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Published August 29, 2006 | public
Journal Article

Summarizing lecture: factors influencing enzymatic H-transfers, analysis of nuclear tunnelling isotope effects and thermodynamic versus specific effects

Abstract

In the articles in this Discussion, a wide variety of topics are treated, including reorganization energy, initially introduced for electron transfers ('environmentally assisted tunnelling'), nuclear tunnelling, H/D and ^(12)C/^(13)C kinetic isotope effects (KIEs), the effect of changes of distal and nearby amino acid residues using site-directed mutagenesis, and dynamics versus statistical effects. A coordinate-free form of semi-classical theory is used to examine topics on data such as tunnelling versus 'over-thebarrier' paths and temperature and pressure effects on KIEs. The multidimensional semi-classical theory includes classically allowed and classically forbidden transitions. More generally, we address the question of relating kinetic to thermodynamic factors, as in the electron transfer field, so learning about specific versus thermodynamic effects in enzyme catalysis and KIEs.

Additional Information

© 2006 The Royal Society. Published online 13 July 2006. One contribution of 16 to a Discussion Meeting Issue: 'Quantum catalysis in enzymes—beyond the transition state theory paradigm'. It is a pleasure to acknowledge the support of this research by the Office of Naval Research and the National Science Foundation. I am pleased to acknowledge too the helpful comments of Prof. M. E. Michel-Beyerle. I have benefitted also from many helpful suggestions, clarification, and comments from participants in this Discussion. It is a pleasure to express my appreciation to them. I thank my coworkers, Meher Prakash and Wei-Chen Chen, for the figures.

Additional details

Created:
August 22, 2023
Modified:
October 23, 2023