Theory of the NO+CO surface reaction model

We derive a pair approximation (PA) for the NO+CO model with instantaneous reactions. For both the triangular and square lattices, the PA, derived here using a simpler approach, yields a phase diagram with an active state for CO-fractions y in the interval y_1 < y < y_2, with a continuous (discontinuous) phase transition to a poisoned state at y_1 (y_2). This is in qualitative agreement with simulation for the triangular lattice, where our theory gives a rather accurate prediction for y_2. To obtain the correct phase diagram for the square lattice, i.e., no active state, we reformulate the PA using sublattices. The (formerly) active regime is then replaced by a poisoned state with broken symmetry (unequal sub- lattice coverages), as observed recently by Kortluke et al. [Chem. Phys. Lett. 275, 85 (1997)]. In contrast with their approach, in which the active state persists, although reduced in extent, we report here the first qualitatively correct theory of the NO+CO model on the square lattice. Surface diffusion of nitrogen can lead to an active state in this case. In one dimension, the PA predicts that diffusion is required for the existence of an active state.Comment: 15 pages, 9 figure

Oscillations and dynamics in a two-dimensional prey-predator system

Using Monte Carlo simulations we study two-dimensional prey-predator systems. Measuring the variance of densities of prey and predators on the triangular lattice and on the lattice with eight neighbours, we conclude that temporal oscillations of these densities vanish in the thermodynamic limit. This result suggests that such oscillations do not exist in two-dimensional models, at least when driven by local dynamics. Depending on the control parameter, the model could be either in an active or in an absorbing phase, which are separated by the critical point. The critical behaviour of this model is studied using the dynamical Monte Carlo method. This model has two dynamically nonsymmetric absorbing states. In principle both absorbing states can be used for the analysis of the critical point. However, dynamical simulations which start from the unstable absorbing state suffer from metastable-like effects, which sometimes renders the method inefficient.Comment: 7 eps figures, Phys.Rev.E - in pres

The Maturation Factors HoxR and HoxT Contribute to Oxygen Tolerance of Membrane-Bound [NiFe] Hydrogenase in Ralstonia eutropha H16 ▿ †

The membrane-bound [NiFe] hydrogenase (MBH) of Ralstonia eutropha H16 undergoes a complex maturation process comprising cofactor assembly and incorporation, subunit oligomerization, and finally twin-arginine-dependent membrane translocation. Due to its outstanding O2 and CO tolerance, the MBH is of biotechnological interest and serves as a molecular model for a robust hydrogen catalyst. Adaptation of the enzyme to oxygen exposure has to take into account not only the catalytic reaction but also biosynthesis of the intricate redox cofactors. Here, we report on the role of the MBH-specific accessory proteins HoxR and HoxT, which are key components in MBH maturation at ambient O2 levels. MBH-driven growth on H2 is inhibited or retarded at high O2 partial pressure (pO2) in mutants inactivated in the hoxR and hoxT genes. The ratio of mature and nonmature forms of the MBH small subunit is shifted toward the precursor form in extracts derived from the mutant cells grown at high pO2. Lack of hoxR and hoxT can phenotypically be restored by providing O2-limited growth conditions. Analysis of copurified maturation intermediates leads to the conclusion that the HoxR protein is a constituent of a large transient protein complex, whereas the HoxT protein appears to function at a final stage of MBH maturation. UV-visible spectroscopy of heterodimeric MBH purified from hoxR mutant cells points to alterations of the Fe-S cluster composition. Thus, HoxR may play a role in establishing a specific Fe-S cluster profile, whereas the HoxT protein seems to be beneficial for cofactor stability under aerobic conditions