A self-consistent equation to derive a discreteness-induced stochastic steady state is presented for reaction-diffusion systems. For this formalism, we use the so-called Kuramoto length, a typical distance over which a molecule diffuses in its lifetime, as was originally introduced to determine if local fluctuations influence globally the whole system. We show that this Kuramoto length is also relevant to determine whether the discreteness of molecules is significant or not. If the number of molecules of a certain species within the Kuramoto length is small and discrete, localization of some other chemicals is brought about, which can accelerate certain reactions. When this acceleration influences the concentration of the original molecule species, it is shown that a novel, stochastic steady state is induced that does not appear in the continuum limit. A theory to obtain and characterize this state is introduced, based on the self-consistent equation for chemical concentrations. This stochastic steady state is confirmed by numerical simulations on a certain reaction model, which agrees well with the theoretical estimation. Formation and coexistence of domains with different stochastic states are also reported, which is maintained by the discreteness. Relevance of our result to intracellular reactions is briefly discussed.
In many biological situations, a species arriving from a remote source diffuses in a domain confined between two parallel surfaces until it finds a binding partner. Since such a geometric shape falls in between two- and three-dimensional settings, the behavior of the macroscopic reaction rate and its dependence on geometric parameters are not yet understood. Modeling the geometric setup by a capped cylinder with a concentric disk-like reactive region on one of the lateral surfaces, we provide an exact semi-analytical solution of the steady-state diffusion equation and compute the diffusive flu…
The quasi-steady-state approximation is widely used to develop simplified deterministic or stochastic models of enzyme catalyzed reactions. In deterministic models, the quasi-steady-state approximation can be mathematically justified from singular perturbation theory. For several closed enzymatic reactions, the homologous extension of the quasi-steady-state approximation to the stochastic regime, known as the stochastic quasi-steady-state approximation, has been shown to be accurate under the analogous conditions that permit the quasi-steady-state reduction of the deterministic counterpart. Ho…
Analytical equations were found for interdigitated electrodes, which considered reversible electrode reactions and pure diffusion within confined spaces. A conformal transformation, obtained by the use of Jacobian elliptic functions, was applied to solve the diffusion equation in steady state. The obtained steady-state current depends on the ratio of elliptic integrals of the first kind, in which their moduli are functions of the relative dimensions of the cell. The current is smaller for shallower cells, but approaches similiar values to those of semi-infinite geometries when the cell is suff…
The Michaelis-Menten enzymatic reaction is sufficient to perceive many subtleties of network modeling, including the concentration and time scales separations, the formal equivalence between bulk phase and single-molecule approaches, or the relationships between single-cycle transient probabilities and steady state rates. Seven methods proposed by different authors and yielding the same famous Michaelis-Menten equation, are selected here to illustrate the kinetic and probabilistic use of rate constants and to review basic techniques for handling them. Finally, the general rate of an ordered mu…
The urea-urease clock reaction is a pH switch from acid to basic that can turn into a pH oscillator if it occurs inside a suitable open reactor. We study the confinement of the reaction to lipid vesicles, which permit the exchange with an external reservoir by differential transport, enabling the recovery of the pH level and yielding a constant supply of urea molecules.For microscopically small vesicles, the discreteness of the number of molecules requires a stochastic treatment of the reaction dynamics. Our analysis shows that intrinsic noise induces a significant statistical variation of the…
Chemical reactions can accelerate, slow down or even be at the very origin of the development of dissolution-driven convection in partially miscible stratifications, when they impact the density profile in the host fluid phase. We numerically analyze the dynamics of this reactive convective dissolution in the fully developed non-linear regime for a phase A dissolving into a host layer containing a dissolved reactant B. We show that for a general A+B$\rightarrow$C reaction in solution, the dynamics vary with the Rayleigh numbers of the chemical species, i.e. with the nature of the chemicals in …
We simulate the nonequilibrium steady state \textit{cis-trans} photoisomerization of retinal chromophore in rhodopsin based on a two-state-two-mode model coupled to a thermal environment. By analyzing the systematic trends within an inhomogeneously broadened ensemble of systems, we find that the steady state reaction quantum yield (QY) correlates strongly with the excess energy above the crossing point of the system, in agreement with the prediction of the short time dynamical wavepacket picture. However, the nontrivial dependence of the QY on the system-environment interaction indicates that …
Nonequilibrium steady state of isothermal biochemical cycle kinetics has been extensively studied, but much less investigated under non-isothermal conditions. However, once the heat exchange between subsystems is rather slow, the isothermal assumption of the whole system meets great challenge, which is indeed the case inside many kinds of living organisms. Here we generalize the nonequilibrium steady-state theory of isothermal biochemical cycle kinetics, in the master-equation models, to the situation in which the temperatures of subsystems can be far from uniform. We first obtain a new thermo…
Here, steady-state reaction networks are inspected from the viewpoint of individual tagged molecules jumping among their chemical states upon the occurrence of reactive events. Such an agent-based viewpoint is useful for selectively characterizing the behavior of functional molecules, especially in the presence of bimolecular processes. We present the tools for simulating the jump dynamics both in the macroscopic limit and in the small-volume sample where the numbers of reactive molecules are of the order of few units with an inherently stochastic kinetics. The focus is on how an ideal spatial…
The study of Chemical Reaction Networks (CRN's) is a very active field. Earlier well-known results \cite{Feinberg:def_01:87, Anderson:product_dist:10} identify a topological quantity called deficiency, for any CRN, which, when exactly equal to zero, leads to a unique factorized steady-state for these networks. No results exist however for the steady states of non-zero-deficiency networks. In this paper, we show how to write the full moment-hierarchy for any non-zero-deficiency CRN obeying mass-action kinetics, in terms of equations for the factorial moments (FM). Using these, we can recursivel…
We consider linear elimination of variables in steady state equations of a chemical reaction network. Particular subsets of variables corresponding to sets of so-called reactant-noninteracting species, are introduced. The steady state equations for the variables in such a set, taken together with potential linear conservation laws in the variables, define a linear system of equations. We give conditions that guarantee that the solution to this system is nonnegative, provided it is unique. The results are framed in terms of spanning forests of a particular multidigraph derived from the reaction…
We present a systematic mathematical analysis of the qualitative steady-state response to rate perturbations in large classes of reaction networks. This includes multimolecular reactions and allows for catalysis, enzymatic reactions, multiple reaction products, nonmonotone rate functions, and non-closed autonomous systems. Our structural sensitivity analysis is based on the stoichiometry of the reaction network, only. It does not require numerical data on reaction rates. Instead, we impose mild and generic nondegeneracy conditions of algebraic type. From the structural data, only, we derive wh…
