Index

A Allylglycine 260 Allylic hydroperoxides 284, 296 Alzheimer's disease 206,433 Aconitase 321 Amide basket-handle hemes Acquired immunodeficiency 106 syndrome (AIDS) 317 Amione oxidases 217 Actinomycin 223, 368 2-Aminophenols 222 Actinomycin D 362 2-Aminophenoxazinone 222 Activated organic peracids 30 Amines 48, 151 Active-site synthesis 95 D-Amino acid oxidase 43, 315 Acyl CoA dehydrogenases 42 o-(L-a-aminoadipoyl)-L-cysteine- Adamantane-6, 6-cyclophane D-valine (ACV) 259 heme-1,5-DeI 100 Ammonia monooxygenase Adamantane heme cyclophane, 210-211 120, 123 Amyotrophic lateral sclerosis Adenine (A) 340 (ALS or Lou Gehrig's disease) Adenosine monophosphate 189,318 (AMP) 38 Anaerobic microorganisms 1, S-Adenosylmethionine 301 313 Aliphatic hydrocarbons 26 Anthracene cyclophanes 111 Alkenes 145 Anthranilate hydroxyl 63 epoxidation 144-147 Antioxidant defense systems 313 vertical ionization potentials Apoprotein B 439 145 Apoprotein E 439 Alkyl hydroperoxides 28 Aquo complexes 13 Allene oxide 403 Arachidonate metabolism 437

451 452 Index

Arachidonic acid(s) 437, 440 342-343, 346, 350, 355, 357, 2-Arachidonoly (2-Linoleoyl 369 phosphatidylcholine) 438 Bleomycin-cobalt (COIl BLM~ 355 Arginine 64 Bleomycin-copper (BLM Cu), Aromatase 26 358-359 Aromatic hydrocarbons 26 Bleomycin-iron (BLM Fe) 346- Aromatic hydroxylases 55, 61, 347, 349-351, 355, 357, 363, 64 372-373 Artherial endothelium 435 Bovine Serum Albumin (BSA) Arthritis 276 379-380 Arthrobacter 412 1,3-Butanediol 402 Artificial proteases 379 Ascorbate (Vitamin C) 317, 361, 371, 380, 382 Ascorbate oxidase 213 C Asthma 276, 435 Atherosclerosis 276,328, 433, Calcitonin 208 435, 437, 440 Calicheamicin 411 Atherosclerotic lesion 434 Calmodulin 383 Atherosclerotic plaque 442 d-Camphor 25 AlP (Adenosine triphosphate) 2 Cancer 433 Autooxidation 279 Capped hemes 112 E-Caprolactone 55 Carbanions 282 B Carbonyl oxide 58 ~-Carotene 141, 439 Bacterialluciferases 51, 53 Catalase(s) 87, 93, 126, 132, 136, Baeyer-Villiger reactions 50, 55 318 Basic/Nucleophilic peroxide 200 Catechol 412 Benzene 401,411-413,423 Catecholase activity 195 trans-Benzene-l,2:4,5-dioxide Catechol dioxygenase enzymes 408 30 Benzene oxide 414,416, Catechol dioxygenases 253- 419-420, 423 254, 286 Benzooxepins 425-426 Catecholl,2-dioxygenase 254 Benzoylacetoneethylenediimine Catechol2,3-dioxygenase 256 6 Ceruloplasmin 439 1,4-Benzyne (1,4-Benzendiyl) C - H activation 198 409-410 Chelated 18-cyclophane 114 Biciyclo [5.1.0] octa-2,4-diene Chelated heme system 96, 102 408 reactions with carbon monoxide Binding dynamics of chelated 102 hemes 97 reactions with oxygen 102 Biotin 384 Chelated heme-t-butyl isocyanide Bleomycin (BLM) 233-237, 239, complex 118 Index 453 m-Chloroperbenzoic acid 47 dopamine ~-monooxygenase Cholest-5-en-3~,7a-diol 441 (D~M) 191 Cholest-5-en-3~,26-diol 441 methane monooxygenase Cholest-5-en-3~-ol-7-one 441 (MMO) 191 Cholesta-3,5-diene-7-one 441 peptidylglycine a-amidating Cholestan-5a,6a-epoxy-3~-ol monooxygenase (PAM) 191 441 phenylalanine hydroxylase Cholestan-5~,6~-epoxy-3~-ol (PAN) 191 441 tyrosinase (Tyr) 191 Cholestan-3~-5a-6~-triol Copper-zinc SOD (Cu ZnSOD) 441 318-319 Cholesterol 439,441,444 Corey mechanism 301 Chromate (CrO~-) 12 Cresolase activity 195, 197,203 Chromomycin A2 363 18-Crown-6 366 Chemically induced electron Cr(phen)~+ 374 exchange luminescence {CuI[HB(3,5-iPr2pzhn 200-201 (CIEEL) 53 {Cu [HB(3,5-iPr2pzh1}z(02) Clavaminate synthase 252 193-194, 196,200-202 Co(DIP)~+ 375 Cu(phen)t 374 Collagen 217, 434-435 Cu(ghen)~+ 374 Continuous wave-electron CuIII(phen)z 369-374 nuclear double resonance Cupric-peroxo complexes 27 (CW-ENDOR) 217 Cupric-water complex 19 Coodination complex 12 Cyclohexanone 55 copper 5, 188 Cyclohexanone monooxygenase hydroxide 12 49-50, 54, 56 oxide 12 Cyclooxygenase 437,439-440 Co(phen)~+ 374 Cyclophane(s) 95 Copper amine oxidases 218 rate constant for binding carbon Copper homeostasis 189 monoxide 113 Copper monooxygenase model rate constant for binding system 197 oxygen 113 Copper monooxygenases 210 Cyclophane heme 99 Copper oxidases 191, 213 5,5,5-Cyclophane heme 114 amine oxidase 191 7,7,7,7-Cyclophane heme ascorbate oxidase 191 114 'blue' multicopper oxidases Cyclophane heme compounds 191 111 cerulopasmin 191, 213 ~-Cyclopropylanine 260 cytochrome c oxidase 191 Cyclopropylcarbinyl radicals galactose oxidase 191 292,299 laccase 191, 213-214 Cysteine 24, 340 phenoazinone synthase 191 Cytochrome bs 88 Copper oxygenases 191, 195 Cytochrome c 88,93 ammonia monooxygenase Cytochrome c oxidase 2, 16, (AMO) 191 19-20, 191, 219-220 454 Index

Cytochrome c oxidase (four• 2,8-Dioxabicyclo[5.1.0]octa-3,5- electron reduction by diene 408 cytochrome c oxidase) 20 4,8-Dioxabicyclo[5.1.0]octa-2,5- Cytochrome c peroxidase 87,90, diene 422 93, 128, 132-133 7,8-Dioxabicyclo[2.2.2]octa-2,5- mechanism of proton-transfer diene 408 catalysis 132-133 7,8-Dioxabicyclo[4.2.0]octa-2,4- Cytochrome oxidase 88, 90 diene 408 Cytochrome P-450 18-26,68,88, Dioxetane(s) 280-281,417 93, 143, 147, 151-152, 154, Dioxetane 52-53 232-233, 235-236, 239, Dioxygen-activating enzymes 18 243-244, 248, 299-300, 315, Dioxygen-activating 325,437 metalloenzymes 22 Cytochrome P-450 Dioxygen activation 21, 23, 126 monooxygenase 190,215 Dioxygenases(s) 2, 18, 211, 277, Cytochromes 88 286,413 Dioxygenase quercetinase 212 Dioxygen binding kinetics 117- 125 D environmental effects on 121-125 Daunomycin 362 Dioxygen bonding 8,9 Deacetoxycephalosporin C Dioxygen carriers 86 synthase 252 Dioxygen complex 5 14, 15-Dehydroarachidonic acid Dioxygen ligand 5 293 Dioxygen reduction 9-10 Denitrifying bacteria 189 Dioxygen reduction by DNA hydrolases 337 complexes 9 DNA ligases 337 Dioxygen reduction by metal Deoxyhemerythrin 238 ions 9 Deoxyhemoglobin 16, 86 Dioxygen storage proteins 15 Desferrioxamine 326 Dioxygen toxicity 30 Diabetes 433 Dioxygen transport 15 Dialkyldioxiranes 137 Direct reactions of peroxidic Dihydroxyacid dehydratase 321 intermediates with substrates 3,4-Dihydroxyphenylalanine 24 (L-DOPA) 64 Diradicals 280 Diiron enzymes 237 Distal side effects 117 Diiron-oxo proteins 237 hydrogen bonding 117 l,l-dimethoxyethylene 406 local polar environment 117 trans-3,4-Dimethyl-1,2-dioxetane pocket steric effects 117 408,418 Distal (reactive) side steric effects Dimethyldioxirane 415-416 110 2,7-Dimethyloxepin 415 dynamics 117-120 5,5-Dimethyl-1-pyrroline-N-oxide electronic effects on 101-103 (DMPO) 339 internal polar effects on 103 Index 455

reversibility 98-100 Endoperoxides 417-418 solvent effects on 103 Enzymes-catalyzed oxidation of steric effects on 103-117 cyclopropylamines 152 Distamycin 365,368 Epinephrine 250 Distamycin A 362 Epoxyeicosatrienoic acids (EEls) Disulfides 48 437 D~A 340, 342-343, 348-349 14, 15-Epoxyeicosatrienoic acid affinity, cleavage probes 383 437 BD~A 341,364,370-372,377 Exo-epoxynorbornane 137 B-form helices 375 2,3-Epoxyoxepin 414-417, 419, circular supercoiled D~A (form 422-424 I) 340 7-Ethoxycoumarin 152 closed circular, superhelical Ethylmethyldioxirane 137 D~A (form I) 341 Extended X-ray absorption fine double-stranded B D~A 344 structure (EXAFS) linear duplex (form III) 341 spectroscopic study 206, nicked circular (form II) 341 255, 261, 285, 288 right-handed helical B-form External monooxygenases 38- 340 39,46,52 single stranded D~A 344 Extradiol-cleavage 258 supercoiled D~A 359,362 Extradiol-cleaving catechol triple helices 366 dioxygenases 257 Z D~A 371, 377 Extradiol-cleaving enzymes 254 D~A cleavage 340-378 DOPA 245,250 Dopamine 205 F Dopamine ~-monooxygenase (D~M) 205 FAD (Flavin adenine Dopamine quinone 218-219 dinucleotide) 37-38,46,48, Down's syndrome 319 55, 64 Fatty acid hydroperoxides 276, 292, 298 Fatty acid radicals 294-295, 298 E [Fe2(BIPhMeh(02CH)4] 239 [Fe2(BPMP)(Jl-02CC2Hsh] + 242 Eicosanoids 436,439,442 Fe(5,5,5)cyclophane 111 Elastin 217 Fe(6,6,6)cyclophane 111 Electron paramagnetic resonance Fe(7,7,7)cyclophane 111 (EPR) 41, 59, 212, 214, 236, Fe(7,7,7,7)cyclophane 111 241-242, 255, 285, 289, 339, Fe(8,8,8,8)cyclophane 111 356 [Fe(EDTA)(OH2)r 360 Electron spin echo envelope [Fe{HB(3,5-i-Prz-pzh} (OBz)- modulation (ESEEM) 217 (CH3C~)] 247 Electrophilic reactivity of ferric• [Fe2(HPTP)OBzf+ 247 hydroperoxide complexes [Fe2(6-Me-HPTP)OBz(H20)f+ 30 247 456 Index

[Fe2(N-Et-HPTB)(OBz) f+ 247 FMN (Flavin mononucleotide) Fenton reactions 322, 338 37 -38, 46, 51, 64 [Fe2(OH)(OAch(Me3 TACN)z] + FMO (FAD-containing 238 monooxygenase) 48,54 [Fe(EDTA)(OH2)]- 560 Free-radical intermediates 150 FeO-O dipole 105 R-state 105 T-state 105 G Fe(phen)~+ 374 Fe~hen)~+ 374 o-Galactose 215 FeI P(Oz) 22 Galactose oxidase 215-217 FeIVp(Oz) 19 Gastrin 208 FeIIIP(OH) 19 Glucose oxidase 44 Ferric complexes 27 Glutathione peroxidases 318 Ferric-heme hydroperoxide Glyceraldehyde-3-phosphate intermediate 25 dehydrogenase 322, 324 Ferric-hydroperoxide Glycolate oxidase 45, 315 intermediates 25 Glyoxylic acid 208 Ferric lipoxygenase 286, 299 Gout 435 Ferric-peroxo species 22 Group-increment(s) 401-402, Ferritin 327, 439 411,421 Ferrous cytochrome c 87 Guanine (G) 340, 344, 376 Ferrous lipoxygenase 288, 301 Fe2[(salmp)zf- 240 [Fe2(TPAh(OAc)z] 246-247 H Fibroblasts 316 Flavin C (4a)-hydroperoxide 47 Heats of reaction 4 Flavin hydroperoxide(s) 40,44, oxygenation of organic 46, 56-58, 62 compounds 4 Flavin hydroxylases 39 Heme 189 Flavin monooxygenase enzymes Heme-containing enzymes 21 21 Heme-containing proteins 15 Flavin monooxygenases 3 Heme-containing system 26 Flavin peroxide 42 Heme (FeTpivPP)-l,2-dimethyl- Flavin reduction 40 imidazole 103 Flavin semiquinone 39 Heme-dioxygen complex 22 Flavins 3, 37-40 Heme protein active sites 85 oxidized 40 Heme proteins 84 reduced 40 Hemerythrin 17 -18, 237, 240- Flavocytochrome b2 45 241 Flavoenzymes 38-39 Heme FeIV -oxo intermediate 25 oxygen-Oz utilizing 38 Heme-oxo complex Flavoprotein hydroxylases 55 ([FeIv(p. )(Or)]+) 23 Flavoprotein oxidases 39, 43 Heme oxygenase 26 Flavoproteins 38 Hemin 136-137 Fluoride (F-) 12 Hemin catalysts 150 Index 457

Hemin-catalyzed epoxidation Hydroperoxide(s) (HOO-) 10, 149 29, 133-135, 143 Hemin-catalyzed oxidation 151 free radical reactions 135-136 Hemocyanin 17-18, 190-191, Hydroperoxo complxes 27,29 196,204 Hydroperoxo-CuII intermediate Hemoglobin 15-18, 86, 92, 202 94-95, 98, 120, 123, 125, 190, Hydroperoxo intermediate 26 327 Hydroperoxo species 22 R-state 94, 98, 99, lOS, 107, Hydroperoxyeicosatetraenoic acid 110, 120, 124 (HPETE) 437 T-state 94, 99, lOS, 107, 120, 5-Hydroperoxyeicosatetraenoic 124 acid 437 Hemostasis 436 Hydroperoxyiron intermediate Z-l,5-Hexadiyne-3-ene 410-411 126 trans-2-Hexanal 276 Hydroperoxyl ( . OOH) 336 cis-3-Hexanol 276 13-Hydroperoxy-9,11- High density lipoproteins octadecadienoic acid 277 (HDL) 439 2(5)-Hydroperoxy High-spin d5 ferric hydro peroxide phosphatidykholine 438 complexes 28 C( 4a)-Hydroperoxypterin 68 High-valent metal complexes Hydroquinone(s) 3, 141, 418 128 Hydroxo complexes 13 High-valent metal-oxo 19 2-Hydroxy-adenine 318, 373 High-valent metal-oxo complexes p-Hydroxybenzoate hydroxylase 27 55 High-valent metal-oxo Hydroxycyclohexadienyl radical intermediates 26 59 Horseradish peroxidase 87, 110, 6-Hydroxy dopa (topa) 217 125, 128, 131, 133-134, 143, 11-Hydroxy-12-13-epoxy-9- 233 octadecenoic acid 277 Horseradish peroxidase• Hydroxyflavin 53, 60, 62 hydroxamic acid complex 8-Hydroxyguanine 318, 350, 373, 125 376 Horseradish peroxidase-oxygen Hydroxyl (OH·) 20, 22, 314-315, complex 124 318,321-327,336,338-339, Human immunodeficiency virus I 349-350,358,361,363,367- (HIV-I) 317 369, 372, 378, 381, 416, 425 Hydrogen peroxide (H20 2) 5, Hydroxylamines 48 20, 40, 43, 46, 48, 55, 58, Hydroxylation of unactivated 61, 65, 69, 86-87, 126, 128, alkanes 24 130, 133-134, 136, 213, 217, 6-Hydroxynicotinate 57 233,244,279,314,317-318, 4-Hydroxynonenal 438, 440-441 321, 322-326, 338, 347-350, p-Hydroxyphenyl acetate 359-360, 362, 371, 374, 378, 3-hydroxylase 62 380-382 p-Hydroxyphenylpyruvate toxicity 320-323 dioxygenase 251-253,300 458 Index

C(4a)-Hydroxypterin 67 Kitajima mechanism 203

I L

Interferons 327 Laccase(s) 191, 213-214 Interleukins 327 Lactate oxidase 44-46 Internal entropies 407 Leukotriene B4 (LTB4) 437 Internal monooxygenases 38 Leukotrienes 327 Intradiol-cleaving catechol Ligand-to-metal a-bonding 8 dioxygenases 256 Ligand-to-metal1t-bonding 13, Intradiol-cleaving enzymes 254 27 Iodosylbenzene(s) 27, 129-132, Limulus II (horseshoe crab) 134, 143, 146, 150, 236 hemocyanin 192 Iron(II) porphyrin-oxygen Linoleic acid 277,287-289, complex 96 295-298, 440 . Iron (Fe)-complexes 5 Lipid hydroperoxides 321, 442 Iron (Fe)-heme complexes 15 Lipid oxidation 433 Iron (FeIV)-oxo complex 11,237, Lipid peroxidation 327, 336 361 Lipoproteins 439 Iron-oxo intermediate 68, 350 Lipoxin 437 Iron-peroxo species 237 Lipoxygenase(s) 30, 276-279, Iron(IV) porphyrin cation radical 284, 286-290, 292-297, 128 299-301, 437-440 Iron (Fe)-porphyrin complex 15 Lipoxygenase inhibitors 276 Iron porphyrin system 27 Low-spin d5 ferric hydroperoxide Iron superoxide dismutase complexes 28 (FeSOD) 261 Low-spin d6 metal(s) 27 -28 Iron(III) tetramesitylporphyrin COIII 27 129, 142 I~II 27 Iron(III) tetrapentafluorophenyl- RhIII 27 porphyrin 142 Luciferases 51-52,54 Isoalloxazine 38-39 Lumazine 54, 57 Isoalloxazine ring system 37 Lumiflavin 47 Isopenicillin N 259 Lymphocyte 31,5 Isopenicillin N synthase (IPNS) Lysine monooxygenase 46 253, 259, 286

M K Macroincrementation 403 a-Ketoacid-dependent Macrophages 435, 440, 442 hydroxylases 253 Magnesium oxide (MgO) 12 Kinetic isotope ef£ect(s) 280,288, Malondialdehyde 438, 440 296-297 Mammalian mitochondrial Index 459

cyctochrome c oxidase 220 E,E 407, 413-414 Mechanisms of dioxygen Z,E 407 activation 20 Z,Z 407,413,417-419 Metal-containing oxygenase Muconic acid 407, 413 enzymes 18 E,E 407,417 Metal-dioxygen biochemistry 15 Z,E 407 Metal-dioxygen chemistry 4 Z,Z 407,412,417 Metal-dioxygen complexes 5-6 Myeloperoxidase 440 Metal-EDTA complexes 359-369 Myoglobin 16-18, 86, 90, 95, 98, Metallobleomycins 342-343, 110, 121, 123, 125, 190, 327 347, 355, 359 Metalloproteins 5 Metal-oxo complexes 11-13,338 N Metal-oxo compounds 12 Metal-peroxo complexes 29 Metal-to-ligand n-backbonding NAD (Nicotinamide adenosine 8 dinucleotide) 315 Methane 18 NADH 46, 48, 55, 62, 241, Methane monooxygenase 315, 323, 358, 371 (MMO) 210,237,241-243, NADH dehydrogenase 321 246, 300 NADPH 46,48, 55, 59, 65, 323 Methanotrophic bacteria 210 NADPH oxidase 439 2-Methyl-3-hydroxyl-5- Naphthalene 424 carboxypyridine (MHPC) Naphthalene oxides 425-426 oxygenase 63 Netropsin 362, 373 Methyl (Trifluromethyl)- NIH shift 151, 423 dioxirane 415 Ni(phen)~+ 374 Microperoxidase 131 Nitric oxide (NO) 64, 85, 288, Microperoxidase-8 134 320-322 Mn(phen)~+ 374 Nitric oxide synthase 64 Model porphyrin complexes 84 Nitrite 189 Mono-1-methylimidazole-meso- Nitrones 48 tetra (a,a,a,a-O• Nitrous oxide 189 pivalamidophenyl) porphyrin Non-basic/electrophilic peroxide iron(II) 96 200 Mononuclear monodentate metal• 'Nonblue' oxidases 215 oxo complexes 15 Nonheme iron centers 232 Monooxygenase(s) 2, 18,203, Nonheme iron enzymes 189- 300,413 190,286 Mossbauer spectroscopy 236, Nonheme iron monooxygenase 240, 244-245, 248, 255, 285, enzymes 28 288 Nonheme metalloenzymes 26 MPE-Fe (Methidiumpropyl• Nonheme systems 26 EDT A-Fe II) 361-363,365 Non-next-nearest neighbor Muconaldehyde 407,413,416, effects 402 424 Noradrenaline 250 460 Index

Norbornene 137, 141, 146 Oxo iron species 129, 138, 322 Norbornyl radicals 146 Oxo ligands 10 Norcaradiene 420 Oxygenase enzymes 18, 21, 30 Norepinephrine 205 Oxygenases 16 N-oxides 48 Oxygen atom (0°) 13 Nuclease activation 326 Oxygen rebound mechanism 24 Nucleic acid affinity cleavage Oxygen (02) storage 15 365-366 Oxygen (02) transport 15 Nucleophilic dioxygen species Oxyhemerythrin 6-7,238 283 Oxyhemocyanin 6-7, 17-18 Oxyhemoglobin 7,22 Oxymyoglobin 22, 91 Oxy-picket fence heme 100 o Ozone 137, 314

Octadecadienoic acid 290 Z,Z-Octa-1,3 ,5,7-tetraene p 408,424 0-0 stretching frequencies and separations 7 Particulate-methane Organic peracids 29 monooxygenase (p-MMO) cr-Organoiron 282 211 Ortho effect 107 E-2,4-Pentadienal 406 7-Oxabicyclo[ 4.1. O]heptane Pentafluoroiodosylbenzene 421 (PFBI) 135, 140 Oxene [Fe v 0] 90, 129, 131, Peptidylglycine a-amidating 133-134, 136, 138-139, monooxygenase (PAM) 208 141-142,153-155,236 Peracids 27, 129 Oxepin 414,416, 419-420, 423, Perepoxides 280-281 426 Perhydroxyl radical (H02) 321 Oxidases 38 Permanganate (Mn04) 12 Oxidases and internal Peroxidase(s) 87, 126, 277, 294, monooxygenases 43 359 Oxidative stress, 323-328 Peroxide (O~-) 4, 338 Oxide (02-) 4, 9, 13, 15 Peroxide shunt 23,233 Oxidized flavin 40 Peroxo complexes 27-28 Oximes 48 CoIII 27 Oxo complexes 13 I~Il 27 Oxo-bridged complexes 11 MovI 27 Oxo-bridged iron RhIII 27 species 11 TiIV 27 E,E-6-0xo-2,4-hexadienoic Jl-peroxo complex 11, 17 acid 414 Jl-peroxo diheme complex 17 Oxoiron [FeIv] 129 yv 27 Oxoiron(V) porphyrin 232 Peroxodicopper (II) oxy-form Oxoiron(IV) porphyrin cation 192 radical complex 233 Index 461

Peroxo ligands 10, 19 Pterin-dependent hydroxylases Peroxo-like complexes 5-6 249 Peroxyl radicals 321 Pterin-dependent iron Peroxynitrite 320-321 hydroxy lases 250 Phagocytes 315, 317, 320, 324 Pterin hydro peroxide 66-68 PHBH 60-61 Pterin hydroxy lases 39, 64 Phenethylamine hydroxylation Pulse radiolysis 44-46 mechanism 207 Purple acid phosphatase 237 Phenol 412,416 Purple lipoxygenase 295 Phenol hydroxylase 62 Putidamonoxin 248-249 Phenoxazinone synthase 222 2H-Pyran 404-407 Phenylalanine 67 2-carboxaldehyde 404, 407, 409 Phenylalanine hydroxylase (P AH) 2-carboxylic acid 404, 407, 409 64-69, 210, 250, 424-425 6-hydroxy 404, 407 6-Phosphogluconate 321 6-hydroxy-2-carboxaldehyde Phospholipase Az 438 407 Phospholipids 439 6-hydroxy-2-carboxylic acid Phthalate dioxygenase 248-249 407 Picket fence heme 95,98 6-methoxy 404, 407 Picket-fence porphyrin 96 4H-Pyran 405 Platelet activating factor Pyridine-5,5-cyclophane 115 (1-0-alkyl-2-acetyl-3- 3,5-Pyridine-5,5-heme phosphocholine, PAF) 438 cyclophane 112 P-nitroperbenzoic acid 30 Pyruvate 45 Pocket hemes 112, 115 Polyunsaturated fatty acid (PUF A) 436 Q Potassium monoperoxysulfate (KHSO ) 350 s Quercetinase 191, 211 Potassium superoxide 7 Quercetin-2,3-diooxygenase 211 Procollagen 252 Quercetin (3',4' ,5,7- Prolyl hydroxylase 249, 251 tetrahydroxyflavonol) 211 Prostacyclin (PGlz) 438 Prostacyclin synthase 437-438 Prostaglandin(s) 327 Prostaglandin Hz 437-438 R Prostaglandin H synthase 300 Prostaglandin 12 437 'Rebound' mechanism 154 Protein .cleavage 378-384 Reduced flavins 39 Protein kinases 324 Reduction of nitrogen-oxide Protocatechuate 3,4-dioxygenase species 189 (peD) 254-256 Resonance Raman spectroscopy Protoheme 84 238,247-248,255-256 Protohemin 84-85, 130 Retrolental fibrophasia 314 Protoporphyrin IX 16, 19 Reversible dioxygen binding 98, Pseudomonas putida 62, 412 190 462 Index

Rheumatoid arthritis 433,435 Staphylococcal nuclease• Ribityl phosphate chain 38 Fe(EOTA) system 382 Ribonucleotide reductases 300 Steric strain effects on kinetic and Rieske-type Fe2S2 cluster 248 equilibrium data 108 Ring correction factor 402 Stopped-flow methods 44-45, RNA 365 49, 56, 148 A-form helices 376 Strain energy, 402 IVSRNA 365 Streptavidin, 384 5 S ribosomal RNA 368 Substrate activation, 30 16 S ribosomal RNA 365 Substrate activation by oxygenase tRNA 365 enzymes 30 tRNAphe 377 Suicide-labeled (N-alkylated) RNA polymerase 373 hemins 149 RNR (ribonucleotide reductase) Suicide labeling 147 237,243 Superoxide (02) 2-5, 10, 41, RNRR1 239 284, 314, 316-318, 320-325, RNR R2 239-242, 244-246 327, 336, 338, 360, 362, 371, ROS (reactive oxygen species) 382 314, 316, 324-325, 327 toxicity 320-323 Rubrerythrin 237 Superoxide dismutase (SOD) 41, (Ru(DIP)~+ 375 65, 189, 191,314, 318-319, RufEhen)~+) 375-377 323, 337, 362, 371 Ru (phen)~+ 375 Superoxo-complexes 5-6 (Ru(TMP)~+) 375-377 Superoxo ligands 10 Symmetry number 407 Synthetic copper-dioxygen s complexes 193

Selenoproteins 318 T Singlet dioxygen (".-1g O2) 7, 279, 281, 296, 299, 314, 318, 339, 377,418 TARF (Tetraacetyl riboflavin) 41 enthalpy of formation 418 Tetra-2, 6-dichlorophenyl Singlet dioxygen-ene reaction porphyrin iron(III) chloride 279, 298 (TOCPPFeCl) 130, 137 Single-oxygen atom donors 22, Tetrahydrobiopterin 39, 64, 27 68-69 Sodium metaperiodate (NaI04) Tetrahydropterin cofactor 249 350 5,10,15,20-Tetrakis (2,4,6- Soybean lipoxygenase 284, 293 triphenylphenyl porphinato) Spin traps 287, 294, 339 (FeTTPPP)-1,2-dimethyl• Standard reduction potential for imidazole complexes 103 one- and two-electron 5,10,15,20-Tetrakis (2,4,6- reduction of dioxygen species triphenylphenyl) porphinato in water 3 iron (II) complex 103 Index 463

Tetramesityl heme 110 Tyrosinase 18, 190, 195-196; Tetramesityl iron (III) porphyrin 202-205 chloride 135 Tyrosine hydroxylase 64,67,69, Tetraphenyl borate 246 249-250 Tetraphenyl hemes 107, 110 Tetraphenyl porphyrin(s) 139 Thermochemical estimations 401 u 13-Thiaarachidonic acid 293 Thiolate rebound mechanism Ubiquinol 439 261 Thiols 48-49 Thrombosis 433,435,437 v Thromboxane (TxA2) 438 Thromboxane A2 437 Vascular endothelial cells 316 Thromboxane synthase 437 -438 Vasopressin 208 Thymine (T) 340 Very low density lipoproteins [{(TMPA)Cuh(02)f+ 193-194 (VLDL) 439 a-Tocopherol 314,317 Vitamin B12 300-301 Topa 218-219 Vitamin C 439 Topaquinone 218-219 Vitamin E 439 Transgenic mice 318 Vitamin K-dependent proteins Trichlomethylperoxyl radical 325 252 Trichloromethyl radical 325 Trifluoroperazine (TFP) 383 Triglycerides 439 z Tropylidene 420 Tryptophan monooxygenase 46 Zn(phen)i+ 374 T-state hemoglobin model 99 Zwitterions 280-281