42299
2018
2018
eng
12
1
article
Macmillan Publishers Limited
London
1
2018-12-13
2018-12-13
--
Strong defocusing of molecular reaction times results from an interplay of geometry and reaction control
Textbook concepts of diffusion-versus kinetic-control are well-defined for reaction-kinetics involving macroscopic concentrations of diffusive reactants that are adequately described by rate-constants—the inverse of the mean-first-passage-time to the reaction-event. In contradiction, an open important question is whether the mean-first-passage-time alone is a sufficient measure for biochemical reactions that involve nanomolar reactant concentrations. Here, using a simple yet generic, exactly solvable model we study the effect of diffusion and chemical reaction-limitations on the full reaction-time distribution. We show that it has a complex structure with four distinct regimes delineated by three characteristic time scales spanning a window of several decades. Consequently, the reaction-times are defocused: no unique time-scale characterises the reaction-process, diffusion- and kinetic-control can no longer be disentangled, and it is imperative to know the full reaction-time distribution. We introduce the concepts of geometry- and reaction-control, and also quantify each regime by calculating the corresponding reaction depth.
Communications Chemistry
10.1038/s42004-018-0096-x
2399-3669
96
Universität Potsdam
PA 2018_82
1785.00
<a href="http://nbn-resolving.de/urn:nbn:de:kobv:517-opus4-422989">Zweitveröffentlichung in der Schriftenreihe Postprints der Universität Potsdam : Mathematisch-Naturwissenschaftliche Reihe ; 527</a>
Creative Commons - Namensnennung, 4.0 International
Denis S. Grebenkov
Ralf Metzler
Gleb Oshanin
Chemie und zugeordnete Wissenschaften
open_access
Referiert
Publikationsfonds der Universität Potsdam
Open Access