PMID: 43249Dec 17, 1979

Mechanism-controlled stereospecificity. Acylation of subtilisin with enantiomeric alkyl and nitrophenyl ester substrates

European Journal of Biochemistry
L Polgár, J Fejes

Abstract

The activation parameters of acylation of subtilisin with alkyl and p-nitrophenyl esters of N-acylamino acid enantiomers were determined. It was found that (1) the activation entropy is much higher with the nitrophenyl esters than with the corresponding methyl esters, (2) the difference in rate constants between enantiomers is 10(4)--10(5) with methyl esters whereas it is only of the order of 10 with nitrophenyl esters. The results indicate that the catalytic mechanism is simpler for nitrophenyl esters than for alkyl esters. The simple mechanism requires only general base catalysis, and thus permits more freedom of motion in the transition state, whereas the complex mechanism involves both general base and general acid catalysis. Furthermore, the strikingly low enantiomeric specificity with nitrophenyl esters indicates that not only binding but also the catalytic mechanism is an important factor in determining the stereospecificity of an enzyme. The activation parameters for enantiomeric nitrophenyl ester reactions suggest that structurally related substrates can be transformed by the enzyme in different conformations which may be energetically similar or not. The energetically different conformations may account for the activa...Continue Reading

References

Jan 1, 1983·Molecular and Cellular Biochemistry·M Philipp, M L BENDER

Citations

Aug 1, 1978·European Journal of Biochemistry·L Polgár, P Halász
Oct 10, 1973·Biochimica Et Biophysica Acta·L Polgár
Nov 15, 1973·European Journal of Biochemistry·L Polgár, P Halász
Oct 15, 1971·Biochemical and Biophysical Research Communications·R A AldenC S Wright
Dec 1, 1969·Proceedings of the National Academy of Sciences of the United States of America·L Polgár, M L BENDER
Sep 1, 1967·Biochemistry·Thomas H Fife, J B Milstien
Jan 1, 1965·Annual Review of Biochemistry·M L BENDER, J KEZDY

Related Concepts

Subtilisins
Acylation
Subtilisin
Substrate Specificity
Enantiomer
Subtilisin 72
Metaplastic Cell Transformation
Alkyl group
Esters
Isomerism

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