Intramolecularity and enzyme modelling: a critique

Intramolecularity and enzyme modelling: a critique A critical reappraisal of the concept of intramolecularity is attempted, but particulary focussed on the effective molarity (EM) criterion and the relationship of intramolecularity to enzymic reactivity. The prevalent ambiguities in the EM concept are addressed and a revised definition (EMrev) is suggested. It is argued that there are fundamental limitations to the use of intramolecular reactions as enzyme models. Although the simplest mechanism for enzymic reactivity is based on transition state stabilisation, an alternative (although complex) possibility is based on the stabilisation of the enzyme. Possible mechanisms for the utilisation of the enzymic free energy for effecting catalysis are discussed. http://www.deepdyve.com/assets/images/DeepDyve-Logo-lg.png Research on Chemical Intermediates Springer Journals

Intramolecularity and enzyme modelling: a critique

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Publisher
Brill Academic Publishers
Copyright
Copyright © 2003 by VSP 2003
Subject
Chemistry; Inorganic Chemistry; Physical Chemistry
ISSN
0922-6168
eISSN
1568-5675
D.O.I.
10.1163/156856703321328451
Publisher site
See Article on Publisher Site

Abstract

A critical reappraisal of the concept of intramolecularity is attempted, but particulary focussed on the effective molarity (EM) criterion and the relationship of intramolecularity to enzymic reactivity. The prevalent ambiguities in the EM concept are addressed and a revised definition (EMrev) is suggested. It is argued that there are fundamental limitations to the use of intramolecular reactions as enzyme models. Although the simplest mechanism for enzymic reactivity is based on transition state stabilisation, an alternative (although complex) possibility is based on the stabilisation of the enzyme. Possible mechanisms for the utilisation of the enzymic free energy for effecting catalysis are discussed.

Journal

Research on Chemical IntermediatesSpringer Journals

Published: Oct 17, 2004

References

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