engleski

On the thermodynamic equilibrium between (R)-2-hydroxyacyl-CoA and 2-enoyl-CoA

A combined experimental and computational approach has been applied to investigate the equilibria between several alpha-hydroxyacyl CoA compounds and their 2-enoyl-CoA derivatives. In contrast to their beta, gamma, and delta-counterparts, the equilibria for the alpha-compounds are relatively poorly characterized but qualitatively appear to be unusually sensitive to substituents. Using a variety of techniques, we have succeeded to measure the equilibrium constants for the reactions beginning from 2-hydroxyglutaryl-CoA and lactyl-CoA. A complementary computational evaluation of the equilibrium constants shows quantitative agreement with the measured values. By examining the computational results, we arrive at an explanation of the substituent sensitivity and provide a prediction for the, as yet unmeasured, equilibrium involving 2-hydroxyisocaproyl-CoA.

enzyme catalysis ; equilibrium constants ; dehydration ; 2-hydroxyacyl-CoA

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