Resonance raman investigations of flavins and flavoproteins

Chapters in this book

1. Frontmatter I
2. Preface V
3. Organizing committee IX
4. Acknowledgements IX
5. Contents XI
6. STRUCTURE AND MECHANISMS OF FLAVOENZYMES
7. Absolute stereochemistry of flavins in enzyme - catalyzed reactions 3
8. Conserved cysteine pairs of mercuric ion reductase: an investigation of function via site-directed mutagenesis 13
9. Reduced forms of native mercuric reductase and their reactions with mercuric compounds - activity vs inhibition 29
10. Rapid-scan stopped-flow studies of the flavoenzyme mercuric reductase during catalytic turnover 33
11. The penultimate cysteines in mercuric reductase aid in the reduction of mercury 41
12. The active center of glutathione reductase at 1.54 A resolution 45
13. Kinetic isotope effect studies on yeast, spinach and human erythrocyte glutathione reductases 55
14. Excited electronic states of flavin-containing coenzyme models 59
15. Trypanothione reductase from Trypanosoma cruzi 69
16. Inactivation of two-electron reduced Escherichia coll glutathione reductase by NADPH and NADH 75
17. Studies on the active site of human erythrocyte glutathione reductase using 6-SCN-FAD and 6-mercapto - FAD 79
18. Protein engineering of glutathione reductase from Escherichia coli 85
19. Studies on the active sites of lipoamide dehydrogenase and glutathione reductase 89
20. Cloning, organisation and nucleotide sequence of the Azotobacter vinelandii gene for lipoamide dehydrogenase 99
21. Reaction of pig heart lipoamide dehydrogenase with monobromoacetone and 1,3-dibromoacetone 103
22. Site-directed mutagenesis of thioredoxin reductase 107
23. Effects of urea on redox properties of streptococcal NADH peroxidase 111
24. Three dimensional structure of baker's yeast flavocytochrome b₂ 123
25. Mechanism of L-lactate dehydrogenation catalyzed by flavocytochrome b.₂ from baker's yeast 133
26. Inactivation of yeast flavocytochrone b.₂ with fluoropyruvate. Modification of the active site histidine 143
27. Evidence for an alteration of the flavin behavior induced by 2-methyl - 2,4 - pentandiol in cerevis iae flavocytochrome b₂ 145
28. Medium chain acyl-CoA dehydrogenase from pig kidney: Aspects of the reductive half - reaction 149
29. Crystal structure of the general acyl-CoA dehydrogenase 159
30. Inactivation of general acyl-CoA dehydrogenase from pig k i dney by the suicide substrate methylenecyclopropylacetyl - CoA. Stucture of one of the covalent flavin-inhibitor adducts 161
31. 2 - Bromo-octanoyl CoA: Apseudo-substrateforgeneral acyl-CoA dehydrogenase 165
32. Reaction of pig kidney medium chain acyl-CoA dehydrogenase with ^ - oxidation intermediates 169
33. Medium chain acyl-CoA dehydrogenase from pig kidney: I n activation of the reduced enzyme by 2-octynoy1-CoA 173
34. Oxidation - reduction of general acyl-CoA dehydrogenase by the butyryl-CoA / crotonyl-CoA couple. A new investigation of the rapid reaction kinetics 177
35. Catalytic versatility of butyryl-CoA dehydrogenase from M. elsdenii 181
36. Oxidation-reduction potential of glutaryl-CoA dehydrogenase from Paracoccus denitrifleans 185
37. ¹³C NMR studies on the complexes and reaction intermediates of D-amino acid oxidase 189
38. ¹³C-,¹⁵N-, and ³¹P- NMR studies on 6-hydroxy-L-nicotine oxidase from Arthrobacter oxidans 197
39. A study on the interaction between reduced D-amino acid oxidase and ligands 201
40. D-Amino acid oxidase from the yeast Rhodotorula gracilis 205
41. Purification and properties of D-aspartate oxidase from beef kidney 209
42. Spectral and kinetic studies on Pseudomonas L-phenylalanine oxidase (deaminating and decarboxylating) 213
43. Time - resolved flavin fluorescence of pyridoxine-5-P oxidase from sheep brain 217
44. An active site thiol in lactate oxidase 225
45. Can methylenetetrahydrofolate reductase be used to evade the methyl trap? 229
46. The catalytic mechanism of DNA photolyase 233
47. FLAVOENZYME STRUCTURE AND ELECTRON TRANSFER MECHANISMS
48. Sequence and structure of Anacvstis nidulans flavodoxin: Comparisons with flavodoxins from other species 249
49. C-13, N-15, and two-dimensional NMR techniques in flavoprotein research 261
50. Two dimensional NMR studies on Megasphaera elsdenii 271
51. Flavodoxin from Anabaena 7120: Uniform N-15 enrichment and nitrogen-15 and phosphorus - 31 NMR investigations of the FMN binding site in the reduced and oxidized states 275
52. Pulse radiolysis studies on flavodoxin 279
53. Resonance raman investigations of flavins and flavoproteins 283
54. Spectral studies on hydrogen bonded alloxazines 287
55. Use of flavin and flavodoxin semiquinones as kinetic probes to elucidate the factors which determine reaction rate constants and biological specificity for electron transfer proteins 291
56. Factors influencing the rate of electron transfer from flavodoxin to cytochrome c. 305
57. A computer graphics model of the complex formed between flavodoxin and the tetraheme cytochrome c.₃ 311
58. Cloning and nucleotide sequence of a bacterial flavodoxin gene: Towards the site-directed mutagenesis of the flavin binding site 315
59. Flavin binding site differences between Photobacterium phosphoreum lumazine protein and Megasphaera elsdenii flavodoxin. An investigation using circular dichroism and fluorescence 319
60. Ferredoxin and ferredoxin-NADP⁺oxidoreductase interactions: Mapping of their binding sites 325
61. Complex formation between ferredoxin-NADP+-oxidoreductase and flavodoxin 335
62. Mechanism of ferredoxin-NADP⁺ reductase reaction NADP radical, semiquinone and fully reduced enzyme-NADP+ charge transfer complex as the reaction intermediates 341
63. In vivo deactivation/activation of ferredoxin-NADP+- oxidoreductase from the cyanobacteria Anabaena variabills 345
64. Isolation from Desulfovibrio desulfuricans of a flavoprotein with NADH-H⁺ oxidoreductase activity towards a protein containing a rubredoxin-like center 349
65. Microsomal electron transport system focused on NADPH-cytochrome P-450 reductase 353
66. Time - resolved fluorescence spectroscopy on NADPH-cytochrome P-450 reductase 357
67. Studies on the reactions of flavin- and nicotinamide nucleotide analogues with a bacterial electron-transferring flavoprotein 361
68. Kinetics of ligand binding, amino acid sequence, and crystallization of Chlorobium and Chromatium flavocytochrome c. 365
69. Redox properties of flavocytochrome c. 371
70. Electron transfer kinetics of phthalate oxygenase reductase, an iron sulfur center containing flavoprotein 377
71. CD and potentiometry of the FAD of nitrate reductase 381
72. Kinetic studies on glutamate synthase from Azospirillum bras ilense 385
73. Redox interactions of the FAD in xanthine oxidase with other centers of the protein 391
74. Laser flash photolysis studies of intramolecular electron transfer between the FAD and Fe/S II centers in xanthine oxidase 403
75. Mechanism of action of chicken liver xanthine dehydrogenase 409
76. Interconversion between O-dependent and NAD - dependent types of rat liver xanthine dehydrogenase 413
77. Reactivity of chicken liver xanthine dehydrogenase containing artificial flavins 417
78. The molybdenum cofactor of milk xanthine oxidase 421
79. Isolation of a cDNA sequence coding for a part of xanthine dehydrogenase from rat liver 425
80. FLAVIN BIOSYNTHESIS/ METABOLISM/ AND MEDICAL ASPECTS
81. Biosynthesis of flavins and deazaflavins 431
82. The icosahedral ß₆₀ capsid of heavy riboflavin synthase (6,7- dimethyl-8-ribityllumazine synthase/riboflavin synthase) 441
83. Characterization of human riboflavin-binding immunoglobulins 445
84. Riboflavin uptake by isolated rat kidney cells 449
85. Purification and characterization of the bifunctional enzyme FAD synthetase from Brevibacterium ammoniapenes 455
86. An update on flavin metabolism in rats and humans 459
87. Effects of quinacrine, tetracycline, adriamycin and chloroquine upon flavin metabolism in rats 473
88. Role of flavoproteins in the neurotoxic action of MPTP 477
89. Biosynthesis of flavoproteins 491
90. Biological and Medical Aspects of D-Amino Acid Oxidase — Biogenesis and in vivo reaction with D-propargylglycine — 501
91. Molecular and cellular biology of D-amino acid oxidase 509
92. Localization of D-amino acid oxidase in rat cerebellum 513
93. Biosynthesis of D-amino acid oxidase and molecular cloning of the cDNA 517
94. Characterization of a partially purified nitroaryl reductase 521
95. FLAVOENZYME HYDROXYLASES
96. Crystallographic studies on the mechanism of hydroxybenzoate hydroxylase from Psudomonas fluorescens 527
97. Applications of deuterium and tritium isotope effects to the elucidation of kinetic mechanisms of flavoprotein hydroxylases 539
98. Chemical modification of tyrosine-38 in j>.-hydroxybenzoate hydroxylase from Pseudomonas fluorescens by 5'-Pfluorosulfonylbenzoyladenosine: A probe for the elucidation of the NADPH binding site? 549
99. Phenol Complexes of Phenol Hydroxylase 553
100. The involvement of SH-groups in cooperativity of phenol binding sites in phenol hydroxylase 557
101. 6-Thiocyanate-FAD and 6-mercapto-FAD as active site probes of phenol hydroxylase 561
102. Hysteretic behavior of anthranilate hydroxylase 565
103. Redox potentials of salicylate hydroxylase 569
104. The oxidative half-reaction of 2-methyl-3-hydroxypyridine-5 - carboxylic acid oxygenase from Pseudomonas sp. MA-1 573
105. Lipid stabilization of the flavin hydroperoxide in the microsomal flavin-containing monooxygenase 577
106. FLAVIN-DEPENDENT BIOLUMINESCENCE
107. One-electron transfers in flavin systems: Relevance to the postulated C1EEL mechanism in bacterial bioluminescence 583
108. Characterization of new "bleached" products obtained on treating flavins and flavoproteins with dithionite 593
109. Flavin-mediated hydrogen peroxide production by biological and chemical photosystems 597
110. On the chemical mechanisms of bacterial luciferase, an updating 601
111. Studies on the mechanism of bacterial bioluminescence. Evidence compatible with a one electron transfer process and a CIEEL mechanism in the luciferase reaction 613
112. Structural analysis of bacterial luciferase 621
113. Sequence similarity between the a subunit of luciferase from Vibrio harvevl and clostridial flavodoxin 633
114. Isolation and characterization of a yellow fluorescent protein from Vibrio fischeri strain Y-1 637
115. Purification and characterization of an unusual nonfluores cent flavoprotein from Photobacterium leiognathi 641
116. Purification and some properties of FP₃₉₀ from P. phosphoreum 647
117. STRUCTURE, MECHANISM, AND BIOSYNTHESIS OF FLAVOENZYMES CONTAINING COVALENTLY-BOUND FLAVINS
118. 8α-Imidazolylflavins: Application of their redox and spectral properties to flavoenzyme systems 653
119. X-ray study of flavoenzymes containing covalently bound flavins 663
120. Structural studies of P-cresol methylhydroxylase 673
121. The chemical and stereochemical course of oxidation of 4- ethylphenol and other 4-alkylphenols by ^-cresol methylhydroxylase 677
122. Redox properties of trimethylamine dehydrogenase 687
123. Redox properties of Escherichia coll fumarate reductase 691
124. Reactions of lumiflavin with aminyl and a-amino radicals of piperazine 695
125. Kinetic probes of the proposed radical mechanism of monoamine oxidase 699
126. Stopped-flow studies on the mechanism of the oxidation of N—methyl - 4 - phenyl - 1 , 2 , 3 , 6 - tetrahydropyridine (HPTP) by monoamine oxidase 705
127. Methoxatin containing methylamine dehydrogenase: Enzyme reduction by primary amines 709
128. Interaction of bacterial sarcosine oxidase with folate derivatives 713
129. Sulfhydryl groups and the binding site of noncovalently bound FAD ofCorvnebacterlum sarcosine oxidase 717
130. Dimethylglycine dehydrogenase from pig liver mitochondria: Purification and properties 721
131. Comparison of partial amino acid sequences deduced from the nucleotide sequence of a bovine adrenal monoamine oxidase cDNA clone to amino acid sequences obtained from bovine liver monoamine oxidase type B 725
132. Covalent binding of FAD to Bacillus subtllis succinate dehydrogenase 729
133. 6 - Hydroxy-D-nicotine oxidase: Expression of the flavoenzyme as a covalently flavinylated polypeptide 737
134. The flavin-binding sites of 6-hydroxy-D- and 6-hydroxy-Lnicotine oxidase 747
135. LIST OF PARTICIPANTS 751
136. AUTHOR INDEX 755
137. SUBJECT INDEX 761
138. Backmatter 777