Deterministic Limit of Intracellular Calcium Spikes.

In nonexcitable cells, global Ca^{2+} spikes emerge from the collective dynamics of clusters of Ca^{2+} channels that are coupled by diffusion. Current modeling approaches have opposed stochastic descriptions of these systems to purely deterministic models, while both paradoxically appear compatible with experimental data. Combining fully stochastic simulations and mean-field analyses, we demonstrate that these two approaches can be reconciled. Our fully stochastic model generates spike sequences that can be seen as noise-perturbed oscillations of deterministic origin, while displaying statistical properties in agreement with experimental data. These underlying deterministic oscillations arise from a phenomenological spike nucleation mechanism.

On the possibility of spontaneous chemomechanical oscillations in adsorptive porous media.

We derive general conditions for the emergence of sustained chemomechanical oscillations from a non-oscillatory adsorption/desorption reaction in a gas/solid porous medium. The oscillations arise from the nonlinear response of the solid matrix to the loading of the adsorbed species. More particularly, we prove that, in order for oscillations to occur, adsorption of the gas must in general cause a swelling of the solid matrix. We also investigate the prototypical case of Langmuir kinetics both numerically and analytically.This article is part of the theme issue 'Dissipative structures in matter out of equilibrium: from chemistry, photonics and biology (part 2)'.

Pigment cell movement is not required for generation of Turing patterns in zebrafish skin.

The zebrafish is a model organism for pattern formation in vertebrates. Understanding what drives the formation of its coloured skin motifs could reveal pivotal to comprehend the mechanisms behind morphogenesis. The motifs look and behave like reaction-diffusion Turing patterns, but the nature of the underlying physico-chemical processes is very different, and the origin of the patterns is still unclear. Here we propose a minimal model for such pattern formation based on a regulatory mechanism deduced from experimental observations. This model is able to produce patterns with intrinsic wavelength, closely resembling the experimental ones. We mathematically prove that their origin is a Turing bifurcation occurring despite the absence of cell motion, through an effect that we call differential growth. This mechanism is qualitatively different from the reaction-diffusion originally proposed by Turing, although they both generate the short-range activation and the long-range inhibition required to form Turing patterns.

Nonequilibrium chemistry in confined environments: a lattice Brusselator model.

In this work, we study the effect of molecular crowding on a typical example of a chemical oscillator: the Brusselator model. We adopt to this end a nonequilibrium thermodynamic description, in which the size of particles is introduced via a lattice gas model. The impenetrability and finite volume of the species are shown to affect both the reaction rates and the diffusion terms in the evolution equations for the concentrations. The corrected scheme shows a more complex dynamical behavior than its ideal counterpart, including bistability and excitability. These results help to shed light on recent experimental and computational studies in biochemistry and surface chemistry, in which it was shown that confined environments may greatly affect chemical dynamics.

Convective mixing induced by acid-base reactions.

When two miscible solutions, each containing a reactive species, are put in contact in the gravity field, local variations in the density due to the reaction can induce convective motion and mixing. We characterize here both experimentally and theoretically such buoyancy-driven instabilities induced by the neutralization of a strong acid by a strong base in aqueous solutions. The diverse patterns obtained are shown to depend on the type of reactants used and on their relative concentrations. They have their origin in a combination of classical hydrodynamic instabilities including differential diffusion of the solutes involved while temperature effects only play a marginal role.

Metastability in Schloegl's second model for autocatalysis: Lattice-gas realization with particle diffusion.

We analyze metastability associated with a discontinuous nonequilibrium phase transition in a stochastic lattice-gas realization of Schloegl's second model for autocatalysis. This model realization involves spontaneous annihilation, autocatalytic creation, and diffusion of particles on a square lattice, where creation at empty sites requires an adjacent diagonal pair of particles. This model, also known as the quadratic contact process, exhibits discontinuous transition between a populated active state and a particle-free vacuum or "poisoned" state, as well as generic two-phase coexistence. The poisoned state exists for all particle annihilation rates p>0 and hop rates h≥0 and is an absorbing state in the sense of Markovian processes. The active or reactive steady state exists only for p below a critical value, p{e}=p{e}(h) , but a metastable extension appears for a range of higher p up to an effective upper spinodal point, p{s+}=p{s+}(h) (i.e., p{s+}>p{e} ). For selected h , we assess the location of p{s+}(h) by characterizing both the poisoning kinetics and the propagation of interfaces separating vacuum and active states as a function of p .

Catalytic reduction of NO2 with hydrogen on Pt field emitter tips: kinetic instabilities on the nanoscale.

The catalytic reduction of NO(2) with hydrogen on a Pt field emitter tip is investigated using both field electron microscopy (FEM) and field ion microscopy (FIM). A rich variety of nonlinear behavior and unusually high catalytic activity around the {012} facets are observed. Our FEM investigations reveal that the correlation function exhibits damped oscillations with a decaying envelope, showing that molecular noise will influence the dynamics of the oscillations. The dependence of the oscillatory period on the P(H(2))/P(NO(2)) pressure ratios is analyzed. Similar patterns are reported under FIM conditions. Corresponding density functional theory (DFT) calculations for the adsorption of NO(2) on Pt{012} in the presence of an external electric field are performed in order to gain an atomistic understanding of the underlying nonlinear phenomena.

A simple model to describe the effect of electrostatic interactions on the composition of mixed self-assembled monolayers.

Due to intermolecular interactions, the surface composition of mixed self-assembled monolayers often differs markedly from the solution composition. In the case of charged surfactants, large deviations from the ideality have been reported. The effect of the electrostatic interactions between charged compounds on the surface composition is examined using a simple gas lattice model, in the Bragg-Williams approximation. The interaction potential is obtained from the Debye-Huckel treatment of electrolytic solutions. The model is able to explain and reproduce the deviations observed experimentally, both qualitatively and quantitatively. The key role played by the ionic strength on the surface composition is emphasized.

Promoter-induced reactive phase separation in surface reactions.

Promoters are adsorbed mobile species which do not directly participate in a catalytic surface reaction, but can influence its rate. Often, they are characterized by strong attractive interactions with one of the reactants. We show that these conditions lead to a Turing instability of the uniform state and to the formation of reaction-induced periodic concentration patterns. Experimentally such patterns are observed in catalytic water formation on a Rh(110) surface in the presence of coadsorbed potassium.

Propagating waves in one-dimensional discrete networks of coupled units.

We investigate the behavior of discrete systems on a one-dimensional lattice composed of localized units interacting with each other through nonlocal, nonlinear reactive dynamics. In the presence of second-order and third-order steps coupling two or three neighboring sites, respectively, we observe, for appropriate initial conditions, the propagation of waves which subsist in the absence of mass transfer by diffusion. For the case of the third-order (bistable) model, a counterintuitive effect is also observed, whereby the homogeneously less stable state invades the more stable one under certain conditions. In the limit of a continuous space the dynamics of these networks is described by a generic evolution equation, from which some analytical predictions can be extracted. The relevance of this mode of information transmission in spatially extended systems of interest in physical chemistry and biology is discussed.