Structure and reactivity of the so-called stable yellow corrinoids

Chapters in this book

1. Frontmatter I
2. Preface VII
3. CONTENTS IX
4. Chapter 1. CHEMISTRY OF CORRINOIDS. TOTAL SYNTHESIS OF VITAMIN B₁₂
5. Introductory remarks for opening of 3rd European Symposium on vitamin B₁₂ 1
6. Introductory remarks. Historical perspectives on the isolation of crystalline vitamin B₁₂ 7
7. New and old problems in the structure analysis of vitamin B₁₂ 19
8. Synthetic vitamin B₁₂ 37
9. Chemical synthesis of corrinoids: current problems and recent advances 89
10. Recent studies on the synthesis of vitamin B₁₂ 119
11. New reactions of the chromophoric system of vitamin B₁₂ derivatives 137
12. Structure and reactivity of the so-called stable yellow corrinoids 141
13. Concerning the structure of so-called yellow products obtained from naturally occurring metal-free corrinoids 149
14. Correlation of vitamin B₁₂ methanolysis products with cobyrinic methyl ester amides prepared from hydrogenobyrinic acid amides 155
15. Preparation and X-ray structural analyses of a cobyrinic acid diamide and the corresponding rhodium analogue 159
16. Concerning a new corrinoid from municipal sludge 163
17. Steric course of the substitution by vitamin B_12s as studied by ¹H-NMR spectroscopy 169
18. Synthesis and X-ray analysis of a porphyrin-type Co(I)-complex 171
19. Stereochemistry of the formation and cleavage of the Co-C bond in a vitamin B₁₂ model 173
20. The structure of superoxocobalamin, a single crystal ESR study 175
21. NMR studies of a novel form of vitamin B₁₂ 179
22. Circular dichroism study of organocobalamins 183
23. Concerning electronic, CD and ORD spectra of isomeric pairs of several (Co-methyl)-corrinoids 189
24. Some properties of cobalaminhexacyanoferrate 193
25. Temperature-jump kinetics of the "base-on" - "base-off" equilibrium of methylcobalamin 199
26. Electrochemistry of vitamin B₁₂. Equilibria, kinetics and mechanisms in the B_12a - B_12r - B_12s oxido-reduction 203
27. Electrochemistry of vitamin B₁₂. Alkyl cobalamins and cobinamides 213
28. Chapter 2. BIOSYNTHESIS OF CORRINOIDS
29. Recent biosynthetic researches on vitamin B₁₂ 217
30. Intermediary metabolism of cobyrinic acid biosynthesis 247
31. On the methylation process in cobyrinic acid biosynthesis 279
32. Biogenesis of tetrapyrrole compounds (porphyrins and corrinoids), and its regulation 293
33. Factor I ex Clostridium tetanomorphum: proof of structure and relationship to vitamin B₁₂ biosynthesis 315
34. On the biosynthesis of the 5,6-dimethylbenzimidazole moiety of vitamin B₁₂ 317
35. The enzyme system of propionic acid bacteria transforming riboflavin into 5,6-dimethylbenzimidazole 323
36. Straight approaches to the nucleotide loop 331
37. Ribosomal proteins share in vitamin B₁₂ biosynthesis 345
38. The ribosomal proteins L2, L5, L18 and L25 involved in vitamin B₁₂ biosynthesis 359
39. Formation and role of vitamin B₁₂ in Protaminobacter ruber and Rhizobium meliloti 361
40. Chapter 3. CORRINOID DEPENDENT ENZYMES AND REACTIONS. MODEL SYSTEMS
41. Current status of the mechanism of action of B₁₂ - coenzyme 373
42. A stereochemical approach to the diol dehydratase reaction 389
43. Coenzyme B₁₂-dependent diol dehydratase - distribution and metabolic role in Enterobacteriaceae, enzymological properties and interaction with coenzyme B₁₂ 413
44. Adenosylcobalamin-dependent glycerol dehydratase interaction with substrates and their analogs 431
45. Glycerol dehydratase from Aerobacter aerogenes 437
46. The mechanism of action of methylmalonyl-CoA mutase as studied with isotope labelling and synthetic models 439
47. Recent studies on the mechanism of action of ethanolamine ammonia-lyase 461
48. Studies on the mechanism of reactions catalysed by ethanolamine ammonia-lyase 471
49. Steric course of the ethanolamine-ammonia lyase reaction 485
50. The chemical synthesis and coenzymatic properties of analogs of adenosylcobalamin in the ribonucleotide reductase reaction 489
51. Review of the EPR of B_12r and B₁₂ -dependent enzyme reactions 505
52. Vitamin B₁₂: current problems and recent advances 511
53. The role of corrinoids in the total synthesis of acetate from C0₂ 529
54. Mechanisms for B₁₂ -dependent methylation 539
55. Nonenzymic models for the enigmatic coenzyme B₁₂-dependent carbon-skeleton rearrangements 557
56. The mechanism of action of coenzyme B₁₂ 575
57. Model systems for adenosylcobalamin dependent enzymic reactions 587
58. Bridged cobaloximes as vitamin B₁₂ models 599
59. Modified adenosylaobalamin: model systems for the active sites of corrinoid-dependent enzymes 605
60. Chapter 4. ANALOGUES AND ANTAGONISTS OF VITAMIN B₁₂
61. Naturally occurring vitamin B₁₂ antagonists and their potential therapeutic value 609
62. Structures of some vitamin B₁₂ analogues and their biological as well as biochemical functions 625
63. Novel metal-free corrinoids and metal analogues 635
64. Preparation of ferribalamin, the Fe(III)-analogue of vitamin B₁₂ 647
65. Chapter 5. VITAMIN B₁₂ ASSAY
66. Vitamin B₁₂ assay: an evaluation of radiodilution assay using cobinamide to increase specificity 649
67. Effect of residual extract products and the type of binders (R or IF) on serum vitamin B₁₂ levels by radioisotope dilution assay 655
68. Differential assay of cobamides in serum using R-protein radioisotopic dilution assay, E.coli and E.gracilis assays 657
69. Rapid determination of corrinoids by high performance liquid chromatography 663
70. Determination of the plasma cobalamins by one-dimensional thin-layer chromatography 665
71. Chemical quantitation of corrinoids 671
72. Enzymatic estimation of vitamin B₁₂ 673
73. Essential prerequisites for the analysis of cyanocobalamin in biochemically complex samples using radiometric competitive binding assays 675
74. Chapter 6. ABSORPTION, TRANSPORT AND DISTRIBUTION OF VITAMIN B₁₂
75. Distribution of cobalamins in the animal body 681
76. Vitamin B₁₂ in membrane mimetic agents - theoretical considerations and practical applications 695
77. Transport of vitamin B₁₂ in Escherichia coli 711
78. The plasma transport of cobalamin (Cbl) 725
79. Soluble and membrane-bound vitamin B₁₂ transport proteins 743
80. The origin and clinical implications of vitamin B₁₂ binders - the transcobalamins 765
81. Large vitamin B₁₂-binding proteins and complexes in human serum 777
82. Heterogeneity of antibodies against B₁₂ binders in pernicious anaemia 791
83. The intraluminal phase of vitamin B₁₂ transport in humans 803
84. Polymorphic variants of transcobalamin II rare alleles in family studies 807
85. Relationship between cobalophilin releasing and functional state of polymorphonuclear granulocytes 813
86. The significance of vitamin B₁₂ binders in the central nervous system 821
87. In vitro acid dissociation of cobalamin-transcobalamin II complexes formed in vivo: a probe in the study of TC II-kinetics 827
88. Calcium dependencies in the binding of transcobalamins to subcellular particles of liver cells 833
89. The effect of antibiotics on transcobalamin II synthesis in rabbit liver cell culture 837
90. Solubilization and characterization of the transcobalamin II acceptor from human placenta and rabbit liver 843
91. Strength of binding of methyl-, 5 '-deoxyadenosyl-, cyano- and hydroxocobalamin to human transcobalamin I and II and intrinsic factor 851
92. Adsorptive endocytosis of transcobalamin II-vitamin B₁₂ by isolated rat liver parenchymal cells 855
93. Species specificity between TC II, TC II-Cbl uptake and anti-TC II 861
94. Transcobalamin II polymorphism in african populations 863
95. Transcobalamins during induction of nutritional cobalamin deficiency in the fruit bat 867
96. Heterogeneity of transcobalamin II demonstrated by isoelectric focusing in urea 873
97. Radioimmunosorbent determinations of unsaturated and total transcobalamin II in human serum 877
98. The "dU suppression test" and "thymidine suppression test": evidence for reciprocal relationship between the "de novo" and "salvage" pathways of DNA synthesis 881
99. TC II deficiency: observations with deoxyuridine suppression test 889
100. Spectral studies on hog intrinsic factor and hog non-intrinsic factor 895
101. Amino terminal sequence of hog non-intrinsic factor and hog intrinsic factor 905
102. Subunit structure of the pig ileal intrinsic factor receptor 909
103. Cobinamide blocking assay for intrinsic factor 917
104. Intracelular transport of vitamin B₁₂ in enterocytes 919
105. Evidence for the chief cell as the source of intrinsic factor secretion in the rat 921
106. Long-term treatment of pernicious anemia patients with intrinsic factor 929
107. An analogy of cobalamin membrane transport: an intestinal receptor for heme 933
108. A simplified method for quantitative determination of vitamin B₁₂ absorption 939
109. Vitamin B₁₂ absorption studies with plastic whole body counter in patients with gastroenterological operation 945
110. Affinity photo-release purification of cobalamin-binding proteins 949
111. Effect of pentagastrin in vitamin B₁₂ absorption in the guinea pig 955
112. Synthesis of cobalamin coenzymes in the rat and their secretion from the liver into plasma and bile 961
113. The pattern of cobalamins in human erythrocytes 967
114. Presence of sulfitocobalamin in cell extracts. Resolution and identification by SP-Sephadex C-25 cation exchange chromatography 971
115. Mitochondrial cobalamins: types, sources, and functions with evidence of their noninvolvement in mitochondrial DNA synthesis 975
116. Chapter 7. PHYSIOLOGY AND PATHOLOGY OF VITAMIN B₁₂
117. Studies on vitamin B₁₂ and ubiquinone 979
118. Haematological aspects of cobalamin deficiency 991
119. The neurology of vitamin B₁₂ deficiency 1001
120. Clinioal diseases related to defioienoies of vitamin B₁₂ transport proteins 1009
121. Effects of methylaobalamin on peripheral neuropathies or experimentally-induced neuropathies 1017
122. Inherited deficiencies of the deoxyadenosylcobalamin (Ado-Cbl) dependent L-methylmalonyl-CoA mutase system: clinical and biochemical aspects 1019
123. An investigation of a possible role for coenzyme B₁₂ in ribonucleotide reduction in rabbit bone marrow 1025
124. Participation of cAMP in regulation of coenzyme B₁₂ dependent glycerol dehydratase synthesis from Klebsiella pneumoniae ATCC 85955 1029
125. Carbon monoxide oxidation by Clostridia: evidence for the involvement of a corrinoid-like compound 1033
126. The in vivo effects of nitrous oxide on human bone marrow - a morphological, biochemical and cell cycle study 1037
127. Interconversion of cobalamins in human lymphocytes in vitro and the influence of nitrous oxide on synthesis of cobalamin coenzymes 1045
128. Studies on cobalamin and folate metabolism in rats exposed to nitrous oxide (N₂O) 1055
129. Alterations in mammalian cells induced by inactivation of vitamin B₁₂ with nitrous oxide 1061
130. High ascorbic acid intake and vitamin B₁₂ status in the rat 1065
131. Ability of megadoses of vitamin C to destroy vitamin B₁₂ and cobinamide and to reduce absorption of vitamin B₁₂ (with a note on B₁₂ radioassays) 1069
132. Interaction between methylcobalamin and some amino acids in single cell proteins 1079
133. Methylcobalamin and the modification of proteins in vitro 1085
134. Deoxyadenosylcobalamin and the process of methylation of tRNA in model systems 1091
135. The participation of coenzyme B₁₂ in the synthesis of DNA by Propionibacterium shermanii 1095
136. Recent advances in cobalamin metabolism: abnormalities in coenzyme distribution in tumor development and in inherited metabolic disease 1101
137. On some properties of the effect and metabolism of different cobalamins in tumor-bearing rats 1113
138. Gastric cancer as a risk factor in pernicious anaemia 1119
139. Interference with cobalamin metabolism and tumour growth by an analogue of methylcobalamin 1125
140. Vitamin B₁₂ requirement for replication of mouse leukemia L1210 cells: functional relevance to folate metabolism 1127
141. Vitamin B₁₂ and folia acid interrelations: a new look 1131
142. The effect of hypothyroidism on histidine oxidation and folate-dependent enzyme levels 1139
143. Cobalamin-dependent methionine synthesis and the regulation of the metabolism of activated folic acid derivatives in cultured human lymphoblasts 1145
144. Author and Citation Index 1149
145. Subject Index 1171
146. Collection of Photographs from the Symposium 1213