Methylation of platinum by methylcobalamin
Incubation of micromolar levels of potassium hexachloroplatinate (K/sub 2/PtCl/sub 6/) and methylcobalamin (MeB-12) results in the complete conversion of MeB-12 to aquocobalamin (aquoB-12). Demethylation is optimal at approximately pH 2.0 and is accelerated by the addition of potassium tetrachloroplatinate (K/sub 2/PtCl/sub 4/). The reaction is stoichiometric between MeB-12 and the K/sub 2/PtCl/sub 6/ added (1:1). Isosbestic points at 492, 367, and 335 nm during the course of the reaction indicate that MeB-12 is demethylated to aquoB-12 with no accumulation of corrinoid intermediates. Higher alkylcobalamins and methylcobinamide react at much slower rates compared with MeB-12. Incubation of 40..mu..M K/sub 2/ PtCl/sub 6/ with either 40..mu..M (Me-/sup 14/C)MeB-12 or (Me-/sup 3/H)MeB-12 followed by lyophilization converts 70% of the label to a stable form that is associated with platinum upon subsequent paper chromatography and electrophoresis. There is no preferential loss of /sup 3/H relative to /sup 14/C in the reaction product. Difference spectra indicated that the platinum reaction product had an absorption maximum at 260 nm. When 50 ..mu..moles each of (Me-/sup 14/C)MeB-12 and K/sub 2/PtCl/sub 6/ were reacted and subjected to Sephadex G-15 chromatography, the /sup 14/C label eluted with 260 nm of absorbing material. Further chromatography on Sephadex G-15 and CM-cellulose yielded a labeled ultraviolet-absorbing product with a /sup 14/C/Pt ratio of 1.2. The overall recovery was 36 to 42% on the basis of the /sup 14/C. The /sup 14/C-Pt product has absorption maximums at 260 nm and 208 nm, with a minimum at 240 nm (A/sub 240/ nm/A/sub 260/ nm = 0.5). Proton-nuclear magnetic resonance (NMR) spectroscopy confirmed the presence of an H-C-Pt covalent bonding pattern (J for /sup 1/H, /sup 195/Pt = 78.2 Hz; tau for /sup 194/Pt-Me + /sup 196/Pt-Me = 6.956).
- OSTI ID:
- 6696882
- Resource Relation:
- Conference: Biological implications of metals in the environment, Richland, WA, Sep 1975
- Country of Publication:
- United States
- Language:
- English
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Related Subjects
ORGANIC
PHYSICAL AND ANALYTICAL CHEMISTRY
PLATINUM COMPOUNDS
BIOCHEMICAL REACTION KINETICS
METHYLATION
VITAMIN B-12
CARBON
CARBON 14 COMPOUNDS
CHEMICAL BONDS
CHLORINE COMPOUNDS
CHROMATOGRAPHY
COVALENCE
LABELLED COMPOUNDS
NMR SPECTRA
CHEMICAL REACTIONS
DRUGS
ELEMENTS
HALOGEN COMPOUNDS
HEMATINICS
HEMATOLOGIC AGENTS
KINETICS
NONMETALS
REACTION KINETICS
SEPARATION PROCESSES
SPECTRA
TRANSITION ELEMENT COMPOUNDS
VITAMIN B GROUP
VITAMINS
400301* - Organic Chemistry- Chemical & Physicochemical Properties- (-1987)