title: Are there dynamical effects in enzyme catalysis? Some thoughts concerning the enzymatic chemical step.
abstract: We offer some thoughts on the much debated issue of dynamical effects in enzyme catalysis, and more specifically on their potential role in the acceleration of the chemical step. Since the term 'dynamics' has been used with different meanings, we find it useful to first return to the Transition State Theory rate constant, its assumptions and the choices it involves, and detail the various sources of deviations from it due to dynamics (or not). We suggest that much can be learned about the key current questions for enzyme catalysis from prior extensive studies of dynamical and other effects in the case of reactions in solution. We analyze dynamical effects both in the neighborhood of the transition state and far from it, together with the situation when quantum nuclear motion is central to the reaction, and we illustrate our discussion with various examples of enzymatic reactions.
authors.affiliation: Departamento de Química Física, Universidad de Valencia, Spain. Electronic address: ignacio.tunon@uv.es.
authors.forename: Iñaki
authors.initials: I
authors.lastname: Tuñón
authors.affiliation: Ecole Normale Supérieure-PSL Research University, Chemistry Department, Sorbonne Universités-UPMC University Paris 06, CNRS UMR 8640 Pasteur, 24 rue Lhomond, 75005 Paris, France. Electronic address: damien.laage@ens.fr.
authors.forename: Damien
authors.initials: D
authors.lastname: Laage
authors.affiliation: Ecole Normale Supérieure-PSL Research University, Chemistry Department, Sorbonne Universités-UPMC University Paris 06, CNRS UMR 8640 Pasteur, 24 rue Lhomond, 75005 Paris, France; Department of Chemistry and Biochemistry, University of Colorado, Boulder, CO 80309-0215, USA. Electronic address: james.hynes@colorado.edu.
authors.forename: James T
authors.initials: JT
authors.lastname: Hynes
mesh_terms: D055162:Biocatalysis; D004058:Diffusion; D004789:Enzyme Activation; D004798:Enzymes / Q000737:chemistry / Q000378:metabolism*; D004926:Escherichia coli / Q000201:enzymology; D007700:Kinetics; D008954:Models, Biological; D011487:Protein Conformation; D011522:Protons; D011789:Quantum Theory; D013762:Tetrahydrofolate Dehydrogenase / Q000737:chemistry / Q000378:metabolism; D014732:Vibration
chemical_list: D004798:Enzymes; D011522:Protons; D013762:Tetrahydrofolate Dehydrogenase
keywords: Dynamical effects; Enzyme catalysis; Transition State Theory