Intramoleculanty and enzyme modelling: a critique

摘要

A critical reappraisal of the concept of intramolecularity is attempied, but particulary foeussed on the effective molurily (EM) criterion and the relationship of intramoleeukirity to enzyniic 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 enzyniic 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 enzymie free energy for effecting catalysis are discussed.