Rudolph Marcus (2006) - Enzymatic catalysis: experiments, theory and computations, a unified view

Rudolph Marcus (2006)

Enzymatic catalysis: experiments, theory and computations, a unified view

Rudolph Marcus (2006)

Enzymatic catalysis: experiments, theory and computations, a unified view

Abstract

There are many experimental and theoretical studies on the mechanism of enzyme catalysis. The theoretical studies largely involve comparison with reaction rates, ranging from kinetic isotope effects to effects of site-specific mutations, and are typically computationally intensive. Because of the difficulty in executing computations for the slow time scale of milli- to microseconds often characteristic of these reactions, the computational studies are typically made in conjunction with transition state theory. That theory is commonly used to treat chemical reaction rates. In pre-computational days, approximate concepts and equations were used instead to analyze rate experiments.

The question we address in this talk is whether one can formulate a theory-based equation, perhaps akin to that used for electron transfer reactions, for interpreting experiments and computations, to “unify” the diverse field. Authors have recognized that the transfer of light particles, such as protons from one reactant to another, common to enzymatic reactions, has some similarity to the transfer of an electron from one reactant to another. A simple theoretical equation for electron transfer reactions served to coordinate a vast body of experimental data and later provided guidance and insight into subsequent computations. In this lecture, we consider the similarity and differences of H–, H+ and H• transfers compared to electron transfers and formulate an approximate theoretical expression. Comparison can be made with experimental and computational results to explore its usefulness as a “unifier” of current results.

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