The simplest way to describe the influence of the relative diffusion of the reactants on the time course of bimolecular reactions is to modify or renormalize the phenomenological rate constants that enter into the rate equations of conventional chemical kinetics. However, for macromolecules with multiple inequivalent reactive sites, this is no longer sufficient, even in the low concentration li...

The fluctuation-dissipation theorem, one of the central theorems in thermal dynamics, breaks down in out-of-equilibrium systems. The idea of effective temperature coming from the extensions of that theorem has been recently introduced to study glasses and has proved to be a key concept for out-of-equilibrium systems. Gene networks involve stochastic chemical kinetics and are far from equilibriu...

We present a simple algorithm for the simulation of stiff, discrete-space, continuous-time Markov processes. The algorithm is based on the concept of flow averaging for the integration of stiff ordinary and stochastic differential equations and ultimately leads to a straightforward variation of the the well-known stochastic simulation algorithm (SSA). The speedup that can be achieved by the pre...

Stochastic chemical kinetics describes the time evolution of a well-stirred chemically reacting system in a way that takes into account the fact that molecules come in whole numbers and exhibit some degree of randomness in their dynamical behavior. Researchers are increasingly using this approach to chemical kinetics in the analysis of cellular systems in biology, where the small molecular popu...

The second entropy theory for nonequilibrium thermodynamics is extended to the nonlinear regime and to systems of mixed parity (even and odd functions of molecular velocities). The steady state phase space probability density is given for systems of mixed parity. The nonlinear transport matrix is obtained and it is shown to yield the analog of the linear Onsager-Casimir reciprocal relations. It...

We consider random nondirected networks subject to dynamics conserving vertex degrees and study, analytically and numerically, equilibrium three-vertex motif distributions in the presence of an external field h coupled to one of the motifs. For small h, the numerics is well described by the "chemical kinetics" for the concentrations of motifs based on the law of mass action. For larger h, a tra...

A model of barrier crossing dynamics governed by fractional Gaussian noise and the generalized Langevin equation is used to study the reaction kinetics of single enzymes subject to conformational fluctuations. The direct application of Kramers's flux-over-population method to this model yields analytic expressions for the time-dependent transmission coefficient and the distribution of waiting t...

Molecular recognition is a central issue for nearly every biological mechanism. The analysis of molecular recognition to date has been conducted within the framework of classical chemical kinetics, in which the kinetic orders of a reaction have positive integer values. However, recent theoretical and experimental advances have shown that the assumptions inherent in this classical framework are ...

Recently the application of the quasi-steady-state approximation (QSSA) to the stochastic simulation algorithm (SSA) was suggested for the purpose of speeding up stochastic simulations of chemical systems that involve both relatively fast and slow chemical reactions [Rao and Arkin, J. Chem. Phys. 118, 4999 (2003)] and further work has led to the nested and slow-scale SSA. Improved numerical eff...

In literature on chemistry education it has often been suggested that students, at high school level and beyond, can benefit in their studies of chemical kinetics from computer supported activities. Use of system dynamics modeling software is one of the suggested quantitative approaches that could help to develop students’ knowledge about chemical kinetics and chemical equilibrium and to remedi...