Aconitase 321 Acquired Immunodeficiency Syndrome (AIDS

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Aconitase 321 Acquired Immunodeficiency Syndrome (AIDS 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.
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