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Mechanistic studies of two amino acid racemases of broad substrate specificity from Pseudomonas striata and Aeromonas caviae

✍ Scribed by Kevin Reynolds; Jennifer Martin; Shu-Jane Shen; Nobuyoshi Esaki; Kenji Soda; Prof. Dr. Heinz G. Floss


Book ID
102910355
Publisher
John Wiley and Sons
Year
1991
Tongue
English
Weight
830 KB
Volume
31
Category
Article
ISSN
0233-111X

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✦ Synopsis


The conversion of ~-[a-~H]alanine in H 2 0 and unlabeled L-alanine in 'H,O into D-alanine, under nearly irreversible conditions, with the amino acid racemase from Pseudomonas striata showed significant internal transfer of the cc-hydrogen. This result has been interpreted as being indicative of a single base mechanism for the racemization.

The relative rates of deuterium incorporation into unlabeled D-and L-methionine by the two amino acid racemases of broad substrate specificity from P . striata and Aeromonas cauiue, were measured in ' H 2 0 . The results showed a markedly different pattern, dependent upon the configuration of the initial substrate; with D-methionhe as substrate deuterium is incorporated into both enantiomers at approximately the same rate, but with L-methionine as substrate deuterium is incorporated considerably faster into the D than the L enantiomer. These results argue against a single base mechanism of racemization for these enzymes and are best rationalized in terms of a double base model where only one of the bases undergoes proton (deuterium) exchange with the solvent while the amino acid is enzyme-bound. The interpretation of the earlier experiment needs to be considered in light of these results.