title: Stochastic kinetics on networks: when slow is fast.
abstract: Most chemical and biological processes can be viewed as reaction networks in which different pathways often compete kinetically for transformation of substrates into products. An enzymatic process is an example of such phenomena when biological catalysts create new routes for chemical reactions to proceed. It is typically assumed that the general process of product formation is governed by the pathway with the fastest kinetics at all time scales. In contrast to the expectation, here we show theoretically that at time scales sufficiently short, reactions are predominantly determined by the shortest pathway (in the number of intermediate states), regardless of the average turnover time associated with each pathway. This universal phenomenon is demonstrated by an explicit calculation for a system with two competing reversible (or irreversible) pathways. The time scales that characterize this regime and its relevance for single-molecule experimental studies are also discussed.
authors.affiliation: Department of Chemistry and ‡Department of Chemistry and Center for Theoretical Biological Physics, Rice University , Houston, Texas 77005, United States.
authors.forename: Xin
authors.initials: X
authors.lastname: Li
authors.forename: Anatoly B
authors.initials: AB
authors.lastname: Kolomeisky
authors.forename: Angelo
authors.initials: A
authors.lastname: Valleriani
mesh_terms: D000465:Algorithms; D002384:Catalysis; D004798:Enzymes / Q000737:chemistry*; D007700:Kinetics; D008956:Models, Chemical; D011336:Probability; D013269:Stochastic Processes
chemical_list: D004798:Enzymes