Effect of ascorbic acid on the degradation of cyanocobalamin and hydroxocobalamin in aqueous solution: a kinetic study.

The degradation kinetics of 5 × 10(-5) M cyanocobalamin (B12) and hydroxocobalamin (B12b) in the presence of ascorbic acid (AH2) was studied in the pH range of 1.0-8.0. B12 is degraded to B12b which undergoes oxidation to corrin ring cleavage products. B12b alone is directly oxidized to the ring cleavage products. B12 and B12b in degraded solutions were simultaneously assayed by a two-component spectrometric method at 525 and 550 nm without interference from AH2. Both degrade by first-order kinetics and the values of the rate constants at pH 1.0-8.0 range from 0.08 to 1.05 × 10(-5) s(-1) and 0.22-7.62 × 10(-5) s(-1), respectively, in the presence of 0.25 × 10(-3) M AH2. The t 1/2 values of B12 and B12b range from 13.7 to 137.5 h and 2.5-87.5 h, respectively. The second-order rate constants for the interaction of AH2 with B12 and B12b are 0.05-0.28 × 10(-2) and 1.10-30.08 × 10(-2) M(-1) s(-1), respectively, indicating a greater effect of AH2 on B12b compared to that of B12. The k obs-pH profiles for both B12 and B12b show the highest rates of degradation around pH 5. The degradation of B12 and B12b by AH2 is affected by the catalytic effect of phosphate ions on the oxidation of AH2 in the pH range 6.0-8.0.

Effect of nicotinamide on the photolysis of cyanocobalamin in aqueous solution.

The photolysis of cyanocobalamin by visible light in the presence of nicotinamide at pH 1.0-7.0 has been studied. The second-order rate constants for the bimolecular interaction of these vitamins have been determined which vary from 9.50 x 10(-3) (pH 1.0) to 1.25 x 10(-3) M(-1) min(-1) (pH 7.0). The rate-pH profile indicates a gradual slow decrease in rate in the pH range 1-3 followed by a relatively fast decrease in the pH range 3-7. The protonated form of cyanocobalamin appears to be more susceptible to photolysis than the non-ionised form. Cyanocobalamin photolysis leads to the formation of hydroxocobalamin at pH 1.0-7.0.