1:418-420
liquid phase,　1:400-420
organic solvents,　1:410-418
radiolysis,　1:395-397
solid phase,　1:420-423
zeolites,　1:421-423
reactive oxygen species generation in biological systems,　3:1265
solvent/solute effects,　1:396
spurs of dense ionization,　1:395-396,401
types/interactions with matter,　1:395,396
IOx radicals
atmospheric,　1:510-511,518-519
stratosphere,　1:510-511
troposphere,　1:518-519
ipso-cyclizations, spirocyclic azidocyclohexadienyl radical formation,　2:1032-1033
ipso substitutions, intermolecular, arylations,　2:1079
Irgacure-907(I-907), photochemical radical-mediated metal nanostructure synthesis,　4:2202,2203
Irgacure-2959 (I-2959), photochemical radical-mediated metal nanostructure synthesis,　4:2201-2202
iron
cellular, reactive oxygen species,　3:1273
chelating agents, preventive antioxidants,　3:1624
ferric perchlorate (Fe(ClO4)3)-mediated radical reactions, fullerenes, 4:2174,　2176-2177
ferromagnetism,　4:2154-2156
reagents, organic electron donor activations,　2:837-840
iron-catalyzed reactions
aerobic oxidations, alcohols, nitroxide-mediated,　2:1119-1121
arylations
benzene,　2:1013-1014
2-iodobenzyl protected aliphatic amines,　2:1013
cross-coupling, alkyl halides,　2:1012-1013
oxidative additions,　2:1012-1014
reductive radical cyclizations, 6-halo-1-hexene,　2:1012
iron complexes
atom transfer radical polymerization,　4:1858-1860
catalyzing reaction cascades,　2:752-754
Fenton chemistry,　3:1272-1273
iron radical complexes, history,　1:4-5
iron(III) salt-mediated synthesis
addition-cyclizations, aryl rings,　2:910-913
α-arylations,　2:924-927
coupling, enolates,　2:924
cyclizations, malonates,　2:922-923
hirsutene synthesis,　2:924
ring opening,　2:932-935
iron-sulfur clusters, SAM-dependent enzymes,　3:1501,1503,1514
iron-sulfur world, radical enzymes,　3:1540
IRP see iodine-mediated radical living polymerization
irreversible S-adenosylmethionine radical enzymes,　3:1517-1525
IRSs see insulin receptor substrate proteins
ISET see inner-sphere electron transfer
Isobutyryl-CoA mutate, mechanism,　3:1508,1512
isocyanide
C-S bond cleavage,　2:803
thioselenations,　2:807
isodasycarpidone, synthesis, selenoester cyclizations,　2:806
isodesmic equations, radical stability,　1:452,453,458,463,469
isodesmic reactions
definition,　1:450
hydrogen transfer,　1:450,452
isolated radicals
gas phase,　1:477-502
generation,　1:482-487
study methods,　1:482
isomerization enthalpies, bond dissociation enthalpy measurement,　1:83
isomerizations
Barton-McCombie deoxygenations,　2:971-972
1-benzyloxy-9,10-anthraquinones,　2:698
isonitriles
additions
heteroatom centered radicals,　2:1038
imidoyl radical fates,　2:1037-1038
telluro derivatives,　2:1046
alkynyl, cyclizations, indole synthesis,　2:1045-1046
[4+1] annulations
iminyl radicals,　2:1043-1044
vinyl radicals,　2:1043
aromatizations, cyclohexadienyl radicals,　2:1044
carbotellurations,　2:959
13C-labelling, carboxylic acids,　2:1042-1043
cleavage, tin-hydride mediated,　2:548
conversion, nitriles,　2:1037
cyanations,　2:1042
deaminations,　2:1042
double radical chalcogenations,　2:1047-1048
electron paramagnetic resonance,　2:1038-1041
formation, imidoyl radical α-fragmentations,　2:1038
functionalizations,　2:1042
isonitriles (continued)
kinetics,　2:1038-1041
polar effects, electrophilic attack,　2:1040
as radical acceptors,　2:1036-1048
radical adducts, kinetics,　2:1038-1041
structural resonance,　2:1036
synthetic applications,　2:1041-1048
isoprene, atmospheric reactions,　1:517,523-525
isoprenoid, biosynthesis, radical enzymes,　3:1536-1537
n-isopropyl radicals, matrix isolation spectroscopy,　1:213-214
isoprostanes (IsoPs)
lipid peroxidation products,　3:1585-1586
human physiological levels,　3:1591
metabolites, nitroxide radical trapping,　2:1100
isoquinalones, synthesis, electrochemically initiated,　2:1193
isothiocyanates (ITCs)
additions, alkyl radicals,　2:1049-1050
annulations, aryl radicals,　2:1050-1051
antioxidant action,　3:1627
as radical acceptors,　2:1049-1051
isotropic g-factors, electron paramagnetic resonance,　1:148,150-151,156,162,163
isotropic hyperfine interactions, DNA radicals,　3:1375
isotropic hyperfine splittings, electron paramagnetic resonance,　1:148,153-156
isotropic spectra, electron paramagnetic resonance,　1:147-170
ITCs see isothiocyanates
IUPAC (International Union of Pure and Applied Chemistry), atmospheric radical chemistry,　1:503
Julia-Lythgoe olefinations, sulfone reductions, samarium diiodide,　2:864-865
(+)-juvabione, synthesis, Norrish reactions,　2:1229
J-values, photochemical reaction rates, atmosphere,　1:505-506
Karplus type relationships, hyperfine splittings, EPR,　1:154,158
Keck allylations, C-glycoside synthesis,　2:1132-1133
Kekule structures, aromatic radicals,　1:11
ketene dithioacetals, oxidations, electrochemically initiated,　2:1177-1180
ketenes
bisadditions, nitroxides,　2:1104
as radical acceptors,　2:1051-1052
ketene silyl acetals, fullerene additions,　4:2189-2190
ketenimines, as radical acceptors,　2:1051-1052
o-ketenimino-substituted benzylic radicals, cyclizations,　2:1052
α-ketenyl alkyl radicals, generation/cyclizations,　2:1052
ketimines, cyclizations, vinyl radicals,　2:720-721
4'-keto abasic sites see C4'-oxidized abasic site
α-keto acids, synthesis, amino acid oxidations,　2:1123
α-keto alkoxyamines, synthesis, TEMPO carbon radical trapping,　2:1097
β-ketoesters
additions, alkenes,　2:902
cyclizations, metal-dependent,　2:919-921
γ-ketoesters, synthesis, intramolecular carbon-carbon bond formation,　2:1145
ketones
additions, aldehydes,　2:906-907
α-alkylations, N-siloxyenamine,　2:606
asymmetric reductions, samarium diiodide, synthetic applications,　2:859
atom transfer radical cyclizations,　2:949
carbon-C bonds, photoinduced homolytic α-cleavage,　1:281-283
cyclizations, metal-dependent,　2:919
3-exo cyclizations, epoxides,　2:995-997
4-exo cyclizations, epoxides,　2:995-997
fragmentations, samarium diiodide, synthetic applications,　2:859-860
fullerene reactions,　4:2182
glycosyl pyridyl sulfone reductions, 1,2-trans-C-glycosides synthesis,　2:1137
H-abstraction, photoinduced radicals,　1:283-286
lipid peroxidation products,　3:1585
perfluoroalkylations, germylenol ethers,　2:606
photoexcitation, hydrogen abstraction,　1:134,135
radical anions, cyclopropylcarbiny1→homoallyl-type rearrangements,　1:302-307
reductions, samarium diiodide,　2:857-860
reductive coupling,　2:1211-1212
reductive cyclizations,　2:1206-1208
ketorolac, synthesis, metal-dependent,　2:927
C-ketosides
intermolecular carbon-carbon bond formation,　2:1141-1142
intramolecular carbon-carbon bond formation,　2:1144-1145
ketyl radical anions
cyclopropylcarbinyl-Aomoallyl-type rearrangements, ring opening,　1:302-307
protonation effects, synthetic applications,　2:855-856
ketyl radicals
acyl-CoA dehydrogenases,　3:1530-1531
additions, indoles, radical/anionic sequences,　2:893-894
DNA photolase,　3:1531-1533
electron bifurcation,　3:1531,1532
2-hydoxyacyl-CoA dehydratases,　3:1526-1529
2-hydoxybutyryl-CoA dehydratase,　3:1529-1530
photochemical synthesis of metal nanostructures,　4:2197,2199,2200,2201,2202,2205
radical enzymes,　3:1525-1534
Kharasch-type reactions
additions,　4:1851,1852
radical chain reaction,　1:62-63,66,75-76
transition metal-catalyzed,　2:1003-1004
see also atom transfer radical addition
KIE see kinetic isotope effects
kinetic equations
nitroxide-mediated polymerization,　4:1819
persistent radical effect,　4:1816,1819
kinetic isotope effects (KIE), hydrogen atom transfer,　1:323-324
kinetic parameters, industrial radical polymerization,　4:1705,1706
kinetic resolutions, oxoammonium salt-mediated, synthetic applications,　2:1117-1118
kinetics
antioxidant activity measurement, phenolic antioxidants,　3:1629-1641
atmospheric radical chemistry,　1:503
atom transfer radical polymerization,　4:1857,1861,1863-1864
competition kinetics,　1:107-108,110-114
3-exo-trig cyclizations,　2:694-698
4-exo-trig cyclizations,　2:698-702
5-endo-dig cyclizations,　2:706-709
cyclopropane ring opening,　1:311-312,313-314
cyclopropylcarbinyl-ehomoallyl-type rearrangements,　1:303-304
EPR spectroscopy,　1:161,165-169
radical decay curves/concentration measurements,　1:165-167
steady-state measurements,　1:167-169
Δ-5-hexenyl radical cyclizations,　1:317
hydrogen atom transfer,　1:100-102,323
isonitrile radical adducts,　2:1038-1041
modelling, controlled/living radical polymerization,　4:1788-1797,1816,1820
organoheteroatom-mediated radical living polymerization,　4:1953-1956
radical cation deprotonations,　1:327-329
radical chain reactions,　1:109-110
radical clocks,　1:107-124
radical polymerization,　4:1737-1784
reactive oxygen species,　3:1267,1268,1271,1273-1275
reversible addition fragmentation chain transfer,　4:1898-1899
ring-closures,　2:632-635
stabilization of silyl radicals, steric effects,　4:2120-2121
thermodynamic correlation, phenolic antioxidants,　3:1646-1650
versus thermodynamics, activation energy,　3:1267,1268,1271
kinetic tables, second-order rate constants,　1:118-122
Knoevenagel adducts, paired electrolysis, cyclobutane synthesis,　2:1184
Kolbe electrolysis,　2:1195-1202
cyclizations,　2:1198-1199
5-exo-trig cyclizations,　2:1199
electron-withdrawing groups,　2:1196,1198-1199
P-chiral bisphosphino ligand synthesis,　2:1201-1202
primary aliphatic carboxylic acid dimerizations,　2:1199-1200
α-silyl acetic acid dimerizations,　2:1200-1201
kp see propagation rate constant
kl see termination rate constant
lactames, iodide conversions,　2:1062
lactams
synthesis
acyl radical cyclizations,　2:721-722
transition metal-catalyzed,　2:1004
β-lactanis
Baeyer-Villager reactions, peptide synthesis,　2:1120
intramolecular homolytic substitutions,　2:640-641
synthesis, fluorous tin hydride-mediated,　2:535
γ-lactams, synthesis, carbamoylmethyl radical 5-endo-trig cyclizations,　2:703-704
lactols, hydroxy, synthesis 5-exo cyclizations,　2:997-998
lactones
Barbier additions, samarium dliodide-mediated,　2:883-884
radical/radical cyclizations, samarium diiodide-mediated,　2:890-891
reductions, samarium diiodide,　2:860
ring contraction/expansions, acyloxy shift,　1:128,129
synthesis
iodine transfers,　2:604
transition metal-catalyzed,　2:1004
γ-lactones, synthesis,　2:902,904-906
large rings, synthesis, unusual cyclizations,　2:711-715
laser flash electron photoinjection, redox potential determination,　1:255-256
laser flash photolysis (LFP)
antioxidant kinetic measurements,　3:1637-1639,1640
characterization of radicals,　1:297-298
DNA excess electron transfer study,　3:1421
DNA hole transfer study,　3:1404,1406
kinetics, electron paramagnetic resonance relationship,　1:161,167
radical cation generation, electron transfer in peptides,　3:1480,1481,1482
rate constant determination, radical clock calibration,　1:107,112,113,117,118
laser induced fluorescence (LIP) spectroscopy, combustion engine research,　1:479
latex particles, emulsion polymerization,　4:1721-1722
lauroyl peroxide, tin-free Barton-McCombie deoxygenations,　2:969
LDL see low density lipoprotein
LDPE see low density polyethylene
leaving groups
intramolecular homolytic substitutions,　2:634-635
phenylselenium, carbon-centered radical generation,　2:805-806
phosphorus-centered radicals,　2:795-796
reversible addition fragmentation chain transfer agents,　4:1896,1897,1904
SRN1 reactions,　1:333,334,335
sulfur-centered radicals,　2:803-804
LEDs see light emitting diodes
LEEs see low-energy electrons
lepadiformine, total synthesis,　2:746
lepadin B, synthesis, xanthates,　2:977-978
lepidopterene, photocatalytic formation,　1:388,389
LET see linear energy transfer
Lewis acid-mediated reactions
atom transfer radical additions, bromines,　2:953
cyclizations
α-carbamoyl radicals,　2:951
α-ester radacals,　1:340
diastereoselective,　2:662-666
enantioselective reactions,　2:668-679
halogen atom transfers, stereoselective reactions,　2:670-672
hydrogen atom transfers, stereoselective reactions,　2:668-670
rearrangements, β-acyloxy alkyl radicals,　1:128
reductions, α-iodo-β-alkoxyesters,　2:662-663
Lewis structures of radicals, stability measurement,　1:452-453
LFP see laser flash photolysis
LIE see laser induced fluorescence
lifetime line broadening, electron paramagnetic resonance,　1:149
lifetimes, excited electronic states, gas phase radicals,　1:493
ligation protocols, block copolymers, reversible addition fragmentation chain transfer polymerization,　4:1908,1912-1916
light, see also photo…
light emitting diodes (LEDs)
metal nanoparticles, light-induced changes,　4:2208-2209
polymer-based,　4:2057
light harvesting, photocatalytic charge separation,　1:365-393
light-induced reactions see photoinduced…
light intensity effects, radical-mediated metal nanostructure synthesis,　4:2204
Li-ion see lithium-ion
linear chain polymers, atom transfer radical polymerization,　4:1873
linear energy transfer (LET), ionizing radiation particles,　1:395-396,397,401,421
linear segmented copolymers, atom transfer radical polymerization,　4:1871-1872
line shapes, electron paramagnetic resonance,　1:148-150
linoleic acid/lino/eates
enzymatic lipid peroxidation,　3:1579-1580
free-radical-mediated lipid peroxidation,　3:1581-1582
nonradical/nonenzymatic lipid peroxidation,　3:1579
lipid functionalization, radical axial additions,　4:2022
lipid hydroperoxides, lipid peroxidation products, human physiological levels,　3:1590
lipid hydroxides, hydroperoxides, lipid peroxidation products,　3:1584-1585
lipid isomerization,　3:1599-1622
bacteria,　3:1617-1619
factors affecting,　3:1615-1619
free radical mechanism,　3:1600-1609
individuating protein damage,　1:309-311
inhibition,　3:1616-1617
oxygen role,　3:1615-1616
thiyl radicals,　3:1601-1604
trans lipids in biological samples,　3:1612-1615
lipidomics, trans lipids in biological samples,　3:1612-1615,1619
lipid peroxidation (LPO),　3:1577-1594
β-carotene, pro-oxidant action,　3:1670,1671,1672
cholesterol,　3:1584-1588
diabetic complications,　3:1693-1694
dynamics,　3:1583-1584
enzymatic,　3:1578,1579-1580
free-radical-mediated,　3:1577,1578,1580-1588
inhibition
β-carotene,　3:1672
phenolic antioxidants,　3:1627-1661
in vivo effects,　3:1577-1578
lipid-oxidation product ratios,　3:1592-1593
low density lipoproteins,　3:1588-1589
mechanisms,　3:1578-1583
the metabolic syndrome,　3:1687-1690
nonradical/nonenzymatic,　3:1578,1579
obese adipose tissue,　3:1691-1692
products,　3:1584-1588
biological effects,　3:1593-1594
biological samples,　3:1583,1588-1589,1590-1593
cytotoxic/cytoprotective effects,　3:1578,1593-1594
oxidative stress markers in vitro,　3:1577-1578,1590-1593
parent lipid ratios,　3:1592-1593
physiological levels in humans,　3:1590-1593
reactions with biomolecules,　3:1588
signaling messengers,　3:1594
lipid peroxyl radicals, peroxidation chain reactions,　3:1581
lipophilic guanosines, self-assembly in the presence of alkali cations,　1:237,238
lipoproteins, apolipoprotein B-containing, the metabolic syndrome,　3:1685
liposomes
cis-trans isomerization,　3:1602,1609-1610,1613
oxidative damage,　3:1616
tandem protein-lipid damage,　3:1608
lipotoxicity, pancreatic β-cells,　3:1680
lipoxygenase (LOX), lipid peroxidation,　3:1578,1579-1580
liquid phase polymerization, viscosity, industrial radical polymerization,　4:1719
liquid phase radical chemistry, radiation-induced radicals,　1:400-420
lithium enolates, trifluoromethylations, organoboranes,　2:605
lithium-ion (Li-ion) batteries,　4:2163
living polymerization, radical versus ionic,　4:1785-1786
living radical polymerization (LRP)
organoheteroatom-mediated,　4:1931-1963
reversible addition fragmentation chain transfer,　4:1895-1929
use of terms,　4:1725
see also controlled/living radical polymerization; controlled reversible-deactivation radical polymerization
living systems see biological systems; in vivo…
lone-pair donation, stabilization of carbon-centered radicals,　1:454,457
long range electron transfer (LRET), radiation-induced radicals in aqueous solutions,　1:403,409
Lorentzian lineshapes, electron paramagnetic resonance,　1:149,150
low-band gap polymers, polymer-based solar cells,　4:2072-2075
low density lipoprotein (LDL)
oxidation,　3:1577,1583
biological samples,　3:1588-1589,1592
low density polyethylene (LOPE), chain transfer to polymer,　4:1779
low-energy electrons (LEEs)
DNA damage
ESR studies,　3:1390-1392
theoretical studies,　3:1392-1393
low molecular weight polymers, reversible addition fragmentation chain transfer agents,　4:1903
low temperature gas-phase studies, Cinetique de Reaction en Ecoulement Supersonique Uniforme,　1:482,496-497
low-temperature plasmas, radical chemistry,　1:480
LOX see lipoxygenase
LPO see lipid peroxidation
LRET see long range electron transfer
LRP see living radical polymerization
luotonin A, synthesis,　2:737,1067
lyconadin A, synthesis, 7-exo/6-exo cascade cyclizations,　2:732
lysine-2,3-aminomutase, SAM-dependent, mechanism,　3:1513-1514,1515-1516,1526
β-lysine-5,6-aminomutase,CoB12-dependent, mechanism,　3:1506,1508,1513-1514,1516,1526
MA see methyl acrylate
macrocycles, synthesis, radical thiol additions,　4:2025,2028,2030
macrocyclic hosts, host-guest complexes,　1:233,234
macro-cyclizations, phthalimide derivatives, photochemical electron transfer-induced,　2:1218-1219
macromolecular architecture see molecular architecture control
macromolecular bottle brush polymers, atom transfer radical polymerization,　4:1878-1879
macromolecular chemistry, radical thiol-X click chemistry,　4:2033-2045
macromolecular design via interchange of xanthates (MADIX)
radical polymerization,　4:1731,1895
see also reversible addition fragmentation chain transfer
macromolecular synthesis, living radicals, room-temperature ionic liquids,　1:434
macrophages, small reactive species generation,　3:1283,1284
macroradical termination, glass effect, polymerization kinetics,　4:1743
MADIX see macromolecular design via interchange of xanthates
magnetic activity of radicals, history,　1:11,12
magnetic bistability, thiazyl radicals,　4:2148-2151
magnetic materials, thiazyl radicals,　4:2147,2148-2151,2154-2156
magnetic ordering, thiazyl radicals,　4:2154-2156
magnetic resonance imaging (MRI)
spin probes, nitroxide contrast agents,　4:1972-1973
see also Overhauser-enhanced magnetic resonance imaging
magnetic resonance techniques
short-lived radicals/radical ions,　1:175-206
see also chemically induced dynamic electron polarization; chemically induced dynamic nuclear polarization
main-chain functional polymers, synthesis, radical thiol-X click chemistry,　4:2033,2035-2037
malonates
additions,　2:947
cerium(IV) ammonium nitrate-mediated to glycals,　2:1142
annulations,　2:947
cyclizations, metal-dependent,　2:921-924
malononitriles, additions/annulations,　2:947
malonylations, indoles, photocatalytic,　2:1077
malonyl radicals
allylations, chiral auxiliaries,　2:660,662
atom transfer radical cyclizations,　2:949
5-exo versus 6-endo cyclizations,　2:949
manganese(III) acetate (MAN)-mediated reactions,　2:901-941
addition-cyclizations
alkenes,　2:913
aryl rings,　2:911-913
additions,　2:913-917
aldehydes, ketones,　2:906-907
alkenes, β-dicarbonyl compounds,　2:907-918
β-dicarbonyl compounds, alkenes,　2:907-918
ketones, aldehydes,　2:906-907
cyclization—rearrangements, Ugi products,　2:912
cyclizations
aldehydes,　2:919
β-ketoesters,　2:919-921
ketones,　2:919
malonates,　2:921-924
dihydrofuran synthesis,　2:907-910
fullerenes,　4:2174-2178
intermolecular arylations, β-dicarbonyl compounds,　2:910
γ-lactone synthesis, acetic acid,　2:904-905
propellane synthesis,　2:909
ring opening,　2:932-935
manganese(III)-catalyzed reactions, pyridine synthesis,　2:785-786
manganese-catalyzed reactions
aldol-type,　2:1014
oxidative additions,　2:1014
manganese complex-catalyzed reactions
cascades,　2:749-752
5-exo/6-endo cyclizations,　2:749
manganese reagents, organic electron donor activations,　2:841-842
Marcus theory
electron transfer,　3:1475,1481,1489,1491,1492
DNA,　3:1401,1402,1403,1413,1422
mass spectrometry (MS)
gas phase radicals
bimolecular reactions,　1:497
generation,　1:486-487
photoionization,　1:487
unimolecular reactions,　1:494
matrix isolation spectroscopy,　1:207-228
alkyl radicals,　1:210-214
aryl radicals,　1:218-225
radical formation,　1:207-208
radical reactions,　1:210
spectroscopic method comparison,　1:208-209
unsaturated radicals,　1:214-218
MCR see methyl-coenzyme M reductase
mechanistic considerations, phenolic antioxidants,　3:1650-1657
mechanistic inhibitors, in SET enzymes, radical cations,　1:310-311
mechanistic probes, radical ions, cyclopropylcarbinyl→homoallyl rearrangements,　1:301
mediators
radical chain reactions,　1:63-65
reductive mediators,　1:66-73
Meerwein arylations, synthetic strategies,　2:1080-1082
melatonin, antioxidant action,　3:1625-1626
(±)-melinoline E, indole alkaloid synthesis,　2:785-786
membrane-bound proteins, electron transfer, energy conversion life processes,　3:1475,1476
membrane models
lipid isomerization,　3:1609-1610
see also liposomes
membranes
lipid peroxidation,　3:1577,1580,1583,1584,1586
permeability, reactive oxygen species,　3:1275-1276
phase-separated antioxidants,　3:1668-1669
properties of saturated/cis and trans fatty acids,　3:1617-1618
spin labels and spin probes,　4:1967,1968,1987
sulfur-containing amino acid residues in peptides/proteins, radical generation,　3:1606
memory of chirality,　2:667-668
menthol, oxidations, azabicyclic N-oxyl radicals,　2:1203
mepivacaine, one-step synthesis,　2:619
2-mercaptoethanol, lipid isomerization,　3:1604
mercury-silicon bond cleavage, tris(silyl)-substituted silyl radical generation,　4:2124
mercury-substituted silyl radicals, persistent and stable,　4:2140-2141
mesicarpine
synthesis
homolytic aromatic substitutions,　2:1066
xanthates,　2:979,981
9-mesityl-10-methylacridinium ion (Aer+-Mes)
C-C bond formation via charge separation,　1:386-389
donor-acceptor linked dyad, photocatalytic charge separation,　1:366-370
gold nanoclusters, 1:368,　369
photocatalytic bromination via charge separation,　1:383-386
photocatalytic oxygenation via electron transfer,　1:370-383
photoexcitation,　1:366-367,370
PMO immobilization,　1:369-370
mesityl-substituted bis(silyl) silicon-centered radicals, persistent and stable,　4:2132,2134
mesolytic cleavage
photoinduced,　1:291-297
carbon-C bonds,　1:293-294
carbon-halogen bonds,　1:294-296
carbon-H bonds,　1:291-292
carbon-Se bonds,　1:296
carbon-Si bonds,　1:292-293
N-S bonds,　1:297
O-Si bonds,　1:294
Se-Se/Si-Se bonds,　1:296-297
meso-tetraor, synthesis,　2:810-811
Met see methionine
the metabolic syndrome,　3:1679-1700
diabetic complications,　3:1692-1694
fatty acids,　3:1685-1690
hyperglycemia,　3:1679-1685
lipid peroxidation,　3:1687-1690,1691-1692
metal-carbon bonds, thermolysis,　1:41
metal-centered radicals, fullerene reactions,　4:2183-2184
metal chelating agents, preventive antioxidants,　3:1623,1624
metal complexes, oxidations, nitroxide-mediated,　2:1106-1108
metal-deactivating preventive antioxidants,　3:1625
metalloproteins, biological chemistry of reactive oxygen species,　3:1272
metallothioneins, lipid isomerization,　3:1608,1609
metal-mediated oxyl radical formation, DNA radicals,　3:1373
metal nanoparticles (MNPs)
bimetallic, radical-mediated photochemical synthesis,　4:2209
morphology, light-induced changes,　4:2207-2208
noble metals, radical-mediated photochemical synthesis,　4:2198-2209
metal nanoparticles (MNPs) (continued)
non-noble metals, radical-mediated photochemical synthesis,　4:2209
postsynthesis photochemical modification,　4:2206-2209
changes to size and morphology,　4:2208-2209
seeded growth,　4:2206,2208
surface chemistry,　4:2209
radical-mediated photochemical synthesis,　4:2197-2210
arrested growth,　4:2204
atmosphere/oxygen effects,　4:2205-2206
bimolecular routes,　4:2200-2201
counterion influence,　4:2205
factors affecting outcome,　4:2204-2206
initiator-free systems,　4:2202-2204
in situ stabilization,　4:2206
light intensity effects,　4:2204
photochemistry advantages,　4:2198
precursors,　4:2198-2200
stoichiometry,　4:2206
unimolecular routes,　4:2201-2202
self-assembly monolayer protection,　1:237-239
metal organic polyhedra (MOP), spin probes,　4:1999-2000
metals
conventional batteries,　4:2163
free-radical-mediated lipid peroxidation,　3:1580
metal substituted-silyl radicals, persistent and stable,　4:2137-2143
methacrylic esters, nitroxide-mediated polymerization,　4:1839
methane
atmospheric reactions,　1:515,519-522
NOx radical effects,　1:521-522
conversions, methanol, boron trichloride-mediated,　2:620
methanol
benzophenone-initiated photoadditions, endocyclic conjugated enones,　2:1142-1143
boron trichloride-mediated synthesis, methane conversions,　2:620
methionine (Met)
carbonate radical reactions,　3:1471-1472
cellular function,　3:1459
hydrogen atom radical reactions,　3:1472
hydroxyl radical reactions,　3:1467-1471
oxidant reaction rates,　3:1426,1427
oxidizing radical reactions,　3:1467-1472
peroxyl radical reactions,　3:1471
radical reactions,　3:1459,1467-1472
relay stations in electron transfer,　3:1484,1485-1487
SAM-dependent enzymes,　3:1502,1514
structure,　3:1461
methoxylated diphenylalkanes, intramolecular coupling,　2:1193
methoxylated phenanthrene, synthesis, electrochemically initiated intramolecular cyclizations,　2:1192-1193
methoxyl radicals, trimethylborane/triphenylborane substitutions,　2:602
methylacrylamides, polymerization, reversible addition fragmentation chain transfer,　4:1904-1905
methylacrylates
controlled/living radical polymerization,　4:1792-1793,1800-1801
organoheteroatom-mediated radical living polymerization,　4:1940,1941
reversible addition fragmentation chain transfer,　4:1896,1904-1905
1-methyl-3-alkylimidazolium cations, room-temperature ionic liquids,　1:433-434
(2S,3S)-3-methylaspartate, glutamate mutase isomerization,　3:1555
2-methy11,3-butadiene see isoprene
methyl chloroform, atmospheric,　1:515-516
methyl-coenzyme M reductase (MCR)
active-site structure,　3:1571
pseudo radical enzymes,　3:1538-1539
theoretical studies,　3:1570-1574
5-methylcytosine
oxidation
hydroxyl radicals,　3:1324-1326
one-electron transfer,　3:1330-1331
methyleneaziridine, cyclization/ring opening cascade reactions,　2:734
methylenecyclohexanes, carboazidations, sulfonyl azides,　2:1030-1031
methylene cyclopropanes, radical/radical cyclizations, samarium diiodide-mediated,　2:890-891
2-methyleneglutarate mutase (MGM)
mechanism,　3:1508,1511-1512
theoretical studies,　3:1551,1552-1553
methylene tetrahydrofurans, gram-scale synthesis, flow microreactor experiments,　2:1243-1244
4-methylguaiacol, horno-coupling, electrochemically initiated,　2:1188-1189
methylmalonyl-CoA mutase (MCM)
active-site structure,　3:1554
Co-C bond homolysis,　3:1550,1551
mechanism,　3:1508,1512,1514
theoretical studies,　3:1553-1555
methyl methacrylate (MMA), bulk polymerization,　4:1789-1791,1792,1793
methyl peroxyl radicals, matrix isolation spectroscopy,　1:212
methyl radicals
matrix isolation spectroscopy,　1:210-212
multiple addition to fullerenes,　4:2172
spin probes for EPR, ring conformation study,　1:158
structure, matrix isolation spectroscopy,　1:210-211
methyl-substituted silyl enol ethers, cyclizations, stannylaminyl radicals,　2:1025
MGM see 2-methyleneglutarate mutase
micelle formation, emulsion polymerization,　4:1721
microemulsion polymerization
industrial processes,　4:1724
reversible addition fragmentation chain transfer,　4:1922-1923,1925
microgels, atom transfer radical polymerization,　4:1876
microorganism defence, reactive oxygen species generation in phagocytes,　3:1263-1264
microorganisms, lipid isomerization in bacteria,　3:1617-1619
mild conditions, alcohol-thiol conversions, Barton-McCombie deoxygenations,　2:971-972
miniemulsion polymerization
industrial processes,　4:1724
nitroxide-mediated polymerization,　4:1821,1822,1840
reversible addition fragmentation chain transfer,　4:1922,1925
minimal polymerization time, controlled/living radical polymerization,　4:1789,1790,1792-1793
mismatched base pairs, DNA hole transfer,　3:1409-1411,1412
mitochondria
free fatty acid effects,　3:1686
free radical production (ROS/superoxide),　3:1681-1682,1683,1684,1686
hyperglycemia effects,　3:1681-1682,1683
reactive oxygen species generation,　3:1261-1262
Mizorolci-Heck reactions
cobalt-catalyzed,　2:1010-1011
titanium-catalyzed,　2:1014-1015
MLVs see multilamella vesicles
MMA see methyl methacrylate
MMD see molar mass distribution
MNPs see metal nanoparticles
MO see molecular orbitals
modelling
DNA hole transfer study,　3:1404-1405,1406,1413
electron transfer,　3:1415,1416,1422,1478-1481,1487
kinetics of controlled/living radical polymerization,　4:1788-1797,1816,1820
membrane models,　3:1609-1610
monolayer generation on silicon surfaces,　4:2096-2100
radical enzymes,　3:1547,1550-1551,1555,1557-1558
modular design, block copolymers, reversible addition fragmentation chain transfer polymerization,　4:1908,1912-1916
molar mass distribution (MMD),　4:1743-1748
molar masses, polymerization kinetics,　4:1743-1749
molecular architecture control
controlled/living radical polymerization,　4:1786,1787-1788,1807,1808
atom transfer RP,　4:1804-1805
nitroxide-mediated polymerization,　4:1801-1802,1840-1843
reversible addition fragmentation chain transfer,　4:1806,1906-1916
molecular clouds, interstellar chemistry,　1:481-482
molecular geometry, DNA radicals, theoretical calculation,　3:1380
molecular hybrids, atom transfer radical polymerization,　4:1876-1877,1879
molecular liquids, ionization, ionic liquid comparison,　1:436
molecular magnets, history,　1:11
molecular orbitals (MO)
single occupied molecular orbit plots,　4:2148
theoretical calculations,　3:1371
molecular oxygen (O2)
cysteine thiyl radical reactions,　3:1466
reductions, tris(trimethylsilyl)silane,　2:568-569
molecular reactive species (ROS/RNS), inflammatory response,　3:1283,1285-1288
molecular recognition, radical spin probes,　4:1987
molecular shuttles, rotaxanes,　1:240,241-244
molecular structures, DFT computation, EPR,　1:156
molecular weight control, polymerization,　4:1870-1871,1899-1903
molecular weight distribution (MWD), polymerization,　4:1931,1932-1933,1935,1937,1956
molecule-based conductors/superconductors, thiazyl radicals,　4:2147-2161
molten salts see ionic liquids
monocompetent systems
nitroxide-mediated polymerization,　4:1820-1821
persistent radical effect,　4:1816
monocytes, reactive oxygen species generation,　3:1263
monolayer protected clusters (MPCs), metal nanoparticles,　1:237-239
monolayers, see also self-assembled monolayers
monoliths, organotellurium-mediated radical living polymerization,　4:1959-1960
monomer reactivity ratios, copolymerization kinetics,　4:1766-1768
monomers
atom transfer radical polymerization,　4:1855-1856
ceiling temperature, radical polymerization,　4:1714
copolymerization parameters,　4:1715
droplets, emulsion polymerization,　4:1721-1722
industrial radical polymerization,　4:1704,1705
organoheteroatom-mediated radical living polymerization,　4:1939-1943
range, nitroxide-mediated polymerization/organometallic radical polymerization,　4:1801
range/functional groups, reversible addition fragmentation chain transfer polymerization,　4:1903-1906
solubility, emulsion polymerization,　4:1721
stabilization in storage and in-process, radical polymerization,　4:1717-1718
monoradicals, history,　1:1-6,8-10,13
monosubstituted alkyl radicals, stability,　1:454-457
monosubstitutions, SRN1 reactions,　1:335,336-337,361
monounsaturated fatty acids (MUFAs)
free-radical-mediated lipid peroxidation,　3:1580
lipid isomerization,　3:1599,1601
structure,　3:1599,1600
MOP see metal organic polyhedra
morpholine, addition to fullerenes,　4:2186
Mott phase, carrier doping, 1,3,5-trithia2,4,6-triazapentalenyl,　4:2156-2157
MPCs see monolayer protected clusters
MPO see myeloperoxidase
MP PLP see multiple-pulse pulsed-laser polymerization
MS see mass spectrometry
MTSL (S (2,2,5,5-tetramethy1-2,5-dihydro-1H-pyrrol-3-yl)methyl methanesulonothioate), cysteine residue spin labeling,　4:1967,1969,1970
MUFAs see monounsaturated fatty acids
multidirectional growth, conventional radical polymerization,　4:1788
multilamella vesicles (MLVs), lipid isomerization,　3:1609
multiple bonds, additions, sulfur-centered radicals,　2:798-803
multiple-pulse pulsed-laser polymerization (MP PLP), propagation rate coefficients,　4:1753-1755
multiple radical additions, fullerenes,　4:2172-2173
multisegmented copolymers, atom transfer radical polymerization,　4:1871-1872
muonium attachment, electron-rich olefin, ionic liquids,　1:434-435
muon spin resonance spectroscopy, ionic liquids,　1:434-435
muscarine, synthesis, thiazole-2[3H]-thione derivative photo-irradiation,　2:1238
mutagenicity studies, 5',8-cyclopurine lesions,　3:1351-1352
mutases
coenzyme B12-dependent enzymes,　3:1506,1507-1508,1511-1514
amino group rearrangement,　3:1508,1513-1514,1516,1526
carbon-skeleton rearrangement,　3:1511-1513
SAM-dependent aminomutases,　3:1513-1514,1515-1516,1526
MWD see molecular weight distribution
myeloperoxidase (MPO)
free-radical generation,　3:1580
hypohalide generation,　3:1579
inflammation,　3:1284
Myers-Saito cycloaromatizations,　2:710-711
N5O5 hydrolysis, stratospheric ozone depletion,　1:513
NADH-ubiquinone oxidoreductase (complex I), reactive oxygen species generation,　3:1261-1262
NADPH oxidases (NOXs)
reactive oxygen species generation,　3:1262-1264
cell signaling,　3:1263-1264
NADPH oxidases (NOXs) (continued)
phagocytes,　3:1263-1264
superoxide radicals, fatty acid effects,　3:1687
NADPH oxidase 2 (NOX2), phagocytic reactive oxygen species generation,　3:1263-1264
(-)-nakadomarin A, synthesis, Barton-McCombie deoxygenations,　2:550
nanomaterials
carbon filament synthesis, atom transfer radical polymerization,　4:1876,1877
see also metal nanoparticles
nanoscale distance measurements, spin labels and spin probes,　4:1971
nanoscale electronic wiring, DNA,　3:1397,1412,1413
nanoscale molecular machines, mechanical interlocking of free radicals,　1:239-244
naphthaldiimide (NDI), DNA hairpin conjugation, electron transfer,　3:1404,1405
naphthalene, electrolysis, biaryl compound synthesis,　2:1185-1186
(S)-naproxine, synthesis, chiral trialkyltin hydride/magnesium bromide,　2:539
NASA (National Aeronautics and Space Administration), atmospheric radical chemistry,　1:503,513
natural product synthesis
carbonyl-alkene coupling, samarium diiodide,　2:874-875
conjugate reductions, samarium diiodide,　2:863-864
7-endo cyclizations,　2:798-799,998-999
heteropinacol coupling,　2:868
intramolecular pinacol coupling, samarium diiodide,　2:867-868
sulfur-centered radicals,　2:798-799
natural product-polymer hybrids, atom transfer radical polymerization,　4:1876-1877,1379
natural triglycerides, lipid isomerization,　3:1603-1604
NDI see naphthaldiimide
near-infrared (FIR) spectroscopy, pulsed-laser polymerization kinetics,　4:1753
Negishi coupling, alkyl-alkyl, nickel-catalyzed,　2:1007
Negishi reagents, zirconium-catalyzed reactions,　2:1016
(+)-nemorensic acid, synthesis, electrochemically initiated,　2:1180
neocryptolepine, synthesis, iminyl radical homolytic aromatic substitutions,　2:1067
neon, matrix isolation,　1:207
neopentyl halides, SRN1 reactions,　1:351-352
neopentyl radicals, electron paramagnetic resonance,　1:160
neophilic rearrangements, Barton-McCombie intermediates, xanthates,　2:971
neophyl-type rearrangements
2-azabenzonorobornanes synthesis, tris(trimethylsilyl)silane-mediated,　2:589-590
dilauroyl peroxide-mediated,　2:1070-1071
synthetic applications,　2:1070-1071
networks of polymers
atom transfer radical polymerization,　4:1876
thiol addition to unsaturated compounds,　4:2041-2044
neutral attachment, monolayer generation on silicon surfaces,　4:2096
neutralization-reionization mass spectrometry (NRMS), gas phase radicals,　1:486-487,494
neutral particles, high-energy, interactions with matter,　1:395,396
neutral radicals
DNA,　3:1300-1302,1372,1375,1388
ionization of ions in ionic liquids,　1:436,437
versus radical cations/anions,　1:301-332
neutrophils
reactive oxygen species generation,　3:1263
small reactive species generation,　3:1283,1284
nickel-catalyzed reactions, oxidative additions,　2:1006-1008
nicotine, synthesis, Hofmann-Loffler-Freytag reaction,　1:131
NIR see near-infrared
nitrate anions, room-temperature ionic liquids,　1:439-440
nitrate esters, rearrangements,　1:126
nitrate radical (NO3), atmospheric,　1:507,508,516,523-524
nitrates, thermolysis,　1:41
nitric oxide
biological systems,　3:1269
radicals causing inflammatory response,　3:1284
radicals from proteins,　3:1439
superoxide reactions,　3:1270
nitric oxide synthase (NOS),　3:1284
nitrites
additions
indium-aminyl radicals,　2:769
nitrogen-centered radical formation,　2:780-781
N-stannylaminyl radicals,　2:768
formation, isonitrile conversion,　2:1037
nitrite esters, photoinduced remote functionalizations,　2:1231-1233
nitrites, thermolysis,　1:41
nitroalkanes, SRN1 reactions,　1:354-355
nitro-fatty acids, lipid peroxidation products,　3:1586,1591
nitrogen
4-exo-trig cyclizations, substituent effects,　2:701
matrix isolation,　1:207
nitrogen-based nucleophiles, SRN1 reactions,　1:339-340
nitrogen-carbon bonds
cleavage, nitrogen-centered radical formation,　2:778-779
formation, carbohydrate synthesis,　2:1160-1162
nitrogen-centered radicals
atom transfer radical additions,　2:774-775
biofuel combustion,　1:479
clocks,　1:117-118
cyclizations, unusual bond formation,　2:716-717
cysteine residue reactions,　3:1465
electron paramagnetic resonance,　1:162-164
enthalpies of formation,　1:95-97
formation,　2:767-781
N-allylsulfonyl compounds,　2:773
azide compounds,　2:767-771
hydrazine compounds,　2:771
imine derivative additions,　2:780-781
N-C bond cleavage,　2:778-779
N-halogen bond cleavage,　2:773-776
N-H bond cleavage,　2:779-780
nitrite additions,　2:780-781
N-N bond cleavage,　2:767-772
N-O bond cleavage,　2:776-778
N-S bond cleavage,　2:772-773
N-thioaryl compounds,　2:772-773
N-thiocarbonylsulfanyl compounds,　2:773
triazene compounds,　2:771-772
history,　1:13
intramolecular remote functionalizations, photoinduced,　2:1234
lipid isomerization,　3:1604-1605
protein radicals,　3:1432-1433,1439-1441
stability measurement,　1:451-453,468-469
nitrogen-containing compounds
antioxidant action,　3:1661-1665,1673
reductions, samarium diiodide,　2:862-863
nitrogen dioxide radicals
additions, 8-oxo-7,8-dihydroguanine radical cation,　3:1309-1310
cysteine residue reactions,　3:1465
guanine radical reactions,　3:1305-1307
lipid isomerization,　3:1604-1605
nitrogen-halogen bonds, cleavage, nitrogen-centered radical generation,　2:773-776
nitrogen heterocycles, synthesis, tris(trimethylsilyl)silane,　2:578
nitrogen-hydrogen bonds, cleavage, nitrogen-centered radical formation,　2:779-780
nitrogen-nitrogen bonds, cleavage, nitrogen-centered radical generation,　2:767-771
nitrogen-oxygen bonds
N-alkoxy compounds, photoinduced homolytic α-cleavage,　1:279-280
cleavage, nitrogen-centered radical formation,　2:776-778
thermolysis,　1:41
nitrogen-sulfur bonds
cleavage, nitrogen-centered radical generation,　2:772-773
photoinduced mesolytic cleavage,　1:297
nitrones
additions, trialkylboranes,　2:609
heteropinacol coupling, samarium diiodide,　2:868-869
reductive coupling, ketones, electrochemically initiated,　2:1211-1212
spin trapping,　4:2002,2004-2005
nitroso compounds, spin trapping,　4:2002,2005
nitrosoperoxycarbonate (ONOOCO2-), inflammatory response,　3:1285-1286
nitroxide decay, termination of nitroxide-mediated polymerization,　4:1819,1826,1833
nitroxide-mediated photopolymerization (NMP2),　4:1844-1845
nitroxide-mediated polymerization (NMP),　4:1799-1802,1813-1850
alkoxyamines,　2:1102-1103,4:1813,1828-1837
applications,　4:1843-1844
bicompetent initiation systems,　4:1821-1822
chain-end functionalization,　4:1840-1843
conditions,　4:1801
controlled architecture,　4:1801-1802,1840-1843
copolymerization,　4:1826-1827,1840,1843,1844
general scheme,　4:1818-1819
industrial processes,　4:1726,1727-1729
initiation stage,　4:1801,1818,1819,1820-1822
key equations,　4:1819
kinetics,　4:1813,1815-1837
macromolecular architecture,　4:1801-1802,1840-1843
main nitroxide families,　4:1827-1828
monocompetent initiation systems,　4:1820-1821
monomers/initiators,　4:1801
nomenclature,　4:1799
phase diagrams,　4:1819-1820
principles,　4:1813-1827
propagation stage,　4:1818,1819,1822-1825
radicals involved,　4:1814-1815
side reactions,　4:1833-1834
side reactions/cross coupling,　4:1818,1819,1825-1826
styrene, flow microreactor experiments,　2:1248,1250
termination stage,　4:1818,1819,1825-1826
types of polymerization,　4:1838-1840
nitroxide radicals
gold nanoparticle,　1:238-239
halogen bonding,　1:232-233
host complexation, ERR studies,　1:233-234
redox reactions,　4:2164-2165
rotaxane capping,　1:244
nitroxides
additions
alkylcatecholboranes, carbon radical generation,　2:1097
catecholboranes, synthetic applications,　2:1097
ketene, synthetic applications,　2:1104
aerobic oxidations, alcohols, metal-catalyzed,　2:1119-1121
alkoxyamine homolysis, synthetic applications,　2:1102-1103
Anelli oxidations, alcohols,　2:1113-1114
antioxidant action,　3:1664-1665,1673
autoxidations, synthetic applications,　2:1123
1,4-benzene diradical trapping, enediyne Bergman cyclizations,　2:1101-1102
calixarene study,　4:1995-1998
carbon radical trapping, olefin additions,　2:1101-1102
catalyst reoxidations,　2:1106-1108
crown-ethers/cryptands,　4:1990,1991
cucurbituril study,　4:1998-1999
cyclodextrin study,　4:1991-1995
dendrimer investigation,　4:1988-1991
electrochemically initiated aminoxyl radical-mediated reactions,　2:1202-1203
importance,　4:1965
MRI contrast agents,　4:1972-1973
as oxidants
metal catalysts/complexes,　2:1106-1108
organic species,　2:1104-1106
single electron transfers,　2:1104-1108
synthetic applications,　2:1104-1123
oxymetric spin probes,　4:1978,1981,1982
pH sensitive spin probes,　4:1974,1975-1976,1979
profluorescent spin labels and spin probes,　4:1986,1987
redox status spin probes,　4:1982-1984,1985
single electron transfers
metal catalysts/complexes,　2:1106-1108
organic species,　2:1104-1106
spin labels and spin probes,　4:1965,1966-1967
biological systems,　4:1965,1967-1987
GSH detection/quantification,　4:1984,1985,1986
oxymetric spin probes,　4:1978,1981,1982
pH sensitive spin probes,　4:1974,1975-1976,1979
profluorescent,　4:1986,1987
redox status spin probes,　4:1982-1984,1985
supramolecular systems,　4:1988-1999
thiol-specific spin labels,　4:1984,1985,1986
stability,　4:1965
nitroxide-mediated polymerization,　4:1819,1826,1833
structure,　4:1966,1967
synthetic applications,　2:1095-1129
thermolysis,　1:42
thiol-specific spin labels, GSH detection/quantification,　4:1984,1985,1986
trapping
aryl radicals,　2:1101-1102
carbon radicals,　2:1095-1102
after cyclizations,　2:1099-1101
unsaturations, synthetic applications,　2:1103-1104
nitroxyl-malonate-mediated radical polymerizations, styrene, flow microreactor experiments,　2:1249-1250
nitroxyl radicals
history,　1:14
nonchain reaction sequences,　1:109
NMP2 are nitroxide-mediated photopolymerization
NMP see nitroxide-mediated polymerization
NMR see nuclear magnetic resonance
NO2, electron-withdrawing group, SRN1 reactions,　1:333,354
NO2 radicals
additions, 8-oxo-7,8-dihydroguanine radical cation,　3:1309-1310
NO2 radicals (continued)
cysteine residue reactions,　3:1465
guanine radical reactions,　3:1305-1307
lipid isomerization,　3:1604-1605
NOx radicals (nitrogen oxide radicals)
stratosphere,　1:507-510,513
troposphere,　1:516,520-523
importance in pollution cleansing,　1:520-522
isoprene oxidation,　1:524-525
transport via PAN,　1:522-523
Nobel Prizes
radical history
awards,　1:14,17,26,30
non-awards,　1:1,3,6,30
noble metal nanoparticles, radical-mediated photochemical synthesis,　4:2198-2209
nojirimycin, synthesis,　2:1218-1219
nonanomeric alcohols, deoxygenations, carbohydrate synthesis,　2:1158-1160
nonanomeric C-radicals, reductions, carbohydrate synthesis,　2:1158-1160
nonaromatic anions, room-temperature ionic liquids,　1:438-442
nonchain reactions, radical kinetics,　1:108-109
noncyclic nitroxides, nitroxide-mediated polymerization,　4:1827,1838
non-enzymatic DNA repair, time resolved chemically induced dynamic nuclear polarization studies,　1:196-197
non-enzymatic/non-radical oxidation of lipids,　3:1578,1579
non-Kekule bi/polyradicals, history,　1:11-12
non-Kolbe synthesis,　2:1195-1196
nonlinear electrical transport, thiazyl radicals,　4:2157-2159
non-radical/non-enzymatic oxidation of lipids,　3:1578,1579
non-radical reactive oxygen species,　3:1259,1260,1271-1272
non-reductive processes, chain reactions,　1:73-78
nonsymmetric reference compounds, radical stabilization energy characterization,　1:451
normalization, ionized ionic liquids,　1:437
normal mode displacement diagrams, methyl radicals,　1:211
Norrish reactions,　2:1227-1231
Norrish type II photoprocesses, hydrogen abstraction,　1:135
Norrish type I reactions
ketones,　1:282
photochemical radical-mediated metal nanostructure synthesis,　4:2200,2201,2202
Norrish-Trommsdorff effect, viscosity increase, industrial radical polymerization,　4:1719
Norrish-Yang cyclobutanol synthesis, hydrogen abstraction,　1:134,135
NOS see nitric oxide synthase
NOXs see NADPH oxidases
NRMS see neutralization-reionization mass spectrometry
N-substituted/N,N-disubstituted acrylamides, nitroxide-mediated polymerization,　4:1838
NT3・(BF4)2
crystal structures,　4:2158
nonlinear electrical transport,　4:2157-2159
n-type semiconducting polymers, polymer-based field-effect transistors,　4:2066-2067
nuclear hyperpolarization, chemically induced dynamic nuclear polarization,　1:176,177
nuclear magnetic resonance (NMR) spectroscopy
radical study,　1:175-176
room-temperature ionic liquids,　1:444,445
see also chemically induced dynamic nuclear polarization
nuclear reactions, high-energy neutral particles interacting with atomic nuclei,　1:395,396
nucleation phase, emulsion polymerization,　4:1721-1722
nucleic acids
spin labels and spin probes,　4:1970-1971
see also DNA
nucleic acid sugar radicals
C1',　3:1362-1365,1367
C2',　3:1359-1362,1367
ribonucleosides,　3:1361,1362
C3',　3:1357-1359,1366
ribonucleosides,　3:1359
C4',　3:1352-1357,1366
C4-AP lesions,　3:1354-1356
ribonucleosides,　3:1356-1357
C5',　3:1346-1351,1366
aerobic conditions,　3:1347-1348
anaerobic conditions,　3:1348-1351
fates,　3:1346-1351
generation,　3:1346
ribonucleosides,　3:1352
formation,　3:1372
hole transfer processes,　3:1388-1390
oxidation,　3:1338,1345-1370
ribonucleosides,　3:1352,1356-1357,1359
nucleobases
oxidation/reduction,　3:1319-1344,1398-1399
see also individual bases
nucleophilic additions
guanine radicals,　3:1302-1305
8-oxo-7,8-dihydroguanine radical cation,　3:1309
nucleophilic carbon-centered radicals, arylations,　2:1059-1067,1074-1076
nucleophilic coupling, following reduction, photoinduced electron-transfer,　1:289
nucleophilic radicals, in vivo,　3:1428
nucleophilic substitutions
electron transfer,　1:333
see also SRN1 reactions
nucleophilic thiol-X reactions,　4:2018
nucleosides, reductions, tris(trimethylsilyl)silane,　2:570
null cycles, stratospheric chemistry,　1:508,509-510,513
number-average degree of polymerization,　4:1746-1747,1899-1900
O(1D) see electrically excited oxygen
O(3P) see ground-state oxygen
obesity,　3:1690-1694
octahedral spin cages, metal organic polyhedra,　4:1999-2000
odd-oxygen
stratosphere,　1:506-509
see also ozone; singlet oxygen
OFETs see organic field-effect transistors
oil-soluble polymerization systems, initiation stage,　4:1821,1822
oleanolic acid derivatives, synthesis, nitrite ester remote functionalizations,　2:1231-1232
olefinations, 1,2-diol reductions, tris(trimethylsilyl)silane,　2:563-564
olefins
additions
aryl radicals,　2:1066-1067,1080-1082
carbon radicals, with nitroxide trapping,　2:1101-1102
oxoammonium cations, alkoxyamine synthesis,　2:1096
vinylsilane epoxides, 1,2-dial synthesis,　2:995
xanthates,　2:976-977
amine-bearing electron-rich, pyrrolidine synthesis,　2:1177-1178
carboaminohydroxylations,　2:1081-1082
carbodiazenylations,　2:1081-1082
4-exo-trig cyclizations,　2:701
oxidative cleavage, sulfur-centered radicals,　2:801-802
oligomerizations
allyl iodoacetate,　2:952
fullerene,　1:386-388
ω-funetionahzed polymers, nitroxide-mediated polymerization,　4:1840-1843
OMRI see Overhauser-enhanced magnetic resonance, imaging
OMRP see organometallic radical polymerization
one-carbon ring expansions, cycloketones, tris(trimethylsilyl)silane,　2:581-582
one-electron oxidations
adenine,　3:1333
concepts,　2:901-904
cytosine,　3:1330
DNA damage,　3:1293-1300,1319-1320,1328-1333
end products of guanine reactions,　3:1300-1311
thermodynamics,　3:1293-1294
following hydrophosphinations, phosphorus-centered radicals,　2:795
guanine,　3:1331-1333
hole migration, guanine lesions in DNA,　3:1298-1300
metal catalysts/complexes, nitroxide-mediated,　2:1106-1108
5-methylcytosine oxidation,　3:1330-1331
organic species, nitroxides,　2:1104-1106
oxidant charge effects, guanine lesions in DNA,　3:1297-1298
reactive oxygen species in biological systems,　3:1266,1267-1271
thymine,　3:1328-1330
tris(silyl)-substituted silyl radical generation,　4:2124-2125
one-electron oxidized G:C, intra-base pair proton transfer, DNA radicals,　3:1385-1386
one-electron oxidized guanine monomers, protonation states, DNA radicals,　3:1384-1385
one-electron reductions
carbonyl groups, ketyl radicals, radical enzymes,　3:1525
fullerenes,　4:2190
organosilicon compounds, stable anion radical generation,　4:2135-2137
radical generation by enzymes,　3:1502
reactive oxygen species in biological systems,　3:1266,1267-1271
tris(silyl)-substituted silyl radical generation,　4:2124-2125
ONOO- see peroxynitrite
ONOOCO21 see nitrosoperoxycarbonate
open chain nitrones, spin trapping,　4:2002,2004-2005
Oppolzer's camphorsultam, stereoselective reactions,　2:660,662
optically active bis-sulfoxide synthesis, nitroxide radical trapping,　2:1100-1101
orbital angular motion, unpaired electrons, EPR,　1:150
organic azides
aminyl radical synthesis,　2:1020
azidosulfonylations,　2:1030-1031
azido-transfers,　2:1028-1031
cyclizations
aryl radicals,　2:1020
dithiocarbonyl radicals,　2:1020-1021
vinyl radicals,　2:1022
as radical acceptors,　2:1020-1034
carbon radicals,　2:1020-1023
heteroatom-centered radicals,　2:1023-1027
reductions, stannylatninyl radicals,　2:1023
organic batteries, polyradicals,　4:2163-2170
organic electron donors
electrochemical induction, synthetic applications,　2:844-845
photoactivation, synthetic applications,　2:832-834
reagent-induced activation
aminium cation-radical salts,　2:842-844
eerie ammonium nitrate,　2:834-837
copper reagents,　2:840-841
hypervalent iodine reagents,　2:844
iron reagents,　2:837-840
manganese reagents,　2:841-842
synthetic applications,　2:834-844
spontaneous electron transfers,　2:817-831
synthetic strategies,　2:817-847
thermal electron transfers,　2:817-831
organic electronic devices,　3:1495-1497
DNA nanoscale electronic wiring,　3:1397,1412,1413
organic field-effect transistors (OFETs),　4:2058-2059
principles,　4:2059
types,　4:2058
see also polymer-based field-effect transistors
organic-inorganic hybrids, atom transfer radical polymerization,　4:1876,1879
organic molecules
atmospheric, 1:514,　525
ethane,　1:522-523
iodine compounds,　1:518
isoprene,　1:523-525
methane,　1:515,519-522
organic monolayers see self-assembled monolayers
organic peroxides
decomposition by antioxidants,　3:1625-1626
industrial use,　4:1707-1708
initiators, polymerization,　4:1707-1710
reactions in biological systems,　3:1271
organic photovoltaic devices,　4:2059
see also polymer-based solar cells
organic solvents, radiation-induced radical reactions,　1:410-418
organic species, oxidations, single electron transfers, nitroxides,　2:1104-1106
organic synthesis, samarium diiodide, synthetic applications,　2:849-900
organized systems, lipid isomerization,　3:1609-1610
organobismuthine-mediated living radical polymerization (BIRP),　4:1932-1958,1960
organoboranes,　2:601-628
additions, enones,　2:611
alcohol deoxygenations,　2:621
alkene additions,　2:603-604
alkenylations,　2:606-607
alkyl iodide hydroxymethylations,　2:621
alkyne additions,　2:603-604
allylations,　2:606-607
arylations,　2:607
autoxidations,　2:602
Barton-McCombie deoxygenations,　2:621
bromine atom transfers,　2:605
as C-centered radicals,　2:607-616
chain transfers,　2:616-620
chlorine atom transfers,　2:605
halide reductions,　2:602-603
N-heterocyclic carbene complexes,　2:620-621
iodine transfers,　2:604-605
lithium enolate trifluoromethylations,　2:605
organoboranes (continued)
oxidative radical hydroxyarylations,　2:617
phenylselenium transfers,　2:605-606
radidal initiations,　2:602-607
radical initiators,　1:42-43
reactivity,　2:601-602
stereoselective hydroxysulfenylations,　2:620
styrylations,　2:606-607
tertiary amine complexes,　2:620
water complexations,　2:621
xanthate-transfers,　2:606
organocatalysis
chiral Bronsted acids,　2:685
enantioselective reactions,　2:679-686
hydrogen bonding-mediated,　2:685-686
SOMO catalysis,　2:680-684
organoheteroatom-mediated living radical polymerization
applications,　4:1958-1960
block copolymers,　4:1945-1949
chain transfer agents,　4:1933-1935,1937,1938
cocatalysts,　4:1935-1937,1956-1958
components,　4:1933-1953
conditions,　4:1937-1939
early development,　4:1932-1933
end group transformation,　4:1949-1953
mechanisms,　4:1953-1958
monomers,　4:1939-1943
synthetic scope,　4:1939-1943
organoiodine-mediated radical living polymerization (IRP),　4:1932-1944,1949,1953-1956
see also reversible chain transfer-catalyzed polymerization
organometallic compounds
pyrolysis, history,　1:6
thermolysis,　1:41
organometallic radical polymerization (OMRP), nitroxide-mediated,　4:1799,1800-1802,1807
organophosphines/organophosphates, antioxidant action,　3:1625
organophotocatalysis, asymmetric a-alkylations, aldehydes,　2:1224-1225
organosilicas, 9-mesityl-10-methylacridinium ion immobilization,　1:369-370
organostibine-mediated living radical polymerization (SBRP),　4:1932-1958,1960
organotellurium, antioxidant action,　3:1625
organotellurium-mediated living radical polymerization (TERP),　4:1932-1960
organo-tin compounds, radical chain mediators,　1:63-65,66
ornithine-4,5-aminomutase, mechanism,　3:1508,1513
orthogonal spin labeling, genetically encoded unnatural amino acids,　4:1967,1970
OSET see outer-sphere electron transfer
osmoylations, meso-tetxaol synthesis,　2:810-811
Ostwald ripening, mini-emulsion polymerization,　4:1724
outer-sphere electron transfer (OSET), atom transfer radical polymerization,　4:1869
Overhauser-enhanced magnetic resonance imaging (OMRI), spin probes,　4:1973-1974
oxazolidines
electrochemically initiated functionalization,　2:1204-1205
ring expansions,　2:1205
oxidant charge effects, one-electron oxidation of guanine,　3:1297-1298
oxidants in the body
endogenous/exogenous sources,　3:1425,1426
protein interactions,　3:1425-1457
reaction rate constants,　3:1425-1426,1427
oxidases, 2-oxoacids, pseudo radical enzymes,　3:1538
oxidation potentials
definition,　1:249
DNA nucleobases,　3:1398-1399
radical tables,　1:258-259,267-270
see also redox potential of radicals
oxidations
alcohols
metal-catalyzed,　2:1119-1121
oxoammonium salts,　2:1108-1117
alkoxyl radical fragmentations, carbohydrates,　2:1166-1168
amino acids,　3:1467-1472
α-keto acid synthesis, Fremy's salt,　2:1123
anilinamides, IBX-mediated,　2:779
carbohydrates, 2,2,6,6-tetramethylpiperidine-N-oxyl,　2:1202-1203
cerium(IV) ammonium nitrate-mediated,　2:901-941
chemoselective, alcohols, oxoammonium salts,　2:1108-1117
dialkyl nitroxides,　2:1096
2,6-di-tert-butylphenol,　2:1188
4,6-dimethylphenol, spirolactone synthesis,　2:1189
1,2-diols, a-diketone formation, oxoammonium salts,　2:1111
DNA,　3:1319-1344,1345-1370,1373,1374-1375,1401,1411-1412
electrochemically initiated
biaryl synthesis,　2:1184-1195
carbohydrates, 2,2,6,6-tetramethylpiperidine-N-oxyl,　2:1202-1203
carboxylic acids,　2:1196-1202
electron-rich aromatic rings,　2:1180-1183
enol ethers,　2:1176-1177
ketene dithioacetals,　2:1177-1180
menthol, azabicyclic N-oxyl radicals,　2:1203
electron-rich aromatic rings,　2:1180-1183
enol ethers,　2:1176-1177
fluoranthene, perylene derivative synthesis,　2:1186-1187
followed by coupling with nucleophiles, photoinduced electron-transfer,　1:288-289
hydrogen abstractions, nitroxide-mediated,　2:1119-1123
IBX-mediated, anilinamides,　2:779
iron(III) salt-mediated,　2:901-941
ketene dithioacetals,　2:1177-1180
lipids, see also lipid peroxidation
manganese(III) acetate-mediated,　2:901-941
menthol, azabicyclic N-oxyl radicals,　2:1203
methionine,　3:1467-1472
nitroxide-mediated
hydrogen abstractions,　2:1119-1123
synthetic applications,　2:1104-1123
nucleic acids, sugar radical formation,　3:1345-1370
nucleobase modification,　3:1319-1344
phenols, benzoquinone synthesis, Fremy's salt,　2:1122
polyaza-substituted ethenes,　2:826-831
polyunsaturated fatty acids with molecular oxygen, radical catalyzed,　3:1577
radical initiation,　1:50
radicals to peroxides, history,　1:2,3-4
tetrathiafulvalenes
arenediazonium salts,　2:819-826
diazonium salts,　2:819-826
synthetic applications,　2:818-826
thioethers,　3:1467-1472
tris(silyl)-substituted silyl radicals,　4:2124-2125,2130
see also one-electron oxidations
oxidative additions,　2:1003-1018
cobalt-catalyzed,　2:1008-1012
iron-catalyzed reactions,　2:1012-1014
manganese-catalyzed,　2:1014
nickel-catalyzed,　2:1006-1008
palladium-catalyzed,　2:1004-1006
silver-catalyzed,　2:1014
titanium-catalyzed,　2:1014-1015
zirconium-catalyzed reactions,　2:1015-1016
oxidative cleavage, olefins, sulfur-centered radicals,　2:801-802
oxidative coupling
chiral ligand-mediated,　2:688-689
metal-dependent,　2:926
oxidative cyclizations
5-cyclodecynone, oxygen-centered radicals,　2:788
cyclopropane synthesis,　2:903-904
oxidative damage
DNA hole transfer,　3:1401,1411-1412
localization/diffusion of oxidants,　3:1425
proteins,　3:1425-1457
oxidative (electron-loss) pathway, DNA radical formation,　3:1373,1374-1375
oxidative fragmentation, room-temperature ionic liquids,　1:440,444
oxidative hydroxymylations, organoboranes,　2:617
oxidative phosphonations, dialkyl phosphites,　2:1086
oxidative radical hydroxyarylations, organoboranes,　2:617
oxidative rearrangements, tertiary allylic alcohols, oxoammonium salts,　2:1110
oxidative stress
biomarkers,　3:1302,1311
DNA reactions,　3:1283-1317
DNA sugar radicals,　3:1345-1370
glucose-derived free radicals, type-2 diabetes,　3:1680-1684
inflammatory response,　3:1283,1288,1302,1311
markers in vitro, lipid peroxidation products,　3:1577-1578,1590-1593
protein damage, sulfur/selenium-containing amino acids,　3:1459
reactive oxygen species in biological systems,　3:1266,1271,1277-1278
see also lipid peroxidation
oxide radical ions, radiation-induced production,　1:401
oxidizing effects, atmospheric cleansing,　1:514-525
oxidizing radical production, water radiolysis,　1:402-403
oxime ethers, tricyclic pyrolidine synthesis, cascade cyclizations,　2:730-731
oximes, reductive coupling, ketones,　2:1211-1212
oxiranyl ketones, aldol reactions, samarium diiodide-mediated,　2:888
2-oxoacids, dehydrogenases/oxidases, pseudo radical enzymes,　3:1538
oxoammonium cations, additions to olefins, alkoxyamine synthesis,　2:1096
oxoammonium salts
desymmetrizations,　2:1117-1118
kinetic resolutions,　2:1117-1118
oxidations
chemoselective, alcohols,　2:1108-1117
synthetic applications,　2:1108-1119
8-oxo-7,8-dihydroguanine (8-oxoG)
biological implications of lesions,　3:1311-1312
oxidation,　3:1333-1334
8-oxo-7,8-dihydroguanine/formylamine (8-oxoG/dF) lesion, hydroperoxyl radical oxidation,　3:1336
8-oxo-7,8-dihydroguanine radical cation (8-oxoG)+
nucleophilic additions,　3:1309
one-electron oxidation,　3:1308-1311
α-oxy-alkyl radicals, decatungstate catalyzed addition to fullerenes,　4:2174
α-oxyaminations, SOMO catalysis, aldehydes,　2:680-681
oxygen.
effects on radical-mediated metal nanostructure synthesis,　4:2205-2206
inhibition, industrial radical polymerization,　4:1718-1719
initiation, radical enzymes,　3:1539
intramolecular homolytic substitutions,　2:644-645
molecular
cysteine thiyl radical reactions,　3:1466
reductions, tris(trimethylsilypsilane,　2:568-569
odd-oxygen, stratosphere,　1:506-509
photochemical reactions, stratosphere,　1:506
role in lipid isomerization,　3:1615-1616
see also ozone; singlet oxygen
oxygenations
B-alkylcatecholboranes,　2:613-616
photocatalytic reactions,　1:370-383
oxygenative tetraamination, fullerenes,　4:2186
oxygen-carbon bonds
cleavage
photoinduced homolysis of aromatic ethers/esters,　1:280-281
radical generation, tin-hydride mediated,　2:549-550
formation, carbohydrate synthesis,　2:1162-1164
oxygen-centered radicals
clocks,　1:118,119
cyclizations, unusual bond formation,　2:717-719
electron paramagnetic resonance,　1:164-165
formation,　2:781-790
fullerene reactions,　4:2180-2182
history,　1:14-16
hydrogen atom transfers,　2:782-783
nitrite ester remote functionalizations,　2:1231-1233
photoinduced remote functionalizations, intramolecular,　2:1231-1234
redox reactions,　4:2164-2165
β-scission,　2:783-785
stability measurement,　1:451-453,466-468
see also reactive oxygen species; superoxide
oxygen-derived species see reactive oxygen species
oxygen-hydrogen bonds, bond dissociation enthalpy, phenolic antioxidant action,　3:1641-1642
oxygen-iodine bonds, iodanes, photoinduced homolytic α-cleavage,　1:278-279
oxygen-silicon bonds, photoinduced mesolytic cleavage,　1:294
N-oxyl radicals, bond dissociation energies,　1:92-93
oxyl radicals
cyclizations, tin hydride-mediated,　2:556
metal-mediated radical formation, DNA radicals,　3:1373
see also nitroxyl radicals
oxymetry, spin probes,　4:1978-1982,1983,1984
oxysterols
cholesterol oxidation products,　3:1586-1587
human physiological levels,　3:1591,1592
ozone
Antarctic hole,　1:511-513,517-518,525
lipid oxidation,　3:1578,1579
stratosphere,　1:505,506-513,525
depletion mechanisms,　1:506,508-509,510-513
troposphere
halogen radicals,　1:517-518
hydroxyl radicals,　1:514-515,517-518
ozone (continued)
isoprene reaction,　1:525
nitrate radicals,　1:516
NOx radical dependent effects,　1:520,521-522,525
organic compound reactions,　1:516,519-525
P3HT see poly(3-hexylthiophene)
P450s, inhibition, N-benzyl-N-cyclopropylamine radical cations,　1:310
PAC see photoacoustic calorimetry
(-)-paeoniflorin, multistep synthesis, oxygen-centered radical remote functionalizations,　2:1233-1234
PAHs see polycyclic aromatic hydrocarbons
paired electrolysis, Knoevenagel adducts, cyclobutane synthesis,　2:1184
pair production, electromagnetic radiation,　1:395,396
palladium-catalyzed reactions
oxidative additions,　2:1004-1006
reoxidants, nitroxides,　2:1106-1108
1-palmitoy1-2-elaidoyl phosphatidyl choline (PEPC), radical isomerization from POPC,　3:1602
1-palmitoy1-2-oleoyl phosphatidyl choline (POPC), radical isomerization to PEPC,　3:1602
PAN see peroxyacetyl nitrate
pancreatic β-cells, glucotoxicity/lipotoxicity,　3:1680
Paneth, F.A., aliphatic radicals,　1:6
paramagnetic..., see also electron paramagnetic resonance
paramagnetic rotaxanes,　1:244
paramagnetic supramolecular systems, EPR,　4:1987
paramagnetic susceptibilities, temperature dependence, 1,3,5-trithia2,4,6-triazapentalenyl,　4:2148,2149
partially saturated pyrimidine-fused azocines, synthesis,　2:713
particles
atmospheric condensed phase processes,　1:504
ionizing radiation,　1:395-396
polar stratospheric cloud,　1:504,512
passivation, silicon surfaces,　4:2082,2084
Pauling's electronegativity equation, radical stabilization energies,　1:99-100
PBTTT copolymer, polymer-based field-effect transistors,　4:2063-2064
PCBM see [6,6]-phenyl-C,51-butyric acid methyl ester
PCDTBT see poly[N-9-hepta-decanyl-2,7-carbazole-alt-5,5-(4',7'-di-2-thieny1-2',1',3'-benzothiadiazole))
PCE see power conversion efficiency
PCET see proton-coupled electron transfer
P-chiral bisphosphino ligands, synthesis, Kolbe electrolysis,　2:1201-1202
PCHT see proton-coupled hole transfer
PCPDTBT see poly[2,6-(4,4-bis-(2-ethylhexyl)-4-cyclopenta[2,1-b;3,4-bldithiophene)-alt-4,7-(2,1,3-benzothiadiazole)]
PDI see polydispersity index
PEDRI see proton electron double resonance imaging
PELDOR see pulse electron double resonance
penitrem building blocks, synthesis, aryl radicals,　2:1084-1085
penitrem indole alkaloids, synthesis, radical/anionic sequences,　2:891-892
pentacyclic alkaloids, synthesis, tris(trimethylsilyl)silane,　2:580
penultimate model (PM), copolymerization propagation,　4:1749-1750
penultimate unit effect (PUE), nitroxide-mediated polymerization,　4:1834-1835
peptide backbones
electron transfer influences,　3:1487-1493
amide bond stepping stones,　3:1490-1493
charges,　3:1489-1490
dipole moments,　3:1487-1493
peptide nucleic acid (PNA), DNA hybrid,　3:1415
peptides
electron transfer,　3:1475-1499
functionalization, radical thiol addition reactions,　4:2022,2024-2025,2026,2027,2028
intramolecular electron transfer, time resolved CIDNP studies,　1:195-196
nanotube-based electrodes,　3:1495
side-chains, electron hopping,　3:1479-1481
single molecules, electron transfer,　3:1496,1497
sulfur-containing amino acid residues, radical generation,　3:1605-1607
synthesis, Baeyer-Villager reactions, TEMPO-mediated,　2:1120
perchlorinated triarylmethyl radicals, history,　1:21-23
perfluoroalkylations, ketones, germylenol ethers,　2:606
perfluoroalkyl iodides, atom transfer radical additions,　2:946
periodic mesoporous organosilicas (PM0s), 9-mesityl-10-methylacridinium ion immobilization,　1:369-370
peroxidases, oxidation of xenobiotics to radicals,　3:1266
peroxidations
antioxidants,　3:1623-1672
lipids,　3:1577-1594
peroxide effects
atom transfer radical addition,　4:1851
halogen radicals, history,　1:17-18
peroxides
history,　1:2,15-16
initiators, industrial radical polymerization,　4:1707-1710
thermolysis,　1:38-39
peroxisomes, fatty acid induced free radical generation,　3:1686-1687
peroxyacetyl nitrate (PAN), tropospheric chemistry,　1:522-523
peroxydisulfuric acid salts see persulfates
peroxy esters, history,　1:16
peroxyl radicals
antioxidants,　3:1623-1672
clocks, phenolic antioxidants,　3:1635-1637
history,　1:2,15-16
methionine reactions,　3:1471
proteins,　3:1430-1431
quenching, phenolic antioxidants,　3:1627-1629
peroxynitrite (ONOO-)
generation, inflammatory response,　3:1283,1284,1285-1286
protein reactions,　3:1439-1441
reactions in biological systems,　3:1272
persistent radical effect (PRE)
consequences,　4:1817-1818
controlled/living radical polymerization,　4:1786-1787,1797-1799,1817-1818
definition,　4:1815-1816
examples,　4:1816-1817,1818
kinetic equations,　4:1816,1819
nitroxide-mediated polymerization,　4:1813,1819
nonchain reaction sequences,　1:108-109
see also atom transfer radical polymerization; stable free radical polymerization
persistent radicals,　1:58,59
applications,　4:2117-2118
history,　1:2-3,7,9-10
initiators, thermolysis,　1:41-42
intermediates, nonchain reactions,　1:108-109
silyl radicals,　4:2117-2146
use of term, 1:449,　4:2118
persulfates (peroxydisulfuric acid salts), initiators, industrial radical polymerization,　4:1709-1710
perylene bisimides (PDI), DNA conjugation, hole transfer,　3:1413
perylene derivatives, electrochemically initiated synthesis,　2:1186-1187
PET see photoinduced electron-transfer
PFETs see polymer-based field-effect transistors
PFL see pyruvate formate lyase
pH dependence, electron transfer,　3:1496,1497
pH measurements, spin probes,　4:1974,1975-1978
phagocytes, reactive oxygen species generation,　3:1263
pharmaceuticals, reactive oxygen species generation,　3:1265-1266
pharmacological antioxidants, effectiveness,　3:1277
phase diagrams, nitroxide-mediated polymerization,　4:1819-1820,1822-1824
phase-separated antioxidants,　3:1668-1669
phase transitions, thiazyl radicals,　4:2147-2154
phenol derivatives, silane-mediated reactions,　2:594-595
phenolic antioxidants,　3:1627-1661
catechols/resorcinols/hydroquinones,　3:1657-1659
kinetic methods,　3:1629-1641
direct measurements,　3:1635-1640
inhibited autoxidation,　3:1630-1635
peroxyl radical clocks,　3:1635-1637
using DPPH,　3:1640-1641
mechanistic considerations,　3:1650-1657
computational insights,　3:1653-1654
H-atom transfer,　3:1651-1653
solvent effects,　3:1654-1655
pyridinols/pyrimidinols,　3:1660-1661
thermodynamic methods,　3:1641-1650
thermodynamics/lcinetics correlation,　3:1646-1650
phenols
conversions, benzoates,　2:697
2,6-dihalogenated, electrochemical coupling,　2:1190-1191
electrolysis, biaryl compound synthesis,　2:1186-1187
hydrogen abstractions, TEMPO-mediated,　2:1121-1122
phenothiazine (PTZ), DNA hairpin conjugation, electron transfer,　3:1404,1405
phenoxides, oxidative coupling, metal-dependent,　2:926
phenoxyl radicals
hydrogen bonded complexes,　1:230
matrix isolation spectroscopy,　1:223-225
reaction pathways,　2:1187
phenoxymethyl radicals, decatungstate catalyzed addition to fullerenes,　4:2173
phenylations, α-iodoesters, organoboranes,　2:607
[6,6]-phenyl-C61-butyric acid methyl ester (PCBM), polymer-based solar cells,　4:2060,2068,2070,2071-2075
phenyl cyclopropyl ketones, radical anion generation,　1:302-303
phenylhydrazines, fullerene reactions,　4:2179-2180
phenyl peroxy radicals, matrix isolation spectroscopy,　1:220,221
phenyl radicals, matrix isolation spectroscopy,　1:208,218-222
2-phenylselenated butadienes, synthesis,　2:808
phenylseleno groups
atom transfer radical additions,　2:956-958
atom transfer radical cyclizations,　2:956-958
carbon-centered radical generation,　2:805-806
transfers
α-heteroatom-substituted radicals,　2:957
organoboranes,　2:605-606
phenyl-substituted bis(silyl) silicon-centered radicals,　4:2132,2134
phenyl-substituted silyl enol ethers, cyclizations, stannylaminyl radicals,　2:1025
phenylthiomethyl radicals, decatungstate catalyzed addition to fullerenes,　4:2173
phosphasilenes, stable anion radicals,　4:2137
phosphate esters, rearrangements,　1:126,128-129,130
phosphates, antioxidant action,　3:1625
β-(phosphatoxy)alkyl radicals, rearrangements,　1:127
phosphines
antioxidant action,　3:1625
aryl radical phosphonylations,　2:1086-1087
phosphine selenides, reductions, tris(trimethylsilyl)silane,　2:565-566
phosphine sulfides, reductions, tris(trimethylsilyl)silane,　2:565-566
phospholipids
cis-trans isomerization,　3:1602
geometry of saturated/cis and trans fatty acids,　3:1617-1618
phosphonations, arenes/phosphines,　2:1086-1087
α-phosphoric enones, reductive alkylations, chiral Lewis acid-mediated,　2:673-674
phosphorous ylides, flash vacuum pyrolysis,　2:706-707
phosphorus-based mediators, phosphorus-centered radicals,　2:796-798
phosphorus-based nucleophiles, SRN1 reactions,　1:339-340
phosphorus-carbon bonds
formation
carbohydrate synthesis,　2:1162
tris(trimethylsilyl)silane-mediated,　2:587-588
phosphorus-centered radicals
cascade reaction hydrophosphinations,　2:794-795
chemistry,　2:790-796
electron paramagnetic resonance,　1:162-164
fullerene reactions,　4:2182
generation
β-eliminations,　2:795-796
homolytic substitutions,　2:796
heterophosphinations,　2:792-794
hydrophosphinations,　2:792-795
as leaving groups,　2:795-796
substituent effects,　2:790-792
unsaturations,　2:792-795
photoacoustic calorimetry (PAC)
bond dissociation enthalpy measurement,　1:83
phenolic antioxidant thermodynamics,　3:1644-1645
photoacoustic spectroscopy, radical characterization,　1:298
photoactivated flavin cofactors, DNA photolase, electron transfer,　3:1482,1483
photoactivated redox processes, radical initiation,　1:51-52
photoadditions, branched-chain sugar synthesis,　2:1142-1143
photocarbonylations, flow microreactor experiments,　2:1253-1256
photocatalytic reactions
bromination, via charge separation, 9-mesityl-10-methylacridinium ion,　1:383-386
cascade reactions,　2:761-763
C-C bond formation via charge separation,　1:386-389
dimerization, anthracene,　1:388,389
malonylations, indoles,　2:1077
9-mesityl-10-methylacridinium ion,　1:366-389
Norrish reactions,　2:1227-1231
oligomerization, fullerene,　1:386-388
oxygenation,　1:370-383
anthracene, via radical ion coupling,　1:370-372
benzylamine,　1:380
DNA cleavage,　1:380-383
electron transfer,　1:370-383
photocatalytic reactions (continued)
9-mesity1-10-methylacridinium ion,　1:370-383
tetraphenylethylene to 1,2-dioxetane,　1:372-374
triphenylphosphene,　1:378-380
p-xylene, reduction of oxygen,　1:374-378
photosynthesis mimics,　1:365
radical ions, charge separation,　1:365-393
ruthenium-mediated
C-H functionalizations, indoles,　2:1226-1227
[2+2] cycloadditions,　2:1221-1222,1223-1224
reductions, alkyl halides,　2:1225-1226
synthetic strategies,　2:1221-1227
photocells, thiazyl radicals,　4:2159
photochemically activated radical initiators,　1:43-49
photochemically generated radicals see photoinduced radicals
photochemically-induced dynamic nuclear polarization (photo-CIDNP),　1:298
photochemically-induced extrusions, carbon monoxide, cyclic ketones,　2:1231
photochemistry
aromatizations, nitroxide-mediated, Hantzsch 1,4-dihydropyridines,　2:1105-1106
carbon radicals,　1:275-297
characterization,　1:297-298
electron transfer,　1:288-297
single step processes,　1:275-288
cleavage
Barton esters
indolizidine alkaloid synthesis,　2:1236-1237
platensimycin synthesis,　2:1235-1236
carbamoyl diethyldithiocarhamate, (-)-aphanophine synthesis,　2:1235
hexamethylditin
camptothecin synthesis,　2:1238-1239
C-glycoside synthesis,　2:1238-1239
homolytic,　1:275-288
mesolytic,　1:291-297
tin reagents,　2:1238-1239
see also photolysis
electron transfer-induced additions,　2:1217-1221
fullerenes
acylations,　4:2173-2174
additions,　4:2172,2179
dimer cleavage,　4:2172
hydrogenation,　4:2184-2185
ion radicals,　4:2186-2191
platinum-centered radicals,　4:2184
silicon-centered radicals,　4:2183,2184
sulfur-centered radicals,　4:2181
glycylglycine, time resolved chemically induced dynamic nuclear polarization,　1:191-193
Hofmann-Loffier-Freytag reactions, dihydrodeoxyepiallocemuine synthesis,　2:1234
isomerizations, 1-benzyloxy-9,10-anthraquinones, via 3-exo-trig closure,　2:698
light induced changes in nanoparticle morphology and size,　4:2207-2208
light intensity effects, radical-mediated metal nanostructure synthesis,　4:2204
nitrogen-centered radicals,　2:1234
Norrish reactions,　2:1227-1231
oxygen-centered radicals,　2:1231-1234
postsynthesis nanostructure modification,　4:2206-2209
proteins,　3:1443-1447
radical-mediated metal nanostructure synthesis,　4:2197-2210
advantages,　4:2198
factors affecting outcome,　4:2204-2206
precursors,　4:2198-2204
radical thiol additions,　4:2019,2020
carbohydrates,　4:2022,2053
colloidal particles,　4:2045,2047,2048
dendrimers,　4:2030,2033
macrocycles,　4:2025,2030
peptides,　4:2025-2029
polymers,　4:2033,2035-2036,2039,2041,2045
surface chemistry,　4:2048-2052
reaction rates, atmosphere,　1:505-506
reactive oxygen species generation in biological systems,　3:1265
reduction of acetone,　4:2199
remote functionalizations,　2:1231-1234
ruthenium-mediated reactions,　2:1221-1227
sulfur-containing biomolecules, time resolved chemically induced dynamic nuclear polarization,　1:193-194
sulfur-containing derivatives,　2:1235-1238
synthetic applications,　2:1217-1241
tin reagents,　2:1238-1239
tris(silyl)-substituted silyl radicals,　4:2130
photo-CIDNP see photochemically induced dynamic nuclear polarization
photoconductivity, thiazyl radicals,　4:2159
photocycloaddition, tertiary amines to fullerenes,　4:2188
photodiodes, peptide-based,　3:1495-1496
photodissociation
atmospheric radical generation,　1:503
stratospheric oxygen/ozone reactions,　1:506
photoelectric effect, high-energy electromagnetic radiation,　1:395,396
photoelectrochemical evaluation techniques, redox potentials,　1:249,255-257
photoelectron transfers, organic donors, synthetic applications,　2:832-834
photoexcited ketones, hydrogen abstraction,　1:135
photofragment spectroscopy, unimolecular reactions, gas phase radicals,　1:493-494
photoinduced bond cleavage see photolysis
photoinduced charge separation, free radical generation, room-temperature ionic liquids,　1:434
photoinduced cyclizations, bromoalkynes, triethylamine,　2:1252-1253
photoinduced electron-transfer (PET),　1:288-297
followed by elimination/addition of neutral species,　1:289-291
mesolytic cleavage,　1:291-297
oxidation followed by electrophilic coupling,　1:288-289
reduction followed by nucleophilic coupling,　1:289
photoinduced radicals,　1:275-300
additions,　1:287-288
characterization techniques,　1:297-298
homolytic cleavage,　1:275-288
hydrogen abstraction,　1:283-287
ketones, history,　1:26
mesolytic cleavage,　1:291-297
one step processes,　1:275-288
precursors, matrix isolation,　1:207-208
photoinduced reactions
aliphatic azides, allenylindium dichloride,　2:1027
comparison with radiation-induced reactions,　1:396
exciton-mediated initiation, monolayer generation on silicon surfaces,　4:2093-2096
remote functionalizations, heteroatom-centered intermediates,　2:1231-1235
photoiniferters, radical initiators,　1:45
photoinitiation
industrial radical polymerization.　4:1711-1712
monolayer generation on silicon surfaces,　4:2093-2096
photochemically activated radical initiators,　1:43-49
polymerization kinetics,　4:1761-1762
SRN1 reactions,　1:334
photoinitiators see photochemically activated radical initiators
photoionization
free radical generation, room-temperature ionic liquids,　1:434
gas phase radicals,　1:479,487-492
absolute cross-section,　1:491
dissociative,　1:490-491
Frank-Condon factors,　1:488-490
ionization energy,　1:488-490
signatures,　1:487-488
state-selected cation source,　1:491-492
photoionization mass spectrometry (PIMS), bond dissociation enthalpy measurement,　1:83
photolysis
free radical generation, room-temperature ionic liquids,　1:433,444
gas phase isolated radical generation,　1:484-485
hydrogen peroxide, history,　1:2,14
matrix isolation of radicals,　1:207-208
radical initiators,　1:43-49
photomasking, surface polymerization, radical thiol-ene process,　4:2048,2049,2050
photomodulation voltammetry, redox potential determination,　1:256-257
photooxidation, proteins,　3:1443-1447
photooxygenation see photocatalytic reactions, oxygenation
photopolymerization, nitroxide-mediated polymerization,　4:1844-1845
photosensitized alkylation, alkenes,　1:288-289
photosynthesis
electron transfer in proteins,　3:1475,1476
mimicking systems,　1:365
photovoltaic devices,　4:2059,2060,2076-2077
see also polymer-based solar cells
phthalimide N-oxyl (PINO), unsaturations,　2:1103-1104
phthalimides
photoinduced electron-transfer
followed by elimination/addition of neutral species,　1:289-291
macro-cyclizations,　2:1218-1219
physiological levels in humans, lipid peroxidation products,　3:1590-1593
physiologically relevant reactive oxygen species,　3:1259-1281
π-conjugated aromatic stacking, DNA charge transfer,　3:1397,1399,1401
π-radicals, geometries, electron paramagnetic resonance,　1:156
π-systems, additions, oxygen-centered radicals,　2:787-790
pigment dispersants, block copolymers, industrial radical polymerization,　4:1728
PIMS see photoionization mass spectrometry
pinacol coupling
samarium diiodide,　2:864-870
stannane-mediated,　2:651-652
pinacol cyclizations, substituent effects,　2:867-868
PINO see phthalimide N-oxyl
piperazinone nitroxide, nitroxide-mediated polymerization,　4:1728
piperidine derivatives, silylations,　2:1205
plasma (blood), lipid peroxidation products,　3:1583,1586,1589,1590-1593
plasma chemistry,　1:480-481
plastics, definition,　4:1701
plastics industry, history and growth,　4:1701-1702
platensimycin synthesis, Barton ester photochemical cleavage,　2:1235-1236
platinum-centered radicals, fullerene reactions,　4:2184
PLEDS see polymer-based light emitting diodes
pleuromutilin synthesis, radical cyclization/intramolecular aldol sequence,　2:893-894
PLP see pulsed-laser polymerization
PM see penultimate model
PMOs see periodic mesoporous organosilicas
PNIPAM-block-PNVP diblock copolymers, organoheteroatom-mediated radical living polymerization,　4:1958
polarity reversal catalysis
benzeneselenol,　2:542
silanes,　2:572-574
polar reactions
following SRN1 reaction, ring closure,　1:342-344
stereoselective crossover reactions,　2:657-658,659
polar stratospheric cloud (PSC) particles, ozone depletion,　1:504,512
polyarylated products, SRN1-Stille tandem reactions,　1:339
polyaza-substituted ethenes, spontaneous electron transfers,　2:826-831
poly[2,6-(4,4-bis-(2-ethylhexyl)-4-cyclopenta[2,1-b;3,4-b']dithiophene)-alt-4,7-(2,1,3-benzothiadiazole)] (PCPDTBT), polymer-based solar cells,　4:2073,2074
1,2-polybutadiene, modifications, xanthates,　2:983-984
polycyclic aromatic compounds, synthesis, xanthates,　2:978-981
polycyclic aromatic hydrocarbons (PAHs), formation in combustion,　1:479
polycyclic indoles, synthesis, addition/cyclization cascades,　2:742-743
polycyclic products
conjugated acyclic triynes,　2:743-744
SOMO catalysis,　2:683-684
polycyclizations, cascade reactions,　2:729-732
poly(3,3'''-dialkyl-quaterthiophene) (PQT), polymer-based field-effect transistors,　4:2063,2064
polydispersities, reversible addition fragmentation chain transfer polymerization,　4:1900,1901,1902,1903,1908
polydispersity index (PDI), reversible addition fragmentation chain transfer polymerization,　4:1901,1902,1903,1904
polyenes, reductive tandem cyclizations,　2:1209
polyfunctionalized cyclohexane analogs, synthesis,　2:1154
polyfunctionalized cyclopentane analogs, synthesis,　2:1149-1153
poly[N-9-hepta-decanyl-2,7-carbazole-alt-5,5-(4',7'-di-2-thienyl-2',1',3'-benzothiadiazole)] (PCDTBT),　4:2065,2066,2067
poly(3-hexylthiophene)(P3HT)
polymer-based field-effect transistors,　4:2061-2062,2064
polymer-based solar cells,　4:2070-2072
polyimide (PI) film microreactors, cyclizations, tris(trimethylsilyl)silane-mediated,　2:1244-1246
polymer applications
batteries,　4:2057-2079,2163-2170
industrially produced polymer types,　4:1702-1703
spin labels and spin probes,　4:1972
polymer-based field-effect transistors (PFETs),　4:2057
advanced materials,　4:2061-2067
basic principles,　4:2058-2059
complementary circuits,　4:2075-2076
copolymers,　4:2063,2065-2066
field-effect mobility,　4:2059
low-cost applications,　4:2075-2076
polymer-based field-effect transistors (PFETs) (continued)
n-type semiconducting polymers,　4:2066-2067
polythiophenes,　4:2061-2065
p-type semiconducting polymers,　4:2061-2066
polymer-based light emitting diodes (PLEDs),　4:2057
polymer-based solar cells (PSCs),　4:2057
advanced materials,　4:2067-2075
basic principles,　4:2059-2061
bulk heterojunction structure,　4:2059,2060,2067-2068
commercial production,　4:2076-2077
low-band gap polymers,　4:2072-2075
polyphenylenevinylenes,　4:2069-2070
polythiophenes,　4:2070-2072
power conversion efficiency,　4:2061,2068-2069
roll-to-roll technique,　4:2076-2077
polymer capsules, synthesis, thiol addition to unsaturated compounds,　4:2045,2047,2048
polymer hydrogels, synthesis, thiol addition to unsaturated compounds,　4:2044-2045
polymeric molecular hybrids, atom transfer radical polymerization,　4:1876-1877,1879
polymerization
ionic/radical polymerization comparison,　4:1785,1786
see also radical polymerization
polymerization inhibitors, industrial radical polymerization,　4:1717-1718
polymerization rate kinetics,　4:1740-1743
polymerization time, dead chain fraction effects,　4:1789,1790
polymer monoliths, organotellurium-mediated radical living polymerization,　4:1959-1960
polymer networks
atom transfer radical polymerization,　4:1876
thiol addition to unsaturated compounds,　4:2041-2044
polymer-supported trialkyltin hydrides,　2:532-534
polyphenylenevinylenes (PPVs), polymer-based solar cells,　4:2069-2070
polyradical batteries,　4:2163-2170
practical applications,　4:2168-2169
radical polymer charge transport and storage,　4:2165-2166
radical polymer configuration,　4:2166-2168
radical redox reactions,　4:2164-2165
polyradicals
history,　1:11-12
self-assembly,　1:237
polysilyl radicals, persistent and stable,　4:2117,2121-2141
polystyrene, see also styrenes, polymerizations
polystyrene oxammonium resins, oxidations,　2:1116
polythiophenes
polymer-based field-effect transistors,　4:2061-2066
polymer-based solar cells,　4:2070-2072
polyunsaturated fatty acids (PUFAs)
lipid isomerization,　3:1599,1602-1603,1615-1616
the metabolic syndrome,　3:1687-1690
peroxidation,　3:1577,1580-1581,1584,1588,1615-1616,1687-1690
structure,　3:1599,1600
population-balance equations, radical polymerization,　4:1739-1740
porous polymeric materials (polymer monoliths), organotellurium-mediated radical living polymerization,　4:1959-1960
porous silicon surfaces, biomolecule attachment, self-assembled monolayers,　4:2082-2083
positional isomer preference, supramolecular lipid organization,　3:1610-1612
postpolymerization functionalization, atom transfer radical polymerization,　4:1877-1878
postpolymerization modification, reversible addition fragmentation chain transfer, "click" chemistry,　4:1905,1913,1916
postsynthesis nanostructure modification, photochemical,　4:2206-2209
potassium organotrifluoroborates, radical generation,　2:617
Povarov cyclizations, electrochemically initiated,　2:1209-1210
power conversion efficiency (PCE), polymer-based solar cells,　4:2061,2068-2069,2071-2072,2074-2075
P(PSI2OD-DD) see N,N-dialkyl-1,7-dibromo-3,4,9,10-perylene diimide and dithienothiophene copolymer
PPVs see polyphenylenevinylenes
PQT see poly(3,3'''-dialkyl-quaterthiophene)
PRE see persistent radical effect
precipitation polymerization, industrial processes,　4:1720
precursors, photochemical radical-mediated metal nanostructure synthesis,　4:2198-2202
pre-equilibrium (initialization) stage, reversible addition fragmentation chain transfer polymerization,　4:1897,1898
preferred conformations, fullerenyl radicals,　4:2171,2172
preventive antioxidants,　3:1623,1624-1626
primary aliphatic carboxylic acids, Kolbe dimerizations,　2:1199-1200
primary amidyl radicals, additions to C=C bonds,　2:772
primary batteries,　4:2163
primary carbon radicals, 4-exo-trig cyclizations,　2:699
profluorescent spin labels and spin probes,　4:1985-1987
prokaryotes, lipid isomerization,　3:1617-1619
prolonged lifetime charge separated state, electron transfer,　1:365,366-370
propagation, radical chain reactions,　1:59-63,108
propagation cycle, SRN1 reactions,　1:334-335
propagation rate coefficients, polymerization kinetics,　4:1750-1752,1753-1755,1762-1766
propagation rate constant (kp), controlled/living radical polymerization,　4:1788-1789,1792-1793
propagation stage
industrial radical polymerization,　4:1712-1714
nitroxide-mediated polymerization,　4:1818,1819,1822-1825
polymerization kinetics,　4:1739-1740,1762-1770
radical polymerization,　4:1737
propane-1,2-diol dehydratase, mechanism,　3:1506,1507,1509,1510,1514
2-propanol, tin-free Barton-McCombie deoxygenations,　2:969
propargyl peroxy radicals, matrix isolation spectroscopy,　1:217
propargyl radicals
dimerization, combustion,　1:479
matrix isolation spectroscopy,　1:216-218
3,3,3-propellane, cascade synthesis,　2:736-737
propellanes, synthesis, manganese(III) acetate-mediated,　2:909
n-propyl radicals, matrix isolation spectroscopy,　1:213-214
protected dicarboxylic acids, anodic oxidations,　2:1197
protected metal nanoparticles, by self-assembly monolayers,　1:237-239
protecting groups, radical translocation,　1:137-139
protein radicals
alkoxyl radicals,　3:1431-1432
aromatic side chains,　3:1433-1436
backbones,　3:1436-1438
fates,　3:1430-1439
nitrogen-centered radicals,　3:1432-1433
peroxyl radicals,　3:1430-1431
side-chain carbon-centered radicals,　3:1430
sulfur-containing amino acids,　3:1433
translocation,　3:1438-1439
proteins
antioxidants,　3:1625-1627
backbones, radical chemistry,　3:1436-1438
cysteine, radical reactions,　3:1467
damage, sulfur-containing amino acid residues,　3:1459-1474
DNA cross links, oxidative lesions,　3:1338
electron transfer,　3:1475-1499
glycation, free radical production,　3:1681,1682
oxidation,　3:1425-1457
consequences,　3:1447-1448
factors affecting,　3:1426-1427
N-halo species,　3:1441-1443
photo-oxidation,　3:1443-1447
reactive nitrogen species,　3:1439-1441
reactive nitrogen species reactions,　3:1439-1441
repair,　3:1448-1450
singlet oxygen,　3:1445-1447
radical enzymes,　3:1501-1546
theoretical studies,　3:1547-1576
radical reactions,　3:1467,3:1428-3:1430
selenocysteine, radical reactions,　3:1467
side-chains
carbon-centered radicals,　3:1430
electron transfer, hopping mechanism,　3:1479-1481
radical production,　3:1430-1436
radical translocations,　3:1438-1439
spin labels and spin probes,　4:1967,1969-1970
structure
electron transfer effects,　3:1478
time resolved chemically induced dynamic nuclear polarization studies,　1:197-198
sulfur-containing amino acid residues, radical generation,　3:1605-1607
tandem protein-lipid damage, radical attack,　3:1607-1609
protonated histidine (His・2H+), hydrogen bonded to To1SQ,　1:229-230
protonated pyridines, arylations,　2:1076
protonation states
glutamate mutase reactions,　3:1555
one-electron oxidized guanine monomers, DNA radicals,　3:1384-1385
proton-coupled electron transfer (PCET)
hydrogen atom transfer mode,　1:325
peptides and proteins,　3:1482,1483
phenolic antioxidant action,　3:1653-1654,1661
sulfur-containing antioxidant action,　3:1666
proton-coupled hole transfer (PCHT), DNA, base cation to sugar radicals,　3:1375
proton electron double resonance imaging (PEDR1), spin probes,　4:1973-1974
protons, radiation-induced production,　1:395,396
proton transfer reactions
intra-base pair, DNA radicals,　3:1385-1386
termination of nitroxide-mediated polymerization,　4:1825
see also hydrogen atom transfer
proximal bisnitroxides, nitroxide-mediated polymerization,　4:1828
proxyl nitroxides, spin labels and spin probes,　4:1967
5 ps spin labeling, nucleic acids,　4:1971
PSC see polar stratospheric cloud
Pschorr reactions, synthetic strategies,　2:1059-1069
PSCs see polymer-based solar cells
pseudo radical enzymes,　3:1537-1539
mechanisms,　3:1502
methyl-coenzyme M reducatase,　3:1538-1539
2-oxoacid dehydrogenases/oxidases,　3:1538
PTBx see thieno[3,4-b]thiophene/benzodithiophene alternating copolymer
PTOC see pyridine-2-thioneoxycarbonyl
PTX see phenothiazine
p-type semiconducting polymers,　4:2061-2066
PUE see penultimate unit effect
PUFAs see polyunsaturated fatty acids
pulsed electrical discharge methods, gas phase isolated radical generation,　1:485
pulsed hyperthermal nozzle, flash vacuum pyrolysis,　1:208
pulsed-laser polymerization (PLP), kinetics,　4:1752-1755
pulse electron double resonance (PELDOR), nanometer distance measurements,　4:1971,1973
pulse radiolysis
radical reaction study,　1:397,423
gas phase,　1:399,400
organic solvents,　1:413,418
proteins/peptides,　1:409
redox potential determination,　1:257
pumiliotoxin C, synthesis, Barton-McCombie deoxygenations,　2:550
pump-probe methodology, characterization of photoinduced radicals,　1:298
(-)-punctatin, synthesis, Norrish reactions,　2:1229-1230
purification, industrial radical polymerization,　4:1719
purine 5',8-cyclonucleosides, DNA oxidation,　3:1338,1340
"push-pull" mechanism, coenzyme B12-dependent eliminases,　3:1510,1511
pyracylene unit, fullerene radicals,　4:2172
pyramidality see degree of pyramidality
pyranosides, C-2 branched, synthesis by sequential additions,　2:1147-1148
pyrazolophenanthridines, synthesis, intermolecular homolytic aromatic substitutions,　2:1062
pyrazolopyridines, synthesis, intermolecular homolytic aromatic substitutions,　2:1062
pyridines
arylations,　2:1076
manganese(II)-catalyzed synthesis,　2:785-786
pyridine-2-thioneoxycarbonyl (PTOC)
esters
history,　1:29-30
radical chain reaction initiation,　1:110,113-114
PTOC thiol method, radical clock calibration,　1:112-113
pyridinols, antioxidant action,　3:1645,1660-1661
pyrimidine hydroperoxyl radicals, DNA lesions,　3:1336-1338
pyrimidine-purine DNA intrastrand cross-links,　3:1335-1336
pyrimidinols, antioxidant action,　3:1645,1660-1661
pyrolysis, gas-phase isolated radical generation,　1:483-484
3,4-fused pyrroleo-3-sulfolenes, cycloadditions with fullerenes,　4:2180
pyrroles
alkylations,　2:1078
synthesis, enamine/β-dicarbonyl compound additions,　2:915
pyrrolidine derivatives
synthesis
iodomethylaziridine derivative annulations,　2:604
oxygen-centered radicals,　2:788-789
pyrrolidines
synthesis
amine-bearing electron-rich olefin oxidations,　2:1177-1178
from N-haloamines, hydrogen atom migration in acidic media,　1:129-131
radical [3+2] annulations,　2:605
pyrrolidinones, synthesis, alkyl radical azidations,　2:804
pyrrolizidines, synthesis, amidyl radical cascade reactions,　2:730-731
pyruvate formate lyase (PFL),　3:1562-1566
QM/MM see quantum mechanics/molecular mechanics
quantum-chemical calculations
electron paramagnetic resonance parameters,　1:155-156
monolayer generation on silicon surfaces,　4:2097-2098
quantum mechanics
isotropic electron paramagnetic resonance parameters,　1:155-156
reaction rate calculation,　1:100
quantum mechanics/molecular mechanics (QM/MM), hybrid procedures, radical enzymes,　3:1547-1548,1550,1551,1557-1558,1566
quantum yields, chain length magnitude, SRN1 reactions,　1:334-335
quaternary centers, installations, chiral Lewis acid-mediated fragmentations,　2:677-678
quenching of radicals
by metal ions, metal nanostructure synthesis,　4:2199,2200
β-carotene,　3:1670
phenolic antioxidants,　3:1627-1629
quinones
additions to B-alkylcatecholboranes,　2:611
additions to trialkylboranes,　2:609
H-abstraction,　1:286-287
R2R see roll-to-roll technique
radiation see ionizing radiation; light...; photo...; ultraviolet
radical acceptors
aliphatic asides,　2:1023-1027
azides,　2:1019-1036
heterocumulenes,　2:1048-1052
inorganic azides,　2:1034-1036
isonitriles,　2:1036-1048
isothiocyanates,　2:1049-1051
ketenes,　2:1051-1052
ketenimines,　2:1051-1052
organic azides,　2:1020-1034
sulfonyl azides,　2:1027-1031
unusual,　2:1019-1057
radical additions see additions
radical/anionic sequences, carbon-carbon bond sequential formation,　2:891-894
radical arylations see arylations
radical chain processes see chain reactions
radical characterization
electron paramagnetic resonance,　1:157-159
matrix isolation spectroscopy,　1:207-228
radical clocks,　1:107-124
acyl radicals,　1:118
advantages/disadvantages,　1:107-108
calibration methods,　1:112-114
carbon radicals,　1:114-117
competition kinetic studies,　1:107-108,110-114
cyckations,　1:89,111,113,114,116-117
kinetic EPR spectroscopy,　1:167
nitrogen radicals,　1:117-118
oxygen radicals,　1:118,119
phenolic antioxidant kinetics,　3:1635-1637
radical conjugate additions (RCA),　2:703-705
see also conjugate additions
radical decay curves, kinetic EPR spectroscopy,　1:165-167
radical dianions, room-temperature ionic liquids,　1:436-437
radical dications, room-temperature ionic liquids,　1:436-437
radical enzymes,　3:1501-1546
aromatic compound reduction,　3:1534-1536
biotechnological applications,　3:1539-1540
coenzyme Bia-dependent,　3:1548-1562
evolution,　3:1540-1541
glycyl radical enzymes,　3:1562-1568
isoprenoid biosynthesis,　3:1536-1537
ketyl radicals,　3:1525-1534
mechanisms,　3:1501,1502-1503
methyl-coenzyme M reductase,　3:1570-1574
oxygen initiated radicals,　3:1539
radical recycling,　3:1501,1502,1503
ribonucleotide reductase,　3:1568-1570
theoretical studies,　3:1547-1576
thiyl radicals,　3:1460
radical equilibrium electron paramagnetic resonance (REqEPR),　3:1642-1644
radical families, atmospheric chemistry,　1:505
radical-generating machinery, radical enzymes,　3:1502-1503,1504-1505
radical-guanine radical reactions, one-electron oxidation of DNA,　3:1305-1308
radical halogenations, history,　1:18
radical induction, photochemical processes,　1:275-300
radical inhibitors, history,　1:27-28
radical initiation,　1:37-55
chain reactions,　1:59,60,62,63
matrix isolation,　1:207-208
monolayer generation on silicon surfaces,　4:2089-2096
overview,　1:37-55
proteins,　3:1428
room-temperature ionic liquids,　1:434-435
thiol addition to unsaturated compounds,　4:2019,2020
radical initiators (RIs),　1:37-55
azo compounds,　1:39-40,43
chain processes,　1:40
controlled/living radical polymerization, chain end functionality,　4:1794-1797
heteroatom—heteroatom/carbon-metal,　1:40-41
history,　1:25-26
hydrogen abstraction,　1:48-49
induced decomposition, history,　1:27
organoboranes,　1:42-43,2:602-607
peroxides,　1:38-39,43
persistent,　1:41-42
photolysis,　1:43-49
radiolysis,　1:37,52
redox reactions,　1:37,50-52
thermolysis,　1:37-42
transition metal complexes,　2:1004
radical interconversions, atmosphere,　1:505,507,508-509,514-515
radical ion coupling
photocatalytic oxygenation of anthracene,　1:370-372
selective electron transfer reactions,　1:365,366
radical ion pairs
amines and fullerenes,　4:2186
radical rearrangements by fragmentation/recombination,　1:126-127
radical ion probes, cyclopropylcarbinyl→homoallyl rearrangements,　1:301
radical ions
chemically induced dynamic electron polarization studies,　1:202-203
clocks, cyclopropylcarbinyl→homoallyl rearrangements,　1:301
dianions/dications,　1:436-437
photocatalytic reactions, charge separation,　1:365-393
radiation-induced production in organic solvents,　1:410,412,413,414,417,418
selectivity versus neutral free radicals,　1:365
versus neutral radicals,　1:301-332
see also ionic liquids
radical mediators, chain reactions,　1:63-73
radical modification, industrial polymers produced by non-radical polymerization techniques,　4:1703
radical nucleophilic substitutions see SRN1 reaction
radical pair mechanism (RPM), chemically induced dynamic nuclear polarization,　1:177
radical pairs (RPs)
CIDNP,　1:175-179
recombination in solvent cage,　1:42
radical-polar crossover reactions, xanthates,　2:978-979
radical polymer, definition,　4:2164
radical polymer batteries,　4:2165-2166
configuration,　4:2166-2168
practical applications,　4:2168-2169
redox reactions,　4:2164-2165
radical polymerization (RP)
applications, industry,　4:1701-1736
benzyl methacrylate flow microreactor experiments,　2:1247,1249
block copolymers, RAFT,　4:1906-1916
chain end functionalities,　4:1788
chemically induced dynamic electron polarization studies,　1:200-202
chemically induced dynamic nuclear polarization,　1:189-190
composition control, ATRP,　4:1873
concentrations,　4:1785
control of topology/composition/functionality, ATRP,　4:1855,1869-1878
convergent synthesis, RAFT,　4:1906,1912-1916
dispersion, RAFT,　4:1923
divergent synthesis, RAFT,　4:1906,1907-1912
emulsions, RAFT,　4:1920-1924
end-group chemistry, RAPT,　4:1916-1919
flow microreactor experiments,　2:1247
fullerenes,　4:2180,2181
functionality control, ATRP,　4:1877-1878,1879
functional polymers, organotellurium radical living polymerization,　4:1958-1960
fundamental reactions,　4:1737-1738
fundamentals of controlled living process,　4:1785-1812
high molecular weight molecules, RAFT,　4:1901-1902
history,　1:28
industrial applications,　4:1701-1736
controlled reversible-deactivation processes,　4:1725-1731
importance,　4:1703
mechanistic aspects,　4:1704-1719
processes,　4:1719-1725
inhibition, RAFT agents,　4:1898
inhibitors, industrial radical polymerization,　4:1717-1718
initiation kinetics,　4:1739,1755-1762
initiation versus termination rates,　4:1785,1786
ionic polymerization process comparison,　4:1785
kinetics,　4:1737-1784
conversion effects on rate coefficients,　4:1742-1743,1773-1775
conversion of monomer into polymer,　4:1740-1743
disproportionation-to-combination ratio,　4:1776-1777
initiation,　4:1739,1755-1762
machinery,　4:1739-1755
propagation,　4:1739,1740,1762-1770
copolymerization,　4:1766-1770
rate coefficients,　4:1762-1766
stages,　4:1739-1740
termination,　4:1739-1740,1770-1777
living ends, RAFT,　4:1901-1902
low molecular weight molecules, RAFT,　4:1903
molecular architecture control,　4:1787-1788,1801-1802,1804-1805,1806
molecular weight control,　4:1931,1932
molecular weights, RAFT,　4:1899-1903
monomer range/functional groups, RAFT,　4:1903-1906
nitroxide-mediated,　4:1813-1850
number-average degree of polymerization, RAFT,　4:1899-1900
organoheteroatom-mediated living radical polymerization,　4:1931-1963
photoinitiation kinetics,　4:1761-1762
polymeric architecture, RAFT,　4:1806,1906-1916
population-balance equations,　4:1739-1740
propagation kinetics,　4:1739,1740,1762-1770
RAFT/ARTP combination,　4:1902
rate of conversion,　4:1740-1743
reaction schemes,　4:1739-1740
retardation, RAFT agents,　4:1898
reversible addition fragmentation chain transfer,　4:1895-1929
room-temperature ionic liquids,　1:434
styrene, nitroxide-mediated, flow microreactor experiments,　2:1248,1250
surface modification
conventional RP versus controlled/living RP,　4:1786,1787
kinetics,　4:1739-1740,1770-1777
radical thiol-ene process,　4:2048-2049,2050,2052
RAFT,　4:1897,1898,1902
termination
rate coefficients,　4:1752-1753,1770-1771
types,　4:1738
see also chain length-dependent termination; initiation-termination balance
thiol addition to unsaturated compounds,　4:2017,2019,2020
click chemistry
branched polymers,　4:2039,2041
functional polymers,　4:2033-2039,2040
polymer networks,　4:2041-2044
topology control, ATRP,　4:1873-1877
unique morphologies, RAFT,　4:1925
see also controlled/living radical polymerization
radical polymers, definition,　4:2164
radical process history,　1:25-30
radical quenching see quenching of radicals
radical-radical coupling, chain reaction termination,　1:60,62
radical-radical interactions, reactive oxygen species,　3:1268-1269
radical/radical sequences, carbon-carbon bond sequential formation,　2:890-891
radical reactivity ratios, copolymerization kinetics,　4:1768-1770
radical rearrangements see rearrangements
radical recombinations, room-temperature ionic liquids,　1:435-436
radical recycling, radical enzyme mechanisms,　3:1501,1502,1503
radical reductions cap reductions
radical scavengers
ascorbate,　3:1268,1271,1277
reactive oxygen species defence,　3:1268,1270-1271,1277
reduced glutathione,　3:1270,1271,1276,1277
thiyl radicals,　3:1270-1271
see also radical trapping
radical Smiles rearrangements, xanthates,　2:778-779
radical stability
boron-centered radicals,　1:469-470,471
carbon-centered radicals,　1:454-465
3-exo-trig cyclizations,　2:694-698
C-C bond cleavage,　1:451
definitions,　1:449-453,4:1965,2118
electronic stabilization,　1:57,58
gas phase,　1:477
history,　1:2,7,10
hydrogen transfer reaction,　1:449-450,451-452
hyperconjugative stabilization,　1:308,454,457
matrix isolation,　1:207-228
nitrogen-centered radicals,　1:451-453,468-469
oxygen-centered radicals,　1:451-453,466-468
relative stability scales, C-/S-/O-/N-/B-centered radicals,　1:470,472-473
silyl radicals,　4:2117
stabilization energies,　1:97-100
steric effects,　1:7,4:2120-2121
sulfur-centered radicals,　1:451-453,465-466
theoretical methods,　1:453-454
thermochemical aspects,　1:449-475
thermodynamic stability,　1:449-453,4:2118-2120
value tables,　1:455-456,459-462,465,466,467,468,470
radical stabilization energy (RSE),　1:97-100
bond dissociation energies relationship,　1:97-98
definitions,　1:450-453
electron paramagnetic resonance,　1:169-170
fragmentation step species, coenzyme B12-dependent enzymes,　3:1555-1556
silyl radicals,　4:2119,2120
value tables,　1:455-456,459-462,465,466,467,468,470
radical stabilizing groups, ring opening reaction rate effects,　1:305
radical substitutions
chain reactions,　1:60-61,62,63
see also SRN1 reaction
radical thiol additions to unsaturated compounds
bioorganic molecule synthesis,　4:2021-2033
click applications,　4:2021-2053
colloidal particles/surface chemistry,　4:2045-2052
mechanisms,　4:2017,2018-2020
polymers,　4:2033-2045
radical trapping
alkenylboron derivatives,　2:622-623
alkylborane species,　2:624
antioxidants,　3:1623,1627-1672
diboron species,　2:624
radiolysis,　1:395
acetone,　1:414-415
acetonitrile,　1:413-414
alcohols,　1:410-412
analysis of products/reactions,　1:396,397
condensed versus gaseous media,　1:397
gases,　1:397
hydrocarbons,　1:417-418
ionic liquids,　1:418-420
liquids,　1:400-420
methods,　1:396-397
principles,　1:395-396
radical initiation,　1:37,52
room-temperature ionic liquids,　1:434,437,441,443,444,445
solids,　1:420-423
solutions,　1:396
tetrahydrofuran,　1:412-413
water,　1:398,400-404
RAFT see reversible addition fragmentation chain transfer
RAGEs see receptors for advanced glycation end products
random copolymerization
nitroxide-mediated polymerization,　4:1840
organoheteroatom-mediated radical living polymerization,　4:1943-1944
random walk model
DNA excess electron transfer study,　3:1415,1416,1422
DNA hole transfer study,　3:1404-1405,1406,1413
rate coefficients, polymerization conversion effects,　4:1742-1743,1773-1775
rate constants
direct measurements,　1:107
indirect determination,　1:107
radical clocks,　1:107-124
synthetic planning,　1:107
unusual cyclizations,　2:695
rate of polymerization,　4:1740-1741
reaction profiles, electron transfer,　3:1477
reaction rates, controlled/living radical polymerization,　4:1787,1788-1797
reaction schemes, radical polymerization,　4:1739-1740
reactive nitrogen species (RNS)
diabetes,　3:1685
DNA reactions,　3:1283,1305-1307,1309-1310
generation in cells,　3:1284
inflammatory response,　3:1283,1284,1285-1286
lipid peroxidation,　3:1577
protein reactions,　3:1439-1441
reactive oxygen species (ROS)
biological chemistry,　3:1259-1281
cellular reactivity,　3:1285-1290
molecular versus radical species,　3:1285-1290
diffusion and compartmentalization,　3:1275-1277
DNA reaction kinetics,　3:1290-1311
drugs/xenobiotics,　3:1265-1266
evolution of life,　3:1261
fatty acids,　3:1685-1690
Fenton chemistry,　3:1272-1273
flavoprotein oxidases,　3:1264,1265
generation in cells, molecular pathways,　3:1283-1285
heme protein autoxidation,　3:1264-1265,1266
history,　3:1260-1261
inflammatory response,　3:1283-1312
intentional generation in cells,　3:1260-1261
interactions,　3:1267
kinetics,　3:1267,1268,1271,1273-1275
lipid peroxidation,　3:1577
mitochondria,　3:1261-1262
molecular,　3:1259,1260,1285-1290
NADPH oxidases,　3:1262-1264
nucleic acids, sugar radical formation,　3:1345-1370
nucleobase modifications,　3:1319-1344
properties,　3:1266-1272
radiation,　3:1265
radical and non-radical,　3:1259,1260,1288-1290
radical reactions,　3:1267-1271
reduction potential,　3:1266-1267
sources,　3:1261-1266
transition metals,　3:1272-1273
two-electron oxidants,　3:1271-1272
the metabolic syndrome
diabetic complications,　3:1693,1694
fatty acids,　3:1685-1690
hyperglycemia,　3:1681-1682,1683,1684
mitochondria,　3:1679,1681-1682,1683,1684,1686
obesity,　3:1691,1692
reactive species
atmospheric chemistry,　1:505
DNA reactions, inflammatory response,　3:1283-1317
reactivity control, silyl radicals,　4:2117
reactivity ratios, copolymerization parameters,　4:1715
reagent-induced activation
organic electron donors
aminium cation-radical salts,　2:842-844
ceric ammonium nitrate,　2:834-837
copper reagents,　2:840-841
hypervalent iodine reagents,　2:844
iron reagents,　2:837-840
manganese reagents,　2:841-842
real time observations, short-lived radicals/radical ions, magnetic resonance techniques,　1:175-206
rearrangements
chain reactions,　1:62
cyclopropylcarbinyl→homoallyl-type,　1:301-307
diradicals, history,　1:7-8
1,2-esters, 2-deoxy sugar synthesis,　2:1158
ester-substituted radicals,　1:125-129
history,　1:7-8,13
hydrogen atom migrations,　1:129-143
monoradicals, history,　1:7-8,13
not involving carbon skeleton reorganization,　1:125-145
radical chain reactions,　1:62
stannylaminyl radicals, aliphatic azide-derived,　2:1023
receptors for advanced glycation end products (RAGEs),　3:1684-1685
rechargeable batteries
conventional,　4:2163
organic,　4:2163-2169
rectifiers, protein-based,　3:1495
redox active transition metals, biological chemistry of reactive oxygen species,　3:1272-1273
redox cycling, reactive oxygen species generation by drugs and xenobiotics,　3:1265
redox-initiated polymerization, industrial radical polymerization,　4:1710
redox potential of radicals
definitions,　1:249-250
determination,　1:249,250-258
competitive q method,　1:253-255
computational electrochemistry,　1:258
cyclic voltammetry,　1:250-253
electrochemical techniques,　1:249,250-255
laser flash electron photoinjection,　1:255-256
photoelectrochemical techniques,　1:249,255-257
photomodulation voltammetry,　1:256-257
pulse radiolysis,　1:257
second harmonic voltammetry,　1:255
thermochemical cycles,　1:257-258
equilibrium constant correlation, ATRP,　4:1866-1868
tables,　1:258-270
redox properties,　1:249-273
evaluation techniques,　1:250-258
reactive oxygen species,　3:1266-1267
spin probes,　4:1982-1984,1985,1988
standards,　1:250
value tables,　1:258-270
redox reactions
cascade reactions,　2:746-763
radical initiation,　1:37,50-52
radical polymer batteries,　4:2164-2165,2166-2167
redox regulation, reactive oxygen species in biological systems,　3:1261,1277-1278
redox status determination, spin probes,　4:1982-1984,1985,1988
redox switching
catenanes,　1:241
rotaxanes,　1:243,244
reduced flavin electron donor, DNA excess electron transfer study,　3:1415
reduced glutathione (GSH) see glutathione (reduced)
reducing agents, catalyst regeneration, atom transfer radical addition/cyclization,　4:1880-1882
reducing radicals, water radiolysis,　1:402,403-404
reduction potentials
definition,　1:249
DNA nucleobases,　3:1398-1399
radicals, tables,　1:258-267
standard,　1:250
reductions
aldehydes, samarium diiodide,　2:857-860
aliphatic azides, dichlorindium bromide,　2:1026
alkoxyl radical fragmentations, carbohydrates,　2:1168-1169
alkyl halides,
nickel-mediated, electrochemically initiated,　2:1208-1211
samarium diiodide,　2:856-857
tris(trimethylsilyl)silane-mediated,　2:1244-1246
amides, samarium diiodide,　2:860
aromatic azides
dichlorindium bromide,　2:1026
triethylsilane,　2:1025-1026
tris(trimethylsilyl)silane,　2:1026
aromatic compounds, radical enzymes,　3:1534-1536
aryl esters, samarium diiodide,　2:860
borohydride-mediated,　2:621
boron derivatives,　2:620-622
carbonyls, samarium diiodide, reaction mechanisms,　2:853-856
carboxylic acids, samarium diiodide,　2:860
conjugated aldol cyclizations, samarium diiodide-mediated,　2:888-889
dialkyl nitroxides,　2:1096
1,3-diesters, samarium diiodide,　2:860
electrochemical nickel-mediated, alkylhalides,　2:1208-1211
electron-deficient alkenes, samarium diiodide,　2:863
esters
samarium diiodide, synthetic applications,　2:860
silicon surfaces, functionalized monolayers,　4:2104-2106
followed by coupling with electrophiles,　1:289
glycosyl pyridyl sulfones, aldehydes/ketones, 1,2-trans-C-glycosides synthesis,　2:1137
halides, organoboranes,　2:602-603
α-heteroatom-substituted carbonyl groups, samarium diiodide,　2:860-862
1-iodoadamantane, fluorous tin hydride-mediated,　2:536
ketones
electrochemical coupling,　2:1211-1212
samarium diiodide,　2:857-860
lactones, samarium diiodide,　2:860
Lewis acid-mediated, α-iodo-β-alkoxyesters,　2:662-663
reductions (continued)
molecular oxygen, tris(trimethylsilyl)silane,　2:568-569
multiply-bonded silicon compounds, stable anion radicals,　4:2135-2137
nickel-mediated, alkylhalides,　2:1208-1211
nitrogen-containing compounds, samarium diiodide, synthetic applications,　2:862-863
noble metal ions, nanoparticle synthesis,　4:2197,2202
nonanomeric C-radicals, carbohydrate synthesis,　2:1158-1160
nucleosides, tris(trimethylsilyl)silane,　2:570
one- and two-electron reductions, fullerenes,　4:2190
organohalides, samarium diiodide,　2:852-853
phosphine selenides, tris(trimethylsilyl)silane,　2:565-566
phosphine sulfides, tris(trimethylsilyl)silane,　2:565-566
radical initiation,　1:50-51
reactive oxygen species,　3:1267,1269
ruthenium-mediated photocatalysis, alkyl halides,　2:1225-1226
silane-mediated,　2:561-599
silylenes, stable anion radicals,　4:2137-2138
stereoselective, α-alkoxy radicals,　2:656
sulfur-containing compounds, samarium diiodide;　2:863-864
thyiyl radicals,　3:1461
tris(silyl)-substituted silyl radical generation,　4:2124-2125
tris(silyl)-substituted silyl radicals,　4:2130
tris(trimethylsilyl)silane-mediated, alkyl halides, flow microreactor experiments,　2:1244-1246
xanthates, N-heterocyclic carbene boranes,　2:621
reductive alkylations
chiral Lewis acid-mediated
α,β-disubstituted enoyls,　2:674-675
enones,　2:676-677
template effects,　2:673-674
α,β-disubstituted enoyls, chiral Lewis acid-mediated,　2:674-675
enones, chiral Lewis acid-mediated,　2:676-677
stereoselective, chiral Lewis acids,　2:672-676
reductive cleavage
alkyl halides, trisffrimethylsilyllsilane,　2:569-570
chalcogens, tris(trimethylsilyl)silane,　2:562-564
ruthenium-mediated photocatalysis, C-Br bonds,　2:1225-1226
reductive coupling
alkenes, ethyl 2-(benzenesulfonylamino)acrylate,　2:613
cyclopentane derivative synthesis,　2:1151
hydrazones, ketones, electrochemically initiated,　2:1211-1212
imines, samarium diiodide,　2:876
ketones
hydrazones, electrochemically initiated,　2:1211-1212
nitrones, electrochemically initiated,　2:1211-1212
oximes, electrochemically initiated,　2:1211-1212
nitrones, ketones, electrochemically initiated,　2:1211-1212
oximes, ketones, electrochemically initiated,　2:1211-1212
reductive cyclizations
carbonyl groups,　2:1206-1208
electrochemically initiated,　2:1206-1209
iron-catalyzed, 6-halo-l-hexene,　2:1012
ketones,　2:1206-1208
silanes,　2:602
tandem, polyenes,　2:1209
reductive decarboxylations, tin hydride-mediated, cyclopropanes,　2:547
reductive dehalogenation, tri-n-butyltin hydride mediated,　1:64
reductive (electron-loss) pathway, DNA radical formation,　3:1373,1374-1375
reductive one-electron transfer, radical generation by enzymes,　3:1502
reductive opening
epoxides, alcohol formation,　2:990-993
titanocene-catalyzed, epoxides,　2:992-993
reductive removal of functional groups, radical chain reactions,　1:66-69
reductive tandem cyclizations, polyenes,　2:1209
reformation, alkoxyamine C-ON bonds, nitroxide-mediated polymerization,　4:1831-1833
Reformatsky reactions, samarium diiodide-mediated,　2:884-887,889
regiochemical trends, Δ-5-hexenyl radicals/radical anions,　1:322-323
regioregularity, polythiophenes, polymer-based field-effect transistors,　4:2061-2062
regioselectivity
additions, thiyl radicals to vinylidenecyclopropane,　2:800
4-exo-trig cyclizations,　2:698-702
cyclizations
aryl radicals,　2:721
6-hepten-l-one radical anions,　1:321-322
Δ-5-hexenyl radicals,　1:318
ring size effects,　2:712
γ-lactone synthesis,　2:904-905
lipid peroxidation,　3:1579-1580
propagation, industrial radical polymerization,　4:1712-1713
relative radical stabilization energies,　1:97-100
relative stability scales, C-/S-/O-/N-/B-centered radicals,　1:470,472-473
relaxation phenomena, electron paramagnetic resonance,　1:148-150
relay amino acids (relay stations)
electron transfer in peptides/proteins,　3:1480-1487
aromatic amino acids,　3:1481-1484
sulfur-containing amino acids,　3:1484-1487
trimethoxyphenylalanine,　3:1480-1481
relay cyclizations, tetrahydrofuran synthesis, (-)-amphidinolide K core,　2:736
remote functionalizations
photoinduced,　2:1231-1235
radical history,　1:29
reorganization energy, electron transfer rate,　3:1475,1477
REqEPR see radical equilibrium electron paramagnetic resonance
reservoir species, stratospheric chemistry,　1:508,509-510
resonance, reaction rate prediction,　1:100
resonance-delocalized radicals, stability measurement,　1:452-453
resonance stabilization
carbon-centered radicals,　1:454-455,457
imidoyl radicals,　2:1038-1039
resonance structures, isonitriles,　2:1036
resorcinols, antioxidant action,　3:1657-1659
respiration
electron transfer in proteins,　3:1475,1476
reactive oxygen species generation,　3:1261-1262
reverse atom transfer radical polymerization,　4:1861-862
reverse-phase high performance liquid chromatography (RP-HPLC), DNA oxidation products,　3:1322
reversible addition fragmentation chain transfer (RAFT) polymerization
advantages/limitations,　4:1807
agents,　4:1896
aqueous homogeneous,　4:1919-1920
ATRP combination,　4:1902
block copolymers
convergent synthesis,　4:1912-1916
divergent synthesis,　4:1907-1912
controlled architecture,　4:1806,1906-1916
degenerative transfer processes,　4:1786,1787,1805-1806
emulsions,　4:1920-1924
end-group chemistry,　4:1916-1919
homogeneous/heterogeneous processes,　4:1919-1925
industrial processes,　4:1726,1730-1731
kinetics,　4:1898-1899
low molecular weight polymer preparation,　4:1903
mechanism,　4:1896-1898
molecular weights,　4:1899-1903
distribution,　4:1899-1901
range/control,　4:1901-1903
monomer range/functional groups,　4:1903-1906
monomers/initiators,　4:1805-1806
organoheteroatom-mediated radical living polymerization comparison,　4:1955
polydispersities,　4:1900,1901,1902,1903
polymeric architectures,　4:1806,1906-1916
radical initiators, chain end functionality,　4:1794-1795
radical polymerization,　4:1895-1929
radical thiol-X click chemistry,　4:2033,2036,2041
transfer agents,　4:1806
transfer constants,　4:1899,1901
unique morphologies,　4:1925
universal agents,　4:1908,1910,1912
reversible additions, lipid isomelization, nitrogen centered radicals,　3:1604
reversible chain transfer-catalyzed polymerization (RTCP),　4:1933-1937,1939-1944,1949,1960
see also organoiodine-mediated radical living polymerization
reversible deactivation of growing chain, controlled/living radical polymerization,　4:1726
reversible redox reactions, radical batteries,　4:2164-2165,2166-2167
reversible termination (RT) mechanism
organoheteroatom-mediated radical living polymerization,　4:1953-1954,1956
see also persistent radical effect
rhenium-centered radicals, fullerene addition,　4:2183
rhodium-catalyzed reactions, hydroborations,　2:612
ribonucleosides
C2' sugar radicals,　3:1361,1362
C3' sugar radicals,　3:1359
C4' sugar radicals,　3:1356-1357
C5' sugar radicals,　3:1352
ribonucleotide reductases (RNRs),　3:1503-1505
classes,　3:1503-1504
electron transfer,　3:1475,1477,1483,1485,1493-1495
mechanism,　3:1505,1507
oxygen initiation,　3:1539
radical generation,　3:1504-1505
theoretical studies,　3:1568-1570
ring closures
5-exo/6-exo radical cyclizations followed by SRN1 reaction,　1:344
acyl radicals, at silicon,　2:648-649
at germanium,　2:650-653
at oxygen,　2:644-645
at selenium,　2:637-644
at tellurium,　2:637-641
at tin,　2:650-653
chiral sulfoxides,　2:636
10-exo-trig closures, benzylic radical synthesis,　2:714-715
EPR studies,　1:169
homolytic substitutions,　2:629-654
intramolecular SRN1 reactions,　1:344-347
kinetics,　2:632-635
β-lactams,　2:640-641
leaving groups,　2:634-635
SRN1 reactions,　1:333,342-347
sulfurs,　2:635-637
O-trityl oximes, diphenyl diselenide effects,　2:809-810
vinyl iodides, at silicon,　2:648
ring conformation study, methyl radical spin probes, EPR,　1:158
ring expansions
cobalt-mediated, cyclopentane-1,3-diones, electrochemically initiated,　2:1210-1211
cycloketones, tris(trimethylsilyl)silane,　2:581-582
electrochemically initiated
cyclopentane-1,3-diones,　2:1210-1211
oxazolidines, vinyl ethers,　2:1205
history,　1:9
lactam synthesis, organic azides,　2:1023-1024
one-carbon, cycloketones, tris(trimethylsilyl)silane,　2:581-582
oxazolidines, vinyl ethers, electrochemically initiated,　2:1205
ring formation
A rings, 1,22-dihydroxynitiane nitiol analogs,　2:1228
xanthate transfers,　2:976-981
ring opening
aziridines, N-tosylamino radical formation,　2:778
cerium(IV) ammonium nitrate-mediated,　2:932-935
cyclopropane, radical anions,　1:303-304
cyclopropanol silyl ethers,　2:934
epoxides, alcohol formation,　2:990-993
EPR studies,　1:168
industrial radical polymerization,　4:1713
iron(III) salt-mediated,　2:932-935
ketyl radical anions,　1:302-307
manganese(III) acetate-mediated,　2:932-935
metal-dependent,　2:932-935
titanocene-mediated, epoxides,　2:990-993
ring opening polymerization (ROP), industrial,　4:1713
RIs see radical initiators
RNA
ribonucleoside sugar radicals,　3:1352,1356-1357,1359,1361,1362
spin labels and spin probes,　4:1970-1971
RNRs see ribonucleotide reductases
RNS see reactive nitrogen species
roll-to-roll (R2R) technique, polymer-based solar cells,　4:2076-2077
room-temperature ionic liquids,　1:433-443
aromatic anions,　1:442-141
cations,　1:411-146
ionization of ions,　1:436-438
nonaromatic anions,　1:438-442
radiation-induced radical reactions,　1:418-420
room-temperature magnetic bistability, thiazyl radicals,　4:2148-2151
ROP see ring opening polymerization
ROS see reactive oxygen species
rotational dynamics, room-temperature ionic liquids,　1:434
rotaxanes,　1:239-244
electrochemical switching,　1:241,242-244
molecular shuttles,　1:240,241-244
paramagnetic,　1:244
structure,　1:239,240
RO-X compounds, oxygen-centered radical formation,　2:781-782
RP HPLC see reverse-phase high performance liquid chromatography
RPs see radical pairs
RSE see radical stabilization energy
RT see reversible termination
RTCP see reversible chain transfer-catalyzed polymerization
ruthenium-catalyzed reactions
aerobic oxidations, alcohols, nitroxide-mediated,　2:1119-1121
atom transfer radical additions,　2:955-956
atom transfer radical cyclizations,　2:955-956
reoxidants, nitroxides,　2:1106
ruthenium complexes
atom transfer radical addition/cyclization,　4:1880,1882
atom transfer radical polymerization,　4:1859,1860
ruthenium-mediated photocatalysis
C-H functionalizations, indoles,　2:1226-1227
[2+2] cycloadditions, enones,　2:1221-1222
reductions, alkyl halides,　2:1225-1226
reductive cleavage, C-Br bonds,　2:1225-1226
synthetic strategies,　2:1221-1227
SA see stilbene dicarboxamide
saccharides
synthesis, radical thiol additions,　4:2022
see also disaccharides; sugars
salt effects, nitroxide-mediated polymerization,　4:1835-1836
SAM (S-adenosylmethionine) see adenosylmethionine
samariations, intermolecular, C-disaccharide synthesis,　2:1139-1141
samarium complex-catalyzed reactions, cascades,　2:759-760
samarium diiodide
additive effects,　2:850-852
aldol-type reactions,　2:884,887-889
asymmetric reductions,　2:859
Barbier reactions,　2:879-884
carbonyl-alkene coupling,　2:870-877
carbonyl-arene cyclizations,　2:875-876
cyclopentane derivative synthesis,　2:1151-1152
ester carbonyl-alkene cyclizations,　2:876-877
fragmentations, ketones,　2:859-860
glycosyl pyridyl sulfone reductions
C-disaccharide synthesis,　2:1140
1,2-trans-C-glycosides synthesis,　2:1137
Grignard reactions,　2:879-884
imine pinacol coupling,　2:868-870
intermolecular carbonyl-alkene coupling,　2:871-872
intermolecular pinacol coupling,　2:865-866
intramolecular carbonyl-alkene coupling,　2:872-876
intramolecular pinacol coupling,　2:866-868
pinacol coupling,　2:864-870
reductions
aldehydes,　2:857-860
alkyl halides,　2:856-857
amides,　2:860
carbonyls, reaction mechanisms,　2:853-856
carboxylic acids,　2:860
electron-deficient alkenes,　2:863
esters,　2:860
α-heteroatom-substituted carbonyl groups,　2:860-862
ketones,　2:857-860
nitrogen-containing compounds,　2:862-863
organohalides,　2:852-853
sulfur-containing compounds,　2:863-864
reductive coupling, imines,　2:876
Reformatsky reactions,　2:884-887
synthetic applications,　2:849-900
samarium intermediates, glycos-l-yl radicals, C-glycoside synthesis,　2:1137
samarium iodide, Lewis acid-mediated diastereoselective reactions,　2:663-664
samarium-mediated reactions, asymmetric electron transfers,　2:686-687
SAMs see self-assembled monolayers
Sandmeyer borylations,　2:624
sarcosine esters, fullerene photochemical reactions,　4:2187
saturated fatty acids, free-radical-mediated lipid peroxidation,　3:1580
saturation effects, radical stability,　1:458,468
SBRP see stibine-mediated living radical polymerization
scandine, additions, C60,　2:1217-1218
Schmittel cycloaromatizations,　2:710-711
Schreiner-pascal cycloaromatizations,　2:710-711
Schulz-Flory distribution, chain-length distribution, polymerization kinetics,　4:1744,1745
Schwartz reagent, zirconium-catalyzed reactions,　2:1015-1016
β-scission
alkoxy radicals,　2:783-785
cyclopropanols,　2:785
polymerization kinetics,　4:1756,1760,1761,1780-1781
SDSL see site-directed spin-labeling
SEC see size-exclusion chromatography
secondary amines, synthesis; tris(trimethylsilyBsilane,　2:565
secondary batteries,　4:2163
see also rechargeable batteries
secondary organic aerosol (SOA), troposphere,　1:514,519,525
second harmonic alternating current voltammetry (SHV), redox potential determination,　1:255
secrotome, adipose tissue,　3:1691
seeded emulsion polymerization, reversible addition fragmentation chain transfer,　4:1921-1922
seeded growth, metal nanoparticles,　4:2206,2208
selective radical generation
radiolysis
halogenated hydrocarbons,　1:416
ionic liquids,　1:419
organic solvent,　1:410,412
water,　1:401-404
selectivity, radical ions versus neutral free radicals,　1:365
selenacephalosporin, synthesis,　2:640
selenapenam, synthesis,　2:640
5-selenapentopyranose derivatives, synthesis,　2:641
selenides
intramolecular homolytic substitutions, kinetics,　2:633-634
phosphine, reductions, tris(trimethylsilyl)silane,　2:565-566
stereoselective atom transfer radical additions/cyclizations,　2:958
selenium
intramolecular homolytic substitutions,　2:582,630-631
tandem radical homolytic substitutions,　2:641-644
selenium-carbon bonds
cleavage
photoinduced mesolytic,　1:296
tin-hydride mediated,　2:550-551
formation, carbohydrate synthesis,　2:1164-1165
selenium-centered radicals
additions, insaturations,　2:808-809
chemistry,　2:804-810
homolytic substitutions,　2:805-808
silicon substitutions,　2:805-806
substitutent effects,　2:804-805
thioselenations, isocyanide,　2:807
tin substitutions,　2:805-806
selenium-containing amino acids
functions,　3:1459
radical reactions,　3:1459,1466-1467,1472
structure,　3:1461
selenium-containing organic molecules, antioxidant action,　3:1625
selenium-selenium bonds, photoinduced mesolytic cleavage,　1:296-297
selenium-silicon bonds, photoinduced mesolytic cleavage,　1:296-297
selenocarbonates, cyclic, synthesis,　2:642
selenochromanes, synthesis,　2:642-643
selenocysteine (SeCys)
cellular function,　3:1459
proteins, radical reactions,　3:1467
radical reactions,　3:1466-1467
structure,　3:1461
selenoesters, synthetic applications,　2:805-809
selenoethers, radical generation, tin hydride-mediated,　2:550-551
selenols, hydrogen transfer to radicals,　3:1460
selenomethionine (SeMet)
cellular function,　3:1459
hydrogen atom radical reactions,　3:1472
structure,　3:1461
selenomilfasartan, synthesis,　2:641
selenothioethers, radical reactions,　3:1467,1472
selenotocopherol, synthesis,　2:639
self-assembled monolayers (SAMs)
α-helical peptides, electron transfer,　3:1488,1496
protection of metal nanoparticles,　1:237-239
silicon surfaces,　4:2081-2116
attachment methods,　4:2089-2096
experimental/theoretical modeling studies,　4:2096-2100
functionalization,　4:2101-2112
perspectives,　4:2112-2114
radical chain propagation,　4:2084-2089
surface preparation,　4:2082-2083
thiol addition to unsaturated compounds,　4:2049-2052
self assembly
colloidal metal nanoparticles,　4:2197-2210
free radicals,　4:1999,2000-2004
lipophilic guanosines,　1:237,238
mechanical interlocking of free radicals,　1:239-244
metal nanoparticle protection,　1:237-239
polyradicals,　1:237
supramolecular radical chemistry,　1:237-244
self-immolative protecting groups, radical translocation,　1:139,140
self-initiated autoxidation, β-carotene,　3:1670,1671
self-termination reactions, nitroxide-mediated polymerization,　4:1825-1826
semibatch (semicontinuous) reactors, industrial radical polymerization,　4:1725
semiconductors
organic molecule substitutes in electronic devices,　3:1495-1497
polymer-based field-effect transistors,　4:2061-2067
n-type,　4:2066-2067
p-type,　4:2061-2066
silicon, surface monolayers,　4:2081-2116
semiquinone radical anions, hydrogen bond effects,　1:229-230
semiquinones, redox cycling,　3:1265,1268
semiquinone state of fiavin
oxygen initiated radical enzymes,　3:1539
SAM-dependent enzymes,　3:1503,1529-1534,1538
semi-radical-mediated polymerization (SRMP),　4:1726
SEPR see steady-state EPR
sequential processes
atom transfer radical addition/cyclization,　4:1882-1884
organic transformations,　4:1884-1887
carbon-carbon bond formation, samarium diiodide-mediated,　2:890-895
radical cyclization-intermolecular trapping, branched-chain sugar synthesis,　2:1146-1147
sequential proton loss electron transfer (SPLET), hydrogen atom transfer mode,　1:324-325
serum proteins, antioxidant action,　3:1625
SET see single electron transfer
SET-CRP see single-electron-transfer-controlled radical polymerization
seven-membered carbocycles, synthesis,　2:1154-1155
SF6 see sulfur hexafluoride
SFRP see stable free radical polymerization
SG1, nitroxide-mediated polymerization,　4:1814,1821,1826,1827,1838,1839
SG-1 (acyclic phosphonylated α-hydro nitroxide), industrial nitroxide-mediated polymerization,　4:1728-1729
Sharpless epoxides, ring opening, enantioselective 5-exo cyclizations,　2:997-998
1,2-shift, esters, radical rearrangements,　1:125-129
short-lived radicals/radical ions, magnetic resonance techniques,　1:175-206
short timescales, radical study by CIDEP/CIDNP,　1:175-204
shrinkage, industrial radical polymerization,　4:1713
SHV see second harmonic alternating current voltammetry
side-chain carbon-centered radicals, proteins,　3:1430
side-chain functional polymers, synthesis, radical thiol-X click chemistry,　4:2033,2035-2037
side reactions, radical thiol addition to unsaturated compounds,　4:2017,2020
σ-bond homolysis, radical generation by enzymes,　3:1502,1506,1509
σ-radicals
geometries, electron paramagnetic resonance,　1:156
stability,　1:463-465
signaling
lipid peroxidation products,　3:1594
radical modification of enzymes,　3:1459
reactive oxygen species,　3:1262,1264,1274
signatures, photoionization of gas phase radicals,　1:487-488
silacycles, synthesis,　2:646
silanes
consecutive radical reaction mediation,　2:574-595
phenol derivative transformations,　2:594-595
polarity reversal catalysts,　2:572-574
reductions,　2:561-599
reductive cyclizations,　2:602
tin-free Barton-McCombie deoxygenations,　2:967-970
silica, organosilicas, 9-mesityl-10-methylacridinium ion immobilization,　1:369-370
silicon, intramolecular homolytic substitutions,　2:632,645-650
silicon-carbon bonds
formation, tris(trimethylsilyl)silane,　2:566-568
photoinduced mesolytic cleavage,　1:292-293
self-assembled monolayers,　4:2081,2084-2089
silicon-centered radicals
5-endo-dig cyclizations,　2:706
electron paramagnetic resonance,　1:161-162
fullerene reactions,　4:2183,2184
history,　1:19
silicon hydrides
defunctionalizations,　2:571-572
unimolecular chain transfers,　2:948
silicon-mercury bond cleavage, tris(silyl)-substituted silyl radical generation,　4:2124
silicon-selenium bonds, photoinduced mesolytic cleavage,　1:296-297
silicon semiconductors, surface monolayers,　4:2081-2116
silicon-silicon bond cleavage, tris(sily1)-substituted silyl radical generation,　4:2122,2124
silicon surfaces,　4:2081-2116
alkene attachment,　4:2085-2086
hydrogen terminated Si(100)/Si(111)
oxidation,　4:2083-2084
preparation,　4:2082-2083
self-assembled monolayer growth,　4:2084-2089
monolayer generation
adventitious oxides/glass reaction vessels,　4:2091-2092
diazonium salts,　4:2092-2093
exciton-mediated initiation,　4:2093-2096
experimental/theoretical modeling studies,　4:2096-2100
fluoride-catalyzed attachment,　4:2096
functionalization,　4:2101-2112
halogen impurity effects,　4:2088-2089
neutral attachment,　4:2096
perspectives,　4:2112-2114
quantum-chemical calculations,　4:2097-2098
radical cations initiation, experimental models,　4:2099-2100
radical initiation,　4:2089-2096
thermal attachment,　4:2089
TTMSS models,　4:2098-2099
UV attachment,　4:2089-2091
oxidation,　4:2081,2082,2083-2084
radical cations initiation, experimental models,　4:2099-2100
self-assembled monolayers,　4:2081-2116
siloxyl monolayers,　4:2087-2088
silyl radicals,　4:2117
surface-centered sayl radicals, monolayer generation,　4:2089-2096
TTMSS models,　4:2098-2099
vinyl radical reactions,　4:2086-2087
N-siloxyenamine, ketone α-alkylations,　2:606
siloxyl monolayers, silicon surfaces,　4:2087-2088
siloxy substituted cylopropanes, ring opening/expansions,　1:309-310
silver-catalyzed reactions,　2:1014
silver complex-catalyzed reaction cascades,　2:756-757
silver nanoparticles
AuCl4- ions, photochemical radical-mediated metal nanostructure synthesis,　4:2202,2203
light induced morphology/size changes,　4:2207-2208
radical-mediated photochemical synthesis,　4:2198,2201,2202,2205-2206
silver radicals, photochemical nanostructure synthesis,　4:2203
α-silyl acetic acids, Kolbe dimerizations,　2:1200-1201
silylated cyclohexadienes
chain reactions,　2:571,573
cyclizations, dienes,　2:594
hydrosilylations, dienes,　2:594
silylated tertiary amines, photoinduced additions, alkynes,　2:1218-1219
silylations, electrochemically initiated, piperidine derivatives,　2:1205
silylenes, reduction, stable anion radicals,　4:2137-2138
silyl enol ethers, cyclizations, metal-dependent,　2:928-929
silyl ether-based protecting groups, hydrogen atom abstraction,　1:138
silyl ethers, cyclopropanol, ring opening, metal-dependent,　2:934
silylheptadienes, cyclizations,　2:739-740
silyllithium radicals, persistent and stable,　4:2138-2140
silylmethyl radicals, 5-endo-trig cyclizations,　2:705-706
silyl radicals
anion radicals,　4:2135-2138
applications,　4:2117
bis(silyl) silicon-centered radicals,　4:2132-2135
conformational analysis in solution, stable radicals,　4:2131-2132
electron paramagnetic resonance parameters,　4:2126-2127,2128,2131
kinetic stabilization,　4:2120-2121
metal substituted,　4:2137-2143
outlook,　4:2143-2144
persistent and stable,　4:2117-2146
anions and metal-substituted radicals,　4:2135-2143
bis(silyl)-substituted radicals,　4:2132-2135
tris(silyl)-substituted radicals,　4:2121-2132
polysilyl radicals,　4:2117,2121-2141
silicon surface chemistry,　4:2117
stability control,　4:2118-2121
structures,　4:2121
thermodynamic stabilization,　4:2118-2120
tris(silyl)-substituted,　4:2121-2132
X-ray crystallography,　4:2125-2126
1,n-silyl translocations, intramolecular homolytic substitutions,　2:650
simultaneous reverse and normal initiation (SR&NI), atom transfer radical polymerization,　4:1862
single bonds, carbon-centered radicals,　1:57,58
single-electron oxidations see one-electron oxidations
single-electron-transfer-controlled radical polymerization (SET-CRP), industrial processes,　4:1730
single-electron transfer (SET)
amines and fullerenes,　4:2186
cyclopropylcarbinyl→homoallyl rearrangement,　1:301
mechanistic enzyme inhibitors,　1:310
nitroxide-mediated,　2:1104-1108
photoinduced
followed by radical cation fragmentation,　1:291
nucleophiles,　1:289
ring opening, N-cyclopropylbenzylamine radical cation,　1:310
versus hydrogen atom transfer, tertiary amine oxidation,　1:310
single-molecules, biomolecular electronic devices,　3:1397,1412,1413,1495,1496,1497
single-pulse pulsed-laser polymerization (SP PLP), termination rate coefficients,　4:1752-1753
single-step electron transfer,　3:1475,1477-1478
single strand breaks (SSBs), DNA damage,　3:1373,1390-1391
singlet oxygen
cholesterol oxidation,　3:1587
DNA oxidation,　3:1319,1320-1321,1333
guanine oxidation,　3:1320-1321,1326
lipid oxidation,　3:1578,1579
protein damage,　3:1445-1447
quenching, β-carotene,　3:1670
singly occupied molecular orbitals (SOM0s)
DNA radicals,　3:1380,1339-1390,1393
heterocyclic thiazyl radicals,　4:2148
SOMO catalysis
cascade cycloadditions,　2:683-684
enantioselective reactions,　2:680-684
polycyclic product synthesis,　2:683-684
ruthenium-mediated photocatalysis,　2:1224-1225
stereoselective radical cyclizations,　2:658
site-directed spin-labeling (SDSL),　4:1967,1970,1971
six-membered rings, synthesis,　2:709-711,742-745
size-exclusion chromatography (SEC),　4:1744,,1748,1762,1763,1765
small cycles, unusual cyclizations,　2:694-702
small models, radical enzymes,　3:1547
small molecule antioxidants,　3:1624-1625,1627
small molecule chain transfer, radical polymerization kinetics,　4:1739,1777-1778
small molecule synthesis, atom transfer radical addition/cyclization,　4:1855,1880-1887
small reactive species
DNA damage,　3:1283-1317
DNA reaction kinetics,　3:1290-1311
generation in cells,　3:1283-1290
inflammatory response,　3:1283-1312
smart cards, radical batteries,　4:2168-2169
Smiles rearrangements, xanthates,　2:778-779
SOA see secondary organic aerosol
SOD see superoxide dismutase
sodium π-butyltellurolate, selenium/tellurium heterocycle formation,　2:638-639
solar cells
basic principles,　4:2059
see also polymer-based solar cells
solid phase, radiation-induced radical reactions,　1:420-423
solid-state chemically induced dynamic nuclear polarization studies,　1:199
solid-state heterocyclic thiazyl radicals,　4:2147-2161
solution based thermal dissociation, "cage" effect,　1:42
solution polymerization systems
industrial processes,　4:1720
nitroxide-mediated polymerization,　4:1820-1822
solvated electrons, radiolysis of ionic liquids,　1:418-419
solvation effects, DNA radical properties,　3:1383-1384
solvent cages, thermolysis,　1:42
solvent effects
Δ-5-hexenyl radical cyclization,　1:319-320
nitroxide-mediated polymerization,　4:1835
phenolic antioxidant action,　3:1654-1655
reaction rates,　1:81
solvents
controlled/living radical polymerization,　4:1791-1792
effects on redox properties,　1:249
high-energy radiation effects,　1:396
one-electron oxidation of guanine,　3:1297-1298
organic, radiolysis,　1:410-418
water, radiolysis,　1:400-410
SOMOs see singly occupied molecular orbitals
soot, formation in combustion,　1:479
Sp see spiroiminodihydantoin
spatial control, photochemical radical-mediated metal anostructure synthesis,　4:2198
SPB see surface plasmon band
species X, persistent radical effect, controlled/living radical polymerization,　4:1786-1787
rac-specionin, total synthesis,　2:1227-1228
spectroscopic methods
characterization of photoinduced radicals,　1:297-298
combustion engine research,　1:479
see also individual techniques
sp-hybridized carbons, cyclizations, aminyl radicals,　2:717-718
spin cages
metal organic polyhedra,　4:1999-2000
verdazyl radicals, self-assembly,　1:237
spin-gap formation versus antiferromagnetic ordering, thiazyl radicals,　4:2151-2152
spin labels and spin probes,　4:1965-2015
biological membranes,　4:1967,1968
biological systems and organic polymers,　4:1966-1987
distance measurements in the nanometer range,　4:1971
EPR, ring conformation study,　1:158
imaging techniques,　4:1972-1975
nitroxide radicals,　4:1965,1966-1967
nucleic acids,　4:1970-1971
oxymetry,　4:1978-1982,1983,1984
pH measurements,　4:1974,1975-1978
profluorescent,　4:1985-1987
protein study,　4:1967,1969-1970
redox status determination,　4:1982-1984,1985,1988
supramolecular systems,　4:1987-2004
spin polarization, electron paramagnetic resonance,　1:153
spin-spin relaxation, electron paramagnetic resonance,　1:149
spin trapping
agents,　4:2002,2004-2005
drawbacks,　4:2003,2005
electron paramagnetic resonance combination,　4:1966,2002,2003,2004-2005
history,　1:28
oxidative stress investigation,　4:2005,2006
spirocycles, synthesis, metal-dependent,　2:913
spirocyclic azidocyclohexadienyl radicals, formation, aromatic azides,　2:1032-1033
spirocyclic cyclohexadienones, synthesis, arene aryl radical additions,　2:1063-1064
spirocyclic cyclopropane radical cation, ring opening,　1:310
spirocyclic C-ketoside derivatives, synthesis, intramolecular carbon-carbon bond formation,　2:1145
spirocyclic vinylcyclopropane, ring expansion,　1:309
spiroiminodihydantoin (Sp), 8-oxoG oxidation,　3:1307,1309-1310,1311-1312
spirolactones, synthesis, electrochemically initiated,　2:1189
SPLET see sequential proton loss electron transfer
spontaneous electron transfers
dithiadiazufulvalenes, synthetic applications,　2:826-831
organic electron donors,　2:817-831
polyaza-substituted ethenes, synthetic applications,　2:826-831
tetrathiafulvalenes, synthetic applications,　2:818-826
spontaneous self assembly see self-assembled…
SP PLP see single-pulse pulsed-laser polymerization
spurs, ionizing radiation,　1:395-396,401
SQUID see superconducting quantum interference device
SR&NI see simultaneous reverse and normal initiation
SR, see also synchrotron radiation
SRMP see semi-radical-mediated polymerization
SRN1 (unimolecular radical nucleophilic substitution) reaction,　1:333-364
activated allyl derivatives,　1:361
activated benzyl derivatives,　1:355-358
activated benzyl halides,　1:360-361
aliphatic substrates,　1:348-361
aromatic substrates,　1:333,336-347
bridged halides,　1:349-351
carbanion nucleophiles,　1:336-338
cycloalkyl halides,　1:348-349
electron-withdrawing groups,　1:354-361
following, 5-exo/6-exo radical cyclizations,　1:344
heterocyclic benzyl analog substrates,　1:358-360
SRN1 (unimolecular radical nucleophilic substitution) reaction (continued)
mechanism,　1:334-335
neopentyl halides,　1:351-352
N/P/As/Sb-based nucleophiles,　1:339-340
perfluoroalkyl halides,　1:352-354
ring closure,　1:342-347
S/Se/Te-based nucleophiles,　1:340-342
α-substituted nitroalkanes,　1:354-355
tin nucleophiles,　1:338-339
vinylic substrates,　1:347-348
SSBs see single strand breaks
SSP see steady-state polymerization
stabilization..., see also radical stability
stabilization constants, enthalpies of formation calculation,　1:91
stabilization energies, radicals,　1:97-100
stabilization of metal nanoparticles,　4:2197,2206
stabilization of monomers, in storage and in-process,　4:1717-1718
stable free radical polymerization (SPRP),　4:1813
advantages/limitations,　4:1806-1807
nitroxide-mediated polymerization,　4:1799-1802
organometallic radical polymerization,　4:1799,1800-1802
persistent radical effect,　4:1786,1787,1797-1799
see also nitroxide-mediated polymerization
stable radicals
definition,　4:1965,2118
silyl radicals,　4:2117-2146
see also radical stability
standard potentials
definition,　1:250
radicals
measurement,　1:258-259
tables,　1:258-270
standard radicals, electron paramagnetic resonance,　1:150-151
standard redox potentials,　1:250
stannane-mediated pinacol coupling, intramolecular homolytic substitutions,　2:651-652
α-stannoimidoyl radicals, indole synthesis, tin hydride-mediated,　2:552-556
stannylaminyl radicals
additions,　2:768-769
aliphatic azide-derived,　2:1023
cyclizations,　2:1023-1025
formation,　2:768
organic azide reductions,　2:1023
O-stannylketyl radicals, 2,3-disubstituted indole synthesis, tin hydride-mediated,　2:553-554
1,4-stannyl migrations, intramolecular homolytic substitutions,　2:649
stannyl radicals
chain additions, isonitriles,　2:1037
cyclizations, alkenyl isothiocyanates,　2:1050
1,5-translocations,　2:652-653
1,n-stannyl translocations, intramolecular homolytic substitutions,　2:651
star polymers, atom transfer radical polymerization,　4:1873-1874
statistical copolymers,　4:1714,1871
steady-state EPR (SEPR), rearrangement kinetics,　1:168-169
steady-state measurements, kinetic EPR spectroscopy,　1:167-169
steady-state polymerization (SSP), kinetics,　4:1740,1741,1750
step-growth polymerization, radical thiol-X click chemistry,　4:2033,2039,2041,2043,2044,2047
stereoblock copolymers, atom transfer radical polymerization,　4:1873
stereochemical trends, Δ-5-hexenyl radicals/radical anions,　1:322-323
stereoelectronic effects
cyclizations,　2:693,703-709
glycos-1-y1 radicals, acrylonitrile additions,　2:1131-1132
radical stability,　1:451,458,460,463
stereosective reactions, see also enantioselective reactions
stereoselective reactions
acyclic 1,2-inductions,　2:655-656
atom transfer radical additions, organoselenides,　2:958
atom transfer radical cyclizations, organoselenides,　2:958
chiral auxiliaries,　2:659-662
chiral chain-transfer reagents,　2:666-667
chiral Lewis acids,　2:668-679
cyclic radicals,　2:658-661
cyclizations,　2:657-659,958
6-hepten-l-one radical anions,　1:321-322
diastereoselective,　2:655-666
enantioselective,　2:666-689
halogen atom transfers, Lewis acid-mediated,　2:670-672
Δ-5-hexenyl radical cyclization,　1:318-319
hydrogen atom transfers, Lewis acid-mediated,　2:668-670
hydroxysulfenylations, organoboranes,　2:620
1,n-inductions,　2:656-657
1,3-inductions,　2:656-657
Lewis acid-mediated,　2:662-666
lipid peroxidation,　3:1579-1580
memory of chirality,　2:667-668
polar crossover reactions,　2:657-658,659
reductions, α-alkoxy radicals,　2:656
reductive alkylations, chiral Lewis acids,　2:672-676
SRN1 reactions,　1:337
1,3-stereoinductions,　2:656-657
styrylations, allcenylindium,　2:606
stereoselective synthesis,　2:655-691
aldols,　2:661-662
1,2-trans-C-glycosides,　2:1137
α-C-glycosides,　2:1137-1139
β-glycosides,　2:1156-1158
tin hydrides,　2:538-540
steric (hinderence) stabilization
carbon-centered radicals,　1:58
radical history,　1:7
silyl radicals,　4:2120-2121
steroid alkaloids, synthesis, nitrogen-centered radical remote functionalizations,　2:1234
steroids, remote functionalizations, benzophenones,　2:1229-1231
stibine-mediated living radical polymerization (SBRP),　4:1932-1958,1960
sticky end sequence, DNA blocks, nanoscale electronic wiring,　3:1412,1413
stilbene dicarboxamide (SA), DNA hairpin conjugation,　3:1401,1402,1404-1406,1408
stilbene diether (SD), DNA hairpin conjugation,　3:1404-1405,1406,1408
stoichiometric factors
antioxidants
catechols/hydroquinones,　3:1657,1658
N-containing compounds,　3:1662,1663,1664,1665
phenols,　3:1629,1632,1633,1648,1655
preventative,　3:1625,1626
radical-mediated metal nanostructure synthesis,　4:2206
storage
metal nanoparticles,　4:2206
monomer stabilization,　4:1717-1718
strained systems, cyclobutylcarbinyl radical trapping, 5-exo-trig cyclizations,　2:699-700
strand breaks, DNA damage,　3:1371,1373,1390-1391
stratosphere,　1:505
Chapman mechanism,　1:506-507
matrix isolation spectroscopy,　1:212
ozone depletion mechanisms,　1:506,508-509,510-513
radical chemistry,　1:506-513,525
halogen radicals,　1:510-511
heterogeneous reactions,　1:511-513
null cycles,　1:509-510
odd-oxygen destruction,　1:507-509
troposphere interaction,　1:505,513,515-516
Strecker synthesis, α-arninoamides,　2:747-748
structural resonance, isonitriles,　2:1036
styrenes
additions, SOMO catalysis,　2:681-682
alkylations, cobalt-catalyzed,　2:1010-1011
cyclopropyl benzene synthesis, cobalt-mediated,　2:1210-1211
double alkylations, alkyl halides, titanium-catalyzed,　2:1014-1015
inhibited autoxidation,　3:1631-1632
organoheteroatom-mediated radical living polymerization,　4:1939-1941
polymerizations
n-butyl acrylate, flow microreactor experiments,　2:1248-1250
flow microreactor experiments,　2:1248-1250
hollow spheres,　4:1925
nitroxide-mediated,　4:1838
styrylations
organoboranes,　2:606-607
stereospecific, alkenylindium,　2:606
substituent effects
bond dissociation energies/atom abstraction rates,　1:102-103
phosphorus-centered radicals,　2:790-792
selenium-centered radicals,　2:804-805
ortho-substituted benzoyl rings, homolytic substitution cascades,　2:738-739
substituted catechols, coupling, anodic oxidations,　2:1205-1207
substituted cyclohexanes, synthesis, titanocene-mediated 6-endo cyclizations,　2:998-999
N-substituted/N,N-disubstituted acrylamides, nitroxide-mediated polymerization,　4:1838
substituted imines, enantioselective reactions, hexylsilane-mediated,　2:595-596
α-substituted nitroalkanes, SRN1 reactions,　1:354-355
4-substituted phenylhydrazine hydrochlorides, fullerene reactions with sodium nitrite,　4:2180
substitutions
aromatic, free-radicals, history,　1:28-29
conjugated Reformatsky reactions, samarium diiodide-mediated,　2:889
electron transfer, history,　1:20
homolytic aromatic,　2:737-739,1059-1080
ipso-type, intermolecular, synthetic strategies,　2:1079
radical chain reactions,　1:60-61,62,63
see also SRN1 reaction
sugars
brominations,　2:1165-1166
synthesis, radical thiol additions,　4:2022
see also nucleic acid sugar radicals
sulbactam, synthesis,　2:640
sulfonyl radicals, additions, isonitriles, five-membered heterocycle synthesis,　2:1045
sulfatase activation, alcohol oxidation to aldehyde, SAM radical enzymes,　3:1520
sulfenic acids, antioxidant action,　3:1625,1646,1666-1667,1673
sulfides
hydrogen transfers, intramolecular homolytic substitution competition,　2:635
intramolecular homolytic substitutions, kinetics,　2:633-634
phosphine, reductions, tris(trimethylsilyl)silane,　2:565-566
sulfinamides, ring-closures,　2:637
sulfinates, ring-closures,　2:637
sulfonamidyl radicals
allylations,　2:1028
formation,　2:775
hydrogen atom migration,　1:131
sulfonate anions, room-temperature ionic liquids,　1:441-442
sulfonate esters, rearrangements,　1:126
sulfones, reductions, Julia-Lythgoe olefinations,　2:864-865
sulfonyl azides, as radical acceptors,　2:1027-1031
sulfonyl radicals, allylations,　2:1028
sulfoxides, antioxidant action,　3:1666
sulfur, see also thio…
sulfur-based mediators, sulfur-centered radicals,　2:796-798
sulfur-carbon bonds, formation, carbohydrate synthesis,　2:1164-1165
sulfur-centered radicals
additions, multiple bonds,　2:798-803
chemistry,　2:796-804
electron paramagnetic resonance,　1:164-165
eliminations,　2:803-804
fragmentations,　2:803-804
fullerene reactions,　4:2180-2182
history,　1:19
hydroxysulfenations,　2:800-801
lipid isomerization,　3:1601-1604,1605,1606
natural product synthesis,　2:798-799
oxidative cleavage, olefins,　2:801-802
stability measurement,　1:451-453,465-466
tandem racemizations, amines,　2:798
see also thiyl radicals
sulfur-containing amino acids
desulfurization,　3:1607-1609
functions,　3:1459
radical formation,　3:1433
radical generation,　3:1605-1607
radical reactions,　3:1459-1474
thioethers/selenothioethers,　3:1467-1472
thiols/selenols,　3:1460-1467
relay stations in electron transfer,　3:1484-1487
structure,　3:1461
thioethers/selenothioethers,　3:1467-1472
thiols/selenols,　3:1460-1467
sulfur-containing biomolecules, time resolved chemically induced dynamic nuclear polarization,　1:193-194
sulfur-containing compounds
antioxidant action,　3:1625,1665-1667,1673
degradative processes, thiyl radical generation,　3:1605
photochemical transformations,　1:193-194,2:1235-1238
reductions, samarium diiodide, synthetic applications,　2:863-864
sulfur dioxide/sulfuric acid, atmospheric,　1:519
sulfur hexafluoride (SF6), radiation-induced radicals in gaseous systems,　1:399
sulfur insertions, SAM radical enzymes,　3:1523-1524
sulfur-nitrogen interactions, heterocyclic thiazyl radicals,　4:2147,2148
sulfur-nitrogen three-electron intermediate
selenothioether radical reactions,　3:1472
thioether radical reactions,　3:1468-1471
sulfur-oxygen three-electron intermediate, thioether radical reactions,　3:1471-1472
sulfurs
intramolecular homolytic substitutions,　2:582,630-631,635-637
ring-closures,　2:635-637
sulfur species, atmospheric reactions,　1:519
sulfur-sulfur bonds, thermolysis,　1:41
sultines, synthesis, alkyl radicals,　2:638
sunlight initiated reactions, history,　1:2,14
superconducting quantum interference device (SQUID), radical polymer batteries,　4:2166
supercooling, thiazyl radicals,　4:2152
superexchange, electron transfer bridges,　3:1477,1478,1479,1490-1491,1492
superoxide dismutases (SODs),　3:1260,1270,1271,1626
superoxide radicals
additions, 8-oxo-7,8-dihydroguanine radical cation,　3:1310
cysteine residue reactions,　3:1464-1465
DNA oxidation,　3:1319,1321,1322
generation
fatty acid effects,　3:1686,1687
hyperglycemia effects,　3:1681-1682,1683
mitochondria,　3:1681-1682,1686
heme protein autoxidation,　3:1264-1265
inflammatory response,　3:1283,1290
mitochondrial respiration,　3:1261
NADPH oxidases,　3:1262-1264
nitric oxide radical interaction,　3:1284
photocatalytic oxygenation,　1:370,389
radiation-induced production,　1:403
radical reactions,　3:1269-1270
superoxide spin adducts,　4:2003,2005,2006
supported tin hydrides,　2:532-534
supramolecular control, radical reactivity, inside zeolites,　1:245
supramolecular lipid organization, positional isomer preferehce,　3:1610-1612
supramolecular radical chemistry,　1:229-248
halogen bonding,　1:232-233
host-guest complexes,　1:233-237
hydrogen bonding,　1:229-232
self-assembly,　1:237-244
spin labels and spin probes,　4:1987-2004
surface-centered silyl radicals, formation, silicon surface monolayers,　4:2089-2096
surface chemistry
metal nanoparticles,　4:2197,2209
plasma effects,　1:480-481
radical thiol addition click chemistry,　4:2045,2048-2052,2053
silicon, self-assembled monolayers,　4:2081-2116
surface plasmon band (SPB), absorption spectra, noble metal nanoparticles,　4:2198
surfactant-free emulsions, RAFT polymerization,　4:1923-1924
surfactants, emulsion polymerization, industrial processes,　4:1721
suspension polymerization
industrial processes,　4:1720-1721
mini-emulsion polymerization comparison,　4:1724
symmetry of reference compounds, radical stabilization energy characterization,　1:451
synchrotron radiation (SR), photoionization of gas phase radicals,　1:479,487,495-496
synergism, antioxidants,　3:1667-1669
synthetic rubber, industrial emulsion polymerization,　4:1721,1723
synthetic strategies
alkoxyamine homolysis, nitroxides,　2:1102-1103
arylations,　2:1059-1093
aryl radicals,　2:1080-1087
intermolecular homolytic aromatic substitutions,　2:1074-1079
intramolecular homolytic aromatic substitutions,　2:1059-1074
atom transfer radical additions, chalcogens/halogens,　2:943-963
atom transfer radical cyclizations, chalcogens/halogens,　2:943-963
boron radical chemistry,　2:601-628
carbohydrates,　2:1131-1174
cascade reactions,　2:729-765
cerium(IV) ammonium nitrate-mediated oxidations,　2:901-941
cyclizations
ATRC, chalcogens/halogens,　2:943-963
metal-dependent,　2:918-932
electrochemically initiated reactions,　2:1175-1215
epoxides, titanocene-catalyzed/mediated reactions,　2:989-1001
flow microreactor experiments,　2:1243-1258
intermolecular homolytic substitutions,　2:1074-1079
intramolecular homolytic substitutions,　2:629-654,1059-1074
iron(III) salt-mediated oxidations,　2:901-941
isonitriles,　2:1041-1048
main group element radicals,　2:767-816
manganese(III) acetate-mediated oxidations,　2:901-941
neophyl-type rearrangements,　2:1070-1071
nitrogen-centered radicals,　2:767-781
nitroxide-mediated oxidations,　2:1104-1123
nitroxides,　2:1095-1129
Norrish reactions,　2:1227-1231
organic electron donors,　2:817-847
electrochemical induction,　2:844-845
photoactivation,　2:832-834
reagent-induced activation,　2:834-844
spontaneous/thermal electron transfers,　2:817-831
oxidations
cerium(IV) ammonium nitrate-mediated,　2:901-941
iron(III) salt-mediated,　2:901-941
manganese(M) acetate-mediated,　2:901-941
oxoammonium salts,　2:1108-1119
oxygen-centered radicals,　2:781-790
phosphorus-centered radicals,　2:790-796
photochemistry,　2:1217-1241
ring opening, metal-dependent,　2:932-935
ruthenium-mediated photocatalysis,　2:1221-1227
samarium diiodide,　2:849-900
additive effects,　2:850-852
carbonyl-alkene coupling,　2:870-877
pinacol coupling,　2:864-870
reaction mechanisms,　2:852-856
selenium-centered radicals,　2:804-810
single electron transfers, nitroxide-mediated,　2:1104-1108
stereoelectronically disfavoured cyclizations, five membered rings,　2:703-709
stereoselective reactions,　2:655-691
sulfur-centered radicals,　2:796-804
tin hydrides,　2:529-560
functional group transformations,　2:540-556
preparation,　2:529-540
titanocene-catalyzed/mediated reactions,　2:989-1001
transition metals,　2:1003-1018
tris(trimethylsilyl)silane-mediated reductions,　2:561-599
unsaturations, nitroxide additions,　2:1103-1104
unusual cyclizations,　2:693-728
carbon-centered radicals,　2:719-724
four-membered rings,　2:698-702
iminyl radicals,　2:717-718
nitrogen-centered radicals,　2:716-717
oxygen-centered radicals,　2:717-719
small cycle synthesis,　2:694-702
stereoelectronically disfavoured,　2:703-709
unusual radical acceptors,　2:1019-1057
xanthates,　2:965-987
T2D see type-2 diabetes
T:A-T triplex DNA structure, hole transfer,　3:1407-1409
TAM see triarylmethyl
tandem base lesions
DNA oxidation,　3:1335-1338
hydroxyl radicals,　3:1292-1293
intrastrand pyrimidine-purine cross-links,　3:1335-1336
pyrimidine hydroperoxyl radicals,　3:1336-1338
tandem conjugate addition-aldol cyclizations, B-alkylcatecholborane-mediated,　2:612
tandem conjugate addition-aldol reactions, trialkylboranes,　2:608
tandem conjugate addition-fragmentation reactions, enantioselective, chiral Lewis acid-mediated,　2:678-679
tandem cyclizations
cross-coupling arylations, cobalt-catalyzed,　2:1008-1009
electrochemically initiated, polyenes,　2:1209
2β-iodo glucopyranosides, branched-chain sugar synthesis,　2:1147-1148
Lewis acid-promoted, aryltelluro groups,　2:959
metal-dependent,　2:928-932
tris(trimethylsilyl)silane-mediated,　2:590-592
tandem enantioselective conjugate addition-radical alkoxyaminations, B-alkylcatecholboranes,　2:615
tandem homolytic addition/substitution reactions
cyclic alkoxysilane synthesis,　2:646
selenides,　2:641-644
tandem protein-lipid damage, radical attack,　3:1607-1609
tandem racemizations, amines, sulfur-centered radicals,　2:798
tandem reactions, tris(trimethylsilyl)silane-mediated,　2:587-593
targeted degree of polymerization (DPT)
controlled/living radical polymerization,　4:1788,1789,1790-1791,1792
dead chain fraction relationship,　4:1789,1790-1791,1792
definition,　4:1789
TBADT see tetrabutylammonium decatungstate
TBARS see thiobarbituric acid reactive substances
TDAE see tetrakisdimethylaminoethene
TD-DFT see time dependent density functional theory
tellurides, intramolecular homolytic substitutions, kinetics,　2:633-634
tellurium, intramolecular homolytic substitutions,　2:631
tellurium-containing antioxidants,　3:1625
tellurium-mediated living radical polymerization (TERP),　4:1932-1960
β-telluroacrylamides, synthesis,　2:960-961
telluro derivatives, additions, isonitriles,　2:1046
temperature, 10 hour half-life, thermolysis,　1:38,39
temperature control, industrial radical polymerization,　4:1719-1720,1721
temperature-dependent phase transitions, thiazyl radicals,　4:2149-2152
template effects, reductive alkylations, chiral Lewis acid-mediated,　2:673-674
temporal control, photochemical radical-mediated metal nanostructure synthesis,　4:2198
TEMPO (2,2,6,6-tetramethylpipericline-1-oxyl radical)
1,4-benzene diradical trapping, enediyne Bergman cyclizations,　2:1101-1102
bond dissociation energies,　1:92-93
carbohydrate oxidations,　2:1202-1203
carbon radical trapping
after cyclizations,　2:1099-1101
enamine a-oxyaminations,　2:1097-1099
hydroxy group installation,　2:1096-1097
dendrimer investigation,　4:1988-1989
electrochemically initiated reactions,　2:1202-1203
gold nanoparticle monolayer protection,　1:238-239
halogen bonding,　1:232-233
hydrogen abstractions
alcohols,　2:1119-1121
catechols,　2:1121-1122
phenols,　2:1121-1122
-malonate, additions to alkenes,　2:1247
nitroxide-mediated polymerization,　4:1816,1827,1838,1839
nitroxides, spin labels and spin probes,　4:1966,1967
nonchain reaction sequences,　1:109
α-oxyaminations, enamines,　2:1097-1099
redox reactions,　4:2164-2165
rotaxanes capping groups,　1:244
stability,　1:449,450
structure,　4:1814,1965
terminal model (TM), copolymerization propagation,　4:1714-1715,1749-1750
termination
polymerization,　4:1738
chain-length-dependent termination,　4:1740,1745-1748,1771-1775,1787,1793-1794
chain-length-independent termination,　4:1741,1743,1745-1746,1747,1753
industrial processes,　4:1717-1719
kinetics,　4:1739-1740,1770-1777,1788-1789,1792-1793
nitroxide-mediated polymerization,　4:1818,1819,1825-1826
radical versus ionic polymerization process,　4:1785
radical chain reactions,　1:60,62,108
SRN1 reactions,　1:334
termination rate coefficients,　4:1752-1753,1770-1771,1773-1775
termination rate constant (k1),　4:1788-1789,1792-1793
TERP see tellurium-mediated living radical polymerization
N-tert-butyl-N-2-methyl-l-phenylpropyl nitroxide (TIPNO), nitroxide-mediated polymerization,　4:1729,1827,1838
tertiary allylic alcohols, oxidative rearrangements, oxoammonium salts,　2:1110
tertiary amines
borane complexes,　2:620
fullerene additions,　4:2187,2188
photoinduced additions, pyrrolizadine synthesis,　2:1220
photoinduced electron transfer, radical addition to alkenes,　1:291-292
silylated, photoinduced additions, alkynes,　2:1218-1219
tertiary carbon radicals, 5-endo-trig cyclizations,　2:705
tethered radicals, additions, unsaturated carbohydrates, branched-chain sugar synthesis,　2:1146-1149
tetraalkylphosphonium benzoate radicals, room-temperature ionic liquids,　1:442
tetrabutylammonium decatungstate (TBADT) catalysis, fullerene radical reactions,　4:2173-2174,2175
tetracyclic nitro compounds, denitrations, tin-hydride mediated,　2:548-549
tetrahydrofuran (THF)
anellated,　2:788-789
radiolysis,　1:412-413
synthesis
cobalt-catalyzed,　2:789
diastereoselective,　2:1180
electrochemically initiated,　2:1176-1177,1179,1180
enol ether oxidations,　2:1176-1177
ketene dithioacetal oxidations,　2:1179
Kolbe electrolysis,　2:1199
metal-dependent,　2:932-933
oxygen-centered radicals,　2:788-789
relay cyclizations,　2:736
samarium diiodide solution,　2:849-895
titanium-mediated radicals,　2:644-645
tetrahydronapthalenes, synthesis,　2:617,911
tetrahydropyrans, synthesis,　2:933-934,1199
tetrakisdimethylaminoethene (TDAE)
coupling, α-bromoketones,　2:828
electron transfers,　2:826-828
reductions, arenediazonium salts,　2:828
N,N,N',Nprime-tetramethyl-1,5-diaminonapthalene (TMDN), DNA conjugation,　3:1416,1417,1418
S(2,2,5,5-tetramethy1-2,5-dihydro-1H-pyrrol-3-yl)methyl methanesulonothioate (MTSL),　4:1967,1969,1970
1,1,4,4,-tetramethyl ioindolin-N-oxyl (TMIO) radical
nitroxide-mediated polymerization,　4:1827
structure,　4:1814
2,2,6,6-tetramethylpiperidine-1-oxyl (and similar) see TEMPO
2,2,6,6-tetramethylpiperidine-N-oxyl-malonate, additions, alkenes,　2:1247
2,2,5,5-tetramethylpyrrotidine-N-oxyl nitroxides, spin labels and spin probes,　4:1967
2,2,5,5-tetramethylpyrroline-N-oxyl nitroxides, spin labels and spin probes,　4:1967
tetranitromethane, additions, B-alkylcatecholboranes,　2:615
meso-tetraol, synthesis,　2:810-811
tetraphenylethylene (TPE), photocatalytic oxygenation to 1,2-dioxetane,　1:372-374
tetrasubstituted alkenes, synthesis, xanthates,　2:983
tetrasubstitutions, SRN1 reactions,　1:335,351,355,358,361
tetrathiafulvalene (TTF),　2:818-826
tetrathiatriarylmethyl radicals, history,　1:24-25
TGBC see top-gate bottom-contact
TGTC see top-gate top-contact
theoretical calculations, redox potential determination,　1:257-258
theoretical modeling studies
DNA damage,　3:1392-1393
DNA radicals,　3:1371
anisotropic hyperfine interactions,　3:1380-1381
excited state properties,　3:1392-1393
ground state properties,　3:1381-1388
monolayer generation on silicon surfaces,　4:2096-2100
radical enzymes,　3:1547-1576
thermal attachment, monolayer generation on silicon surfaces,　4:2089
thermal control, industrial radical polymerization,　4:1719-1720,1721
thermal electron transfers
dithiadiazafulvalenes,　2:826-831
organic electron donors,　2:817-831
polyaza-substituted ethenes,　2:826-831
tetrathiafulvalenes, synthetic applications,　2:818-826
thermal initiation
industrial radical polymerization,　4:1706
radical chain reactions,　1:110
thermally-induced reactions, flow microreactor experiments,　2:1243-1250
thermochemical cycles, redox potential determination,　1:257-258
thermochemistry,　1:81-106
bond dissociation enthalpies,　1:81-100
empirical estimation schemes,　1:84,88
enthalpies of formation,　1:82-97
experimental/ab initio values,　1:84
Hess's Law,　1:81-82
hydrogen transfer kinetics,　1:100-102
literature enthalpy values,　1:85-87
radical stabilization energies and scales,　1:97-100
substituent effects,　1:102-103
thermodynamic parameters
determination, EPR,　1:169-170
redox potential determination,　1:257-258
thermodynamics
activation energy,　3:1267,1268,1271
atom transfer radical polymerization,　4:1863-1869
cyclizations,　2:693
5-endo-dig cyclizations,　2:706-709
kinetics correlation, phenolic antioxidants,　3:1646-1650
phenolic antioxidants,　3:1646-1650
versus kinetics,　3:1267,1268,1271,1646-1650
thermodynamic stability
radicals, definitions,　1:449-453
silyl radicals,　4:2118-2120
thermolysis
azo compounds,　1:39-40
N-O bonds,　1:41
organometallic compounds,　1:41
peroxides,　1:38-39
radical initiation,　1:37-42
S-S bonds,　1:41
thermosensitive micelles, organoheteroatom-mediated radical living polymerization,　4:1958
THF see tetrahydrofuran
thiacarbenium ions, metal-dependent formation,　2:916-917
thiamine diphosphate (ThDP), SAM-dependent enzymes,　3:1519-1520,1522
thiazole-2[3H]-thione derivatives, alkoxy radical generation, photo-irradiation,　2:1238
thiazyl radicals
1,3,2-benzodithiazolyl,　4:2151-2152
conductive/magnetic materials,　4:2147-2161
conductivity,　4:2156-2161
drastic phase transitions,　4:2147-2154
photoconductivity,　4:2159
physical properties,　4:2147-2161
room-temperature magnetic bistability,　4:2148-2151
transition metal complexes,　4:2154-2155
1,3,5-trithia2,4,6-triazapentalenyl,　4:2148-2151,2156-2157
thieno[3,4-b]thiophene/benzodithiophene alternating copolymer (PTBx), polymer-based solar cells,　4:2074
N-thioaryl compounds, nitrogen-centered radical generation,　2:772-773
thiobarbituric acid reactive substances (TBARS), human physiological levels,　3:1591
thiobismuthine (Bi-S) cocatalysts, organoheteroatom-mediated radical living polymerization,　4:1935-1936,1941,1942-1943,1956-1958
α-thio carbamates, electrochemically initiated functionalizations,　2:1205
thiocarbonate thio compounds, reversible addition fragmentation chain transfer agents,　4:1896
thiocarbonyl derivatives, general reaction manifolds,　2:984
thiocarbonyl organosilanes, chain reactions,　2:571
N-thiocarbonylsulfanyl compounds, nitrogen-centered radical generation,　2:773
"thio-click" reaction, use of term,　4:2033
thioenol ethers, amine-bearing, electrochemically initiated cyclizations,　2:1177-1178
thioesters
cleavage, nickel-mediated,　2:1209-1210
see also Barton esters
thioethers
carbon-S bonds, photoinduced homolytic α-cleavage,　1:283
radical generation, tin hydride-mediated,　2:550-551
radical reactions,　3:1467-1472
thiohydroximidate esters, selenotocopherol synthesis,　2:639
α-thioketones, synthesis, metal-dependent,　2:916
thiol-ene addition reactions,　4:2017,2018-2019,2020
clickable,　4:2022,2023-2025,2029-2053
thiol pair reactions, tris(trimethylsilyl)silane,　2:568-571
thiol proteins, hydrogen peroxide reactions,　3:1274-1275
thiols
antioxidant action,　3:1665-1666
aromatic, coupling, anodic oxidations,　2:1205-1207
desulfurations, alkyl radical generation,　2:1047
formation, alcohol conversions, Barton-McCombie deoxygenations,　2:971-972
hydrogen transfer to radicals,　3:1460
ionization,　3:1460
radical addition to unsaturated compounds
click chemistry,　4:2017,2021-2053
mechanisms,　4:2017,2018-2020
radical reactions,　3:1460-1467
thiol-specific nitroxide spin labels, GSH detection/quantification,　4:1984,1985,1986
thiol-yne addition reactions,　4:2017,2018,2019-2020
clickable,　4:2025,2028-2030,2039,2043,2053
thionocarbonates, cyclizations,　2:970
γ-thionocarbonyloxy alkyl radicals, rearrangements,　1:127-128
thiophene backbone structure modification, polythiophenes, polymer-based field-effect transistors,　4:2062-2063
1,2-thiophosphinoylations, alkyne radicals, phosphorus-centered radicals,　2:793-794
thioselenations, isocyanide, selenium-centered radicals,　2:807
thiosulfinates, antioxidant action,　3:1625,1666-1667,1673
thiyl radicals
biological relevance,　3:1502
formation and properties,　3:1460-1461
hydrogen transfer from organic compounds,　3:1460
lipid isomerization,　3:1601-1604
inhibition,　3:1617
liposomes,　3:1610,1611,1612,1613
oxygen role,　3:1616
molecular oxygen reactions,　3:1466
polarity reversal catalysts,　3:1460
reactions in biological systems,　3:1270
regioselective additions, vinylidenecyclopropane,　2:800
S-containing amino acids/peptides,　3:1605-1609
unsaturated carbon addition reactions,　4:2018-2020
Thorpe-Ingold effect, 4-exo-trig cyclizations,　2:699
ThPD see thiamine diphosphate
three-component coupling reactions, tris(trimethylsilyl)silane-mediated,　2:588-589
three-electron intermediate, thioether radical reactions,　3:1468-1472
three-membered rings, synthesis, unusual cyclizations,　2:694-698
thymine (T)
dimer electron acceptor,　3:1415
hydroxyl radical reactions,　3:1291-1292
one-electron oxidation, thermodynamics,　3:1293-1294
oxidation
hydroxyl radicals,　3:1321-1323
one-electron transfer,　3:1328-1330
reduction, DNA charge transfer,　3:1398
thysiferol, synthesis,　2:994
time dependent density functional theory (TD-DFT), DNA radicals,　3:1388,1389-1390,1392
time resolved chemically induced dynamic nuclear polarization (TR-CIDNP),　1:176-177,180-187
applications,　1:190-198
experiment,　1:182-184
inter-/intramolecular electron transfer,　1:194-197
photoreactions
glycylglycine,　1:191-193
sulfur-containing biomolecules,　1:193-194
time-resolved electron paramagnetic resonance (TR-EPR)
antioxidant studies,　3:1640
radical study in real time,　1:175
see also chemically induced dynamic electron polarization
time-resolved fluorescence spectroscopy, photoinduced radicals,　1:298
time-resolved infrared spectroscopy, photoinduced radicals,　1:298
time-resolved photoelectron spectrum, gas phase radicals,　1:492
tin, see also stannane...; stannyl…
tin-centered radicals
electron paramagnetic resonance,　1:161-162
history,　1:19
tin-free modifications, Barton-McCombie deoxygenations,　2:967-970
tin hydride method, carbon radical clock calibration,　1:112-113
tin hydrides,　2:529-560
additions, unsaturated systems, radical generation,　2:551-554
alkyl bromide reduction, radical chain reaction steps,　1:108
carbon-centered radical generation,　2:543-554
C-halogen bond cleavage, radical generation,　2:543-546
fluorous, preparation,　2:534-537
heteroatom-centered radical generation,　2:554-556
as hydrogen-donors,　2:541-542
nitrogen-centered radical generation,　2:554-556
oxygen-centered radical generation,　2:555-556
preparation,　2:530-540
radical chain mediators,　1:63-65
radical generation,　2:542-556
reaction types,　2:540-541
in situ generation,　2:532
stereoselective reactions, preparation,　2:538-540
supported, preparation,　2:532-534
water-soluble, preparation,　2:537-538
tin nucleophiles, SRN1 reaction,　1:338-339
tin reagents
intramolecular homolytic substitutions,　2:650-653
photochemical cleavage,　2:1238-1239
radical chain mediators,　1:63-65,66
TIPNO see N-tert-butyl-N-2-methyl-1-phenylpropyl nitroxide
Titan, atmospheric chemistry,　1:480
titanium-mediated reactions
asymmetric electron transfers,　2:687-688
carbodiazenylations, alkenes,　2:747-748
cascades,　2:746-749
double alkylations, styrenes,　2:1014-1015
fomitellic acid AB ring synthesis,　2:749
oxidative additions,　2:1014-1015
titanocene-mediated reactions
epoxides,　2:989-1001
cyclizations,　2:995-999
reductive opening,　2:990-993
epoxypolyenes, cyclizations.　2:748-749
β-titanoxy radicals, synthesis, epoxides,　2:989-990
TM see terminal model
TMC see transition metal-catalysis
TMDN see N,N,N',Nprime-tetramethyl-1,5-diaminonapthalene
TMIO see 1,1,4,4,-tetramethyl ioindolin-N-oxyl
(TMS)3SiH see tris(trimethylsilyl)silane
α-tocopherol (α-TOH/vitamin E)
antioxidant action,　3:1623,1631
ascorbate synergism,　3:1667,1669
kinetic measurements,　3:1637-1639
TolSQ see 1-(p-tolysulfinyl)-2,5-benzoqinone
1-(p-tolysulfinyI)-2,5-benzoqinone (TolSQ), semiquinone radical anions, hydrogen bonded to protonated histidine,　1:229-230
top-gate bottom-contact (TGBC), organic-based field-effect transistors,　4:2058
top-gate top-contact (TGTC), organic-based field-effect transistors,　4:2058
topological connections, mechanical interlocking of free radicals,　1:239-244
N-tosylamino radicals, formation, aziridine ring opening,　2:778
toxins
radical chain mediators, tri(organo)tin hydrides,　1:63-64,65
reactive oxygen species generation,　3:1265-1266
TPE see tetraphenylethylene
transannular hydrogen abstraction, alkyl radicals,　1:141
trans fatty acids
human health,　3:1599-1600
lipid isomerization,　3:1599-1622
lipidomics of biological samples,　3:1612-1615
transfer constants, reversible addition fragmentation chain transfer,　4:1899-1901
transfer reaction kinetics, polymerization,　4:1739
transient heteroatom-centered radicals, electron paramagnetic resonance,　1:161-165
transient radicals, use of term,　1:449
transition metal..., see also individual metals
transition metal-catalysis (TMC)
atom transfer radical addition,　4:1851,1853-1854,1879-1880
atom transfer radical polymerization,　4:1803-1804,1854-1855,1856-1860
fullerene radical reactions,　4:2174-2178
C-glycoside synthesis,　2:1136
Kharasch-type reactions,　2:1003-1004
oxidative additions,　2:1003-1018
transition metal-centered radicals, fullerene reactions,　4:2183-2184
transition metal complexes
atom transfer radical polymerization,　4:1803-1804
thiazyl radicals,　4:2154-2155
transition metal ions, chelating agents,　3:1623,1624
transition metals
biological chemistry of reactive oxygen species,　3:1266,1272-1273
Fenton-like chemistry,　3:1272-1273
transition metal-substituted silyl radicals, persistent and stable,　4:2141-2143
transition states (TSs)
exocyclic closure effects, electronics,　2:714-715
hydrogen atom migration,　1:133
reaction rate prediction,　1:81,100-103
translational dynamics, room-temperature ionic liquids,　1:434
1,5-translocations, stannyl radicals,　2:652-653
translocations
cascade reactions, with cyclizations,　2:735-737
β-glycoside synthesis,　2:1157-1158
trapping
amidyl radicals,　2:976-977
carbon radicals
after cyclizations, nitroxides,　2:1099-1101
nitroxides,　2:1095-1102
cations, tetrathiafulvalenes, sytithetic applications,　2:820-824
cyclopropylacyl radicals,　2:976-977
deactivation/activation process, controlled/living radical polymerization,　4:1786-1787
decarboxylated Barton esters,　2:1236-1237
iminyl radicals,　2:971-972
see also spin trapping
trapping agents, competition kinetics,　1:111
trialkylboranes
carbon-centered radical attack,　2:602
conjugate additions,　2:607-609
β-fragmentations,　2:609-610
heteroatom-centered radical attack,　2:602
triarylmethyl (TAM) radicals
history,　1:2-6,21-25
pH sensitive spin probes,　4:1976-1978,1980
triazenes, nitrogen-centered radical generation,　2:771-772
triazole derivatives, RAFT polymerization,　4:1905
triblock copolymers, nitroxide-mediated polymerization,　4:1843
tributyltin hydride
cyclopentane derivative synthesis,　2:1149-1152
fullerene addition,　4:2184
preparation,　2:531
radical chain processes,　1:40,63-66
1,1,1-trichloroethane see methyl chloroform
trichloromethyl radical
Kharasch reaction,　1:62-63
metal-catalyzed chain reactions,　1:75-76
tricyclic products, enol-ether furan derivative cyclizations,　2:1182
tricyclic pyrolidines, synthesis, oxime ether cascade cyclizations,　2:730-731
tricyclopropyl amine radicals, neutral versus cation,　1:308
triethylamine, cyclizations, bromoalkynes,　2:1252-1253
triethylsilane, aromatic azide reductions,　2:1025-1026
trifluoromethyl acetate anions, room-temperature ionic liquids,　1:441
trifluoromethylations, lithium enolates, organoboranes,　2:605
triglycerides, natural, lipid isomerization,　3:1603-1604
trimethoxyphenylalanine, relay station in two-step electron hopping,　3:1480-1481
trimethylboranes, substitutions, methoxyl radicals,　2:602
tri(organo)tin hydrides, radical chain mediators,　1:63-65
triphenylboranes, substitutions, methoxyl radicals,　2:602
triphenylene cores, synthesis,　2:1191-1192
triphenylmethyl (trityl) oximes, closure, diphenyl diselenide effects,　2:809-810
triphenylmethyl (trityl) radicals
dimer structure,　1:2-3,58
discovery,　1:2-3
formation routes,　1:5
oxymetric spin probes,　4:1979,1981,1983,1984
peroxide formation,　1:2,3-4
pH sensitive spin probes,　4:1976-1978,1980
profluorescent spin labels and spin probes,　4:1986
properties,　1:5-6
redox status spin probes,　4:1984
stability,　1:7,58,4:1965,1966
triphenylmethyl (trityl) triarylmethyl radicals, history,　1:24-25
triphenylphosphene, photocatalytic oxygenation,　1:378-380
triphenyltin hydride, preparation,　2:531
triplet repulsion, hydrogen transfer kinetics,　1:102
triplet silyl biradicals, persistent and stable,　4:2134-2135
tripropyltin hydride, preparation,　2:531
tris(silyl)-substituted silyl radicals
dimerization,　4:2127-2130
EPR,　4:2127,2128,2131
generation,　4:2121-2125
hydrogen abstraction,　4:2122
silicon-mercury bond cleavage,　4:2124
silicon-silicon bond cleavage,　4:2122,2124
oxidation/reduction/ionization,　4:2130
persistent and stable,　4:2121-2132
photochemistry,　4:2130
reactions,　4:2127-2130
stability,　4:2123
structure,　4:2125-2127
tris(trimethylsilyl)silane (TTMSS; (TMS)3SiH),　2:562-571
additions, fluoroalkyl radicals, carbon-carbon multiple bonds,　2:585-586
N-alkoxyamine synthesis,　2:586-587
alkyl halide reductions, flow microreactor experiments,　2:1244-1246
allylations,　2:584-585
autoxidations,　2:568-569
carbocyclizations,　2:574-575
carbon-carbon bond formation,　2:583-585
carbon-phosphorus bond formation,　2:587-588
carbon-silicon bond formation,　2:566-568
cascade reactions,　2:587-593
cyanations,　2:584-585
cyclic amine synthesis,　2:576-577
cyclic ether synthesis, 2:575,　577
cyclizations,　2:579,590-592
cyclonucleoside synthesis,　2:590
decarbonylations, acyl derivatives,　2:563-565
dehalogenations,　2:562-563
desulfidations, phosphine sulfides,　2:565-566
1,2-dial reductions, olefin synthesis,　2:563-564
domino reactions,　2:592-593
β-eliminations,　2:584-585
enantioselective reactions,　2:583-584
furan synthesis,　2:575-576
homolytic aromatic substitutions,　2:586-587
hydrogen abstractions,　2:561-562
hydrosilylations,　2:566-568
intermolecular reactions,　2:583-587
internal homolytic substitutions,　2:582
model silicon surface, monolayer generation,　4:2098-2099
multistep reaction mediation,　2:574
neophyl-type rearrangements,　2:589-590
nitrogen heterocycle synthesis,　2:578
nucleoside reductions,　2:570
olefinations, 1,2-diol reductions,　2:563-564
one-carbon ring expansions, cycloketones,　2:581-582
oxidations, molecular oxygen,　2:568-569
as reducing agent,　2:561-599
reductions
aromatic azides,　2:1026
nucleosides,　2:570
phosphine selenides,　2:565-566
phosphine sulfides,　2:565-566
selenides, phosphine,　2:565-566
sulfides, phosphine,　2:565-566
reductive cleavage,　2:562-566,569-570
secondary amine synthesis,　2:565
tandem cyclizations,　2:590-592
tandem reactions,　2:587-593
thiol pair reactions,　2:568-571
trisubstituted alkyl radicals, stability,　1:457-463,464
trisubstitutions, SRN1 reactions,　1:335,339,361
1,3,5-trithia2,4,6-triazapentalenyl (TTTA)
carrier doping for Mott phase,　4:2156-2157
crystal structures,　4:2150
room-temperature magnetic bistability,　4:2148-2151
trityl see triphenylmethyl
Trommsdorff/Trommsdorff-Nomish effect, polymerization kinetics,　4:1742-1743
troposphere,　1:504-505
complexity,　1:513-514
radical chemistry,　1:513-525
aqueous-phase oxidants,　1:519
chain oxidation of CO/CH4,　1:519-522
halogen radicals,　1:516-519
HOx radicals,　1:514-516,519-522,525
isoprene oxidation,　1:523-525
nitrate radicals,　1:516
organics with 2+ carbon atoms,　1:522-525
ozone reactions,　1:514-515,516,518,520,523,525
PAN,　1:522-523
pollutant cleansing,　1:514-525
stratosphere interaction,　1:505,513,515-516
tryptophan, relay amino acids in electron transfer,　3:1481-1483
TTF see tetrathiafulvalene
TTMSS see tris(trimethylsilyl)silane
TTTA see 1,3,5-trithia2,4,6-triazapentalenyl
TTTA.Cu(hfac),
coordination polymers,　4:2154-2155
crystal structure,　4:2155
tungsten carbenes, functionalized, synthesis, titanocene-catalyzed,　2:994
tunneling mechanisms, DNA charge transfer,　3:1399-1403,1414
two-electron oxidants, reactive oxygen species in biological systems,　3:1266,1271-1272
two-electron reductions, fullerenes,　4:2190
two leaving groups, SRN1 reactions,　1:335,336-337
two-photon two-color laser flash photolysis, characterization of radicals,　1:297
type-2 diabetes (T2D)
complications,　3:1692-1694
free radicals,　3:1679,1680-1684
tyrosine, relay amino acids in electron transfer,　3:1481-1482,1483-1484
tyrosyl radicals, cysteine residue reactions,　3:1465-1466
Ugi products, cyclization-rearrangements, metal-dependent,　2:912
ultrafast spectroscopy, unimolecular reactions, gas phase radicals,　1:492,493,494
ultramicroelectrodes, cyclic voltammetry, redox potential determination,　1:253
ultraviolet (UV), UV-vis spectroscopy, matrix isolation,　1:209
ultraviolet (UV) filters, preventive antioxidants,　3:1623,1624
ultraviolet (UV) irradiation
curing of coatings/inks/adhesives, industrial radical polymerization,　4:1711-1712
DNA damage and repair,　3:1397
monolayer attachment to silicon surfaces,　4:2089-2091
protein photo-oxidation,　3:1443-1447
reactive oxygen species generation in biological systems,　3:1265
umpolung, electrochemical, intramolecular cyclizations,　2:1176
unconjugated monomers, organoheteroatom-mediated radical living polymerization,　4:1940,1943
uniform barrier model, electron transfer in peptides/proteins,　3:1478
unimolecular alkoxyamine initiators, nitroxide-mediated polymerization,　4:1727-1728
unimolecular chain transfers, silicon hydrides,　2:948
unimolecular radical nucleophilic substitution see SRN1
unimolecular reactions, gas phase radicals,　1:479,492-495,498
unimolecular rearrangements, neutral radicals versus radical ions,　1:301
unimolecular routes, photochemical radical-mediated metal nanostructure synthesis,　4:2201-2202
universal agents, reversible addition fragmentation chain transfer,　4:1908,1910,1912
unpaired electrons (UPEs), electron paramagnetic resonance,　1:147-170
unsaturated carbohydrates
additions
branched-chain sugar synthesis,　2:1146-1149
α-C-glycosides synthesis,　2:1137-1139
unsaturated compounds
additions
C-glycoside synthesis,　2:1133-1135
radical dials,　4:2017,2018-2053
tin radicals,　2:551-554
see also carbon—carbon multiple bonds; individual compounds
α,β-unsaturated esters, additions, L-fucos-1-yl radicals,　2:1133
unsaturated fatty acids
lipid isomerization,　3:1599-1622
see also monounsaturated fatty acids; polyunsaturated fatty acids
unsaturated radicals, matrix isolation spectroscopy,　1:214-218
unsaturations
nitroxide additions,　2:1103-1104
phosphorus-centered radicals,　2:792-795
phthalimide N-oxyl,　2:1103-1104
N-unsubstituted spiroindolone, synthesis, organic azides,　2:1033-1034
unsymmetrical ketones, synthesis, photo-carbonylations,　2:1254
unusual cyclizations,　2:693-728
bond formation steps,　2:715-724
carbon-centered radicals,　2:719-724
five membered rings,　2:703-709
five-membered ring synthesis,　2:709-711
four-membered ring synthesis,　2:698-702
large ring synthesis,　2:711-715
medium ring synthesis,　2:711-715
rate constants,　2:695
six-membered ring synthesis,　2:709-711
small cycle synthesis,　2:694-702
three-membered ring synthesis,　2:694-698
unusual radical acceptors,　2:1019-1057
UPEs see unpaired electrons
UV see ultraviolet
vegetable oils, radical thiol additions,　4:2022
veratrol, anodic coupling, anisole,　2:1191-1192
verdazyl radicals, self-assembly of spin cages,　1:237
vertical layers, atmosphere,　1:504-505
vicinal hydroxysulfones, alkene formation, xanthate Barton-McCombie deoxygenations,　2:971
vindoline, dimerizations,　2:1194
(±)-vindoline, synthesis, cascade cyclizations,　2:1081-1082
vinyl acetate, RAFT polymerization,　4:1905
vinylations
B-alkylcatecholboranes,　2:614
xanthates,　2:981-982
α-vinylations, aldehydes, SOMO catalysis,　2:681-682
vinyl azides, iminyl radical generation,　2:770
vinyl epoxides, additions, xanthates,　2:619
vinyl ethers, oxazolidine ring expansions,　2:1205
vinylic substrates, SRN1 reactions,　1:347-348
vinylidenecyclopropane, regioselective additions, thiyl radicals,　2:800
vinyl iodides
cyclizations, Lewis acid effects,　2:665-666
ring-closures, at silicon,　2:648
vinylpinacolborane, Giese-type additions,　2:623
vinyl radicals
[4+1] annulations, isonitriles,　2:1043
clocks,　1:116-117
cyclizations
aldimines,　2:720-721
ketimines,　2:720-721
organic azides,　2:1022
hydrogen abstraction,　1:137,141
matrix isolation spectroscopy,　1:215-216
ring closures
at silicon,　2:648
at sulfur,　2:636
silicon surface reactions,　4:2086-2087
vinyl substituted cylopropanes, ring opening/expansions,　1:309-310
viologen radicals, rotaxane molecular shuttles,　1:241,243,244
viscosity effects, industrial radical polymerization,　4:1719,1720,1721
visible light
photocatalysis, cascade reactions,　2:761-763
UV-vis spectroscopy, matrix isolation,　1:209
vitamin A,　3:1670,1673
see also β-carotene
vitamin C see ascorbic acid
vitamin E see α-tocopherol
vitamin interactions, antioxidants,　3:1667,1669
voltammetry, see also cyclic; photomodulation; second harmonic
water
gas phase
radiation-induced radicals,　1:398-399
see also water vapour
liquid phase, radiation-induced radical reactions,　1:400-410
radiolysis
gas phase,　1:398-399
oxidizing radicals,　1:402-403
primary radicals,　1:401-402,404-408
radical reactions,　1:404-410
reducing radicals,　1:402,403-404
secondary radicals,　1:402-404,408-410
see also aqueous…
waterborne polymer dispersions, industrial emulsion polymerization,　4:1722-1723
water-insoluble monomers, emulsion polymerization,　4:1721-1722
water-soluble monomers, inverse emulsion polymerization,　4:1722
water-soluble polymerization systems, initiation stage, nitroxide-mediated polymerization,　4:1821,1822
water-soluble tin hydrides, preparation,　2:537-538
water vapour, radiation-induced radicals in gaseous systems,　1:398-399
wavefunction-based methods, radical stability determination,　1:454
whitasomnine, synthesis, alkyl selenide arylations,　2:1066
white adipose tissue, oxidative stress,　3:1690-1692
Wohl-Ziegler reaction,　1:18
α-xanthate-α-fluoroacetate, additions, dihydrofuran,　2:606
xanthates
additions
alkenes,　2:976
olefins,　2:976-977
vinyl epoxides,　2:619
allylations,　2:981-982
amidyl radical generation/trapping,　2:976-977
aminomethylations, alkenes,　2:975
Barton-McCombie deoxygenations,　2:965-967
tributyltin hydride-mediated,　2:549-550
cyclizations,　2:976-981
cyclopropylacyl radical generation/trapping,　2:976-977
degenerative transfers,　2:972-983
mechanisms,　2:972-974
group transfers
allylpinacolborane,　2:623
organoboranes,　2:606
radical chain reactions,　1:77,78
homolytic aromatic substitutions, synthetic applications,　2:1066
polycyclic aromatic compound synthesis,　2:978-981
radical-polar crossover reactions,　2:978-979
radical Smiles rearrangements, nitrogen-centered radicals,　2:778-779
reductions, N-heterocyclic carbene boranes,　2:621
reversible addition fragmentation chain transfer,　4:1895,1896,1898,1904,1905-1906,1921
synthetic applications,　2:965-987
tandem cyclizations, branched-chain sugar synthesis,　2:1147-1148
tetrasubstituted alkene synthesis,　2:983
tin-free modifications,　2:967-970
vinylations,　2:981-982
see also dithiocarbonates
xenobiotics, reactive oxygen species generation,　3:1265-1266
xenon, matrix isolation spectroscopy,　1:207
xenon exciplexes, inducing thermal reactions in matrix isolated radicals,　1:210
X-ray crystallography
silyl radicals,　4:2121,2124,2125-2126
bis(silyl)-substituted,　4:2134
disilenes/disilynes,　4:2136-2137
tris(silyl)-substituted,　4:2125-2126,2131
X-rays, interactions with matter,　1:395,396
p-xylene, photocatalytic oxygenation,　1:374-378
xylobovidine, synthesis,　2:1147-1148
ynones, macrocyclization/transannulations,　2:732-733
Zeeman interactions, EPR spectra,　1:148
zeolites
radiation-induced radical reactions,　1:421-423
radical reactions inside framework,　1:245
zinc complex-catalyzed reactions, cascades,　2:755-756
zirconium-catalyzed reactions,　2:1015-1016
zirconocene dichloride, Schwartz reagent generation,　2:1015-1016

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Encyclopedia of radicals in chemistry, biology and materials

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