Cellular automaton rules conserving the number of active sites

This paper shows how to determine all the unidimensional two-state cellular automaton rules of a given number of inputs which conserve the number of active sites. These rules have to satisfy a necessary and sufficient condition. If the active sites are viewed as cells occupied by identical particles, these cellular automaton rules represent evolution operators of systems of identical interacting particles whose total number is conserved. Some of these rules, which allow motion in both directions, mimic ensembles of one-dimensional pseudo-random walkers. Numerical evidence indicates that the corresponding stochastic processes might be non-Gaussian.Comment: 14 pages, 5 figure

Quenched noise and over-active sites in sandpile dynamics

The dynamics of sandpile models are mapped to discrete interface equations. We study in detail the Bak-Tang-Wiesenfeld model, a stochastic model with random thresholds, and the Manna model. These are, respectively, discretizations of the quenched Edwards-Wilkinson equation with columnar, point-like and correlated noise, with the constraint that the interface velocity is either zero or exactly one. The constraint, embedded in the sandpile rules, gives rise to another noise component. This term has for the Bak-Tang-Wiesenfeld model long-range on-site correlations and reveals that with open boundary conditions there is no spatial translational invariance.Comment: 4 pages, 3 figure

Effect of ELF e.m. fields on metalloprotein redox-active sites

The peculiarity of the distribution and geometry of metallic ions in enzymes pushed us to set the hypothesis that metallic ions in active-site act like tiny antennas able to pick up very feeble e.m. signals. Enzymatic activity of Cu2+, Zn2+ Superoxide Dismutase (SOD1) and Fe2+ Xanthine Oxidase (XO) has been studied, following in vitro generation and removal of free radicals. We observed that Superoxide radicals generation by XO is increased by a weak field having the Larmor frequency fL of Fe2+ while the SOD1 kinetics is sensibly reduced by exposure to a weak field having the frequency fL of Cu2+ ion.Comment: 18 pages, 4 figure

Evidence for product-specific active sites on oxide-derived Cu catalysts for electrochemical CO2 reduction

Carbon dioxide electroreduction in aqueous media using Cu catalysts can generate many different C2 and C3 products, which leads to the question whether all products are generated from the same types of active sites or if product-specific active sites are responsible for certain products. Here, by reducing mixtures of 13CO and 12CO2, we show that oxide-derived Cu catalysts have three different types of active sites for C–C coupled products, one that produces ethanol and acetate, another that produces ethylene and yet another that produces 1-propanol. In contrast, we do not find evidence of product-specific sites on polycrystalline Cu and oriented (100) and (111) Cu surfaces. Analysis of the isotopic composition of the products leads to the prediction that the adsorption energy of *COOH (the product of the first step of CO2 reduction) may be a descriptor for the product selectivity of a given active site. These new insights should enable highly selective catalysts to be developed

Influence of a confined methanol solvent on the reactivity of active sites in UiO-66

UiO-66, composed of Zr-oxide bricks and terephthalate linkers, is currently one of the most studied metal-organic frameworks due to its exceptional stability. Defects can be introduced in the structure, creating undercoordinated Zr atoms which are Lewis acid sites. Here, additional BrOnsted sites can be generated by coordinated protic species from the solvent. In this Article, a multilevel modeling approach was applied to unravel the effect of a confined methanol solvent on the active sites in UiO-66. First, active sites were explored with static periodic density functional theory calculations to investigate adsorption of water and methanol. Solvent was then introduced in the pores with grand canonical Monte Carlo simulations, followed by a series of molecular dynamics simulations at operating conditions. A hydrogen-bonded network of methanol molecules is formed, allowing the protons to shuttle between solvent methanol, adsorbed water, and the inorganic brick. Upon deprotonation of an active site, the methanol solvent aids the transfer of protons and stabilizes charged configurations via hydrogen bonding, which could be crucial in stabilizing reactive intermediates. The multilevel modeling approach adopted here sheds light on the important role of a confined solvent on the active sites in the UiO-66 material, introducing dynamic acidity in the system at finite temperatures by which protons may be easily shuttled from various positions at the active sites

Copper active sites in biology

[no abstract

Modulating active sites in MOFs for improved Lewis acid or base catalysis

International audienc

Kinetics of Anchoring of Polymer Chains on Substrates with Chemically Active Sites

We consider dynamics of an isolated polymer chain with a chemically active end-bead on a 2D solid substrate containing immobile, randomly placed chemically active sites (traps). For a particular situation when the end-bead can be irreversibly trapped by any of these sites, which results in a complete anchoring of the whole chain, we calculate the time evolution of the probability $P_{ch}(t)$ that the initially non-anchored chain remains mobile until time $t$. We find that for relatively short chains $P_{ch}(t)$ follows at intermediate times a standard-form 2D Smoluchowski-type decay law $ln P_{ch}(t) \sim - t/ln(t)$, which crosses over at very large times to the fluctuation-induced dependence $ln P_{ch}(t) \sim - t^{1/2}$, associated with fluctuations in the spatial distribution of traps. We show next that for long chains the kinetic behavior is quite different; here the intermediate-time decay is of the form $ln P_{ch}(t) \sim - t^{1/2}$, which is the Smoluchowski-type law associated with subdiffusive motion of the end-bead, while the long-time fluctuation-induced decay is described by the dependence $ln P_{ch}(t) \sim - t^{1/4}$, stemming out of the interplay between fluctuations in traps distribution and internal relaxations of the chain.Comment: Latex file, 19 pages, one ps figure, to appear in PR