Toward benchmarking theoretical computations of elementary rate constants on catalytic surfaces: formate decomposition on Au and Cu

With the emergence of methods for computing rate constants for elementary reaction steps of catalytic reactions, benchmarking their accuracy becomes important. The unimolecular dehydrogenation of adsorbed formate on metal surfaces...

Asymmetric radical carboesterification of dienes

The straightforward strategy of building a chiral C-O bond directly on a general carbon radical center is challenging and stereocontrol of the reactions of open-chain hydrocarbon radicals remains a largely unsolved problem. Advance in this elementary step will spur the development of asymmetric radical C-O bond construction. Herein, we report a copper-catalyzed regioselective and enantioselective carboesterification of substituted dienes using alkyl diacyl peroxides as the source of both the carbon and oxygen substituents. The participation of external acids in this reaction substantially extends its applicability and leads to structurally diverse allylic ester products. This work represents the advance in the key elementary reaction of intermolecular enantioselective construction of C-O bond on open-chain hydrocarbon radicals and may lead to the discovery of other asymmetric radical reactions.

A numerical study on the effect of CO2 addition for methane explosion reaction kinetics in confined space

To explore the influence of the CO2 volume fraction on methane explosion in confined space over wide equivalent ratios, the explosion temperature, the explosion pressure, the concentration of the important free radicals, and the concentration of the catastrophic gas generated after the explosion in confined space were studied. Meanwhile, the elementary reaction steps dominating the gas explosion were identified through the sensitivity analysis. With the increase of the CO2 volume fraction, the explosion time prolongs, and the explosion pressure and temperature decrease monotonously. Moreover, the concentrations of the investigated free radicals also decrease as the increase of the CO2 volume fraction. For the catastrophic gas, the concentration of the gas product CO increases and the concentrations of CO2, NO, and NO2 decrease as the volume fraction of CO2 increases. When 7% methane is added with 10% CO2, the increase rate of CO is 76%, and the decrease rates of CO2, NO, and NO2 are 27%, 37%, and 39%, respectively. If the volume fraction of CO2 is constant, the larger the volume fraction of methane in the blend gas, the greater the mole fraction of radical H and the lower the mole fraction of radical O. For radical OH, its mole fraction first increases, and then decreases with the location of peak value of 9.5%, while the CO concentration increases with the increase of the methane concentration. For all the investigated volume fraction of methane, the addition of CO2 reduces the sensitivity coefficients of each key elementary reaction step, and the sensitivity coefficient of reaction promoting methane consumption decreases faster than that of the reaction inhibit methane consumption, which indicates that the addition of CO2 effectively suppresses the methane explosion.

Universally valid reduction of multiscale stochastic biochemical systems using simple non-elementary propensities

Biochemical systems consist of numerous elementary reactions governed by the law of mass action. However, experimentally characterizing all the elementary reactions is nearly impossible. Thus, over a century, their deterministic models that typically contain rapid reversible bindings have been simplified with non-elementary reaction functions (e.g., Michaelis-Menten and Morrison equations). Although the non-elementary reaction functions are derived by applying the quasi-steady-state approximation (QSSA) to deterministic systems, they have also been widely used to derive propensities for stochastic simulations due to computational efficiency and simplicity. However, the validity condition for this heuristic approach has not been identified even for the reversible binding between molecules, such as protein-DNA, enzyme-substrate, and receptor-ligand, which is the basis for living cells. Here, we find that the non-elementary propensities based on the deterministic total QSSA can accurately capture the stochastic dynamics of the reversible binding in general. However, serious errors occur when reactant molecules with similar levels tightly bind, unlike deterministic systems. In that case, the non-elementary propensities distort the stochastic dynamics of a bistable switch in the cell cycle and an oscillator in the circadian clock. Accordingly, we derive alternative non-elementary propensities with the stochastic low-state QSSA, developed in this study. This provides a universally valid framework for simplifying multiscale stochastic biochemical systems with rapid reversible bindings, critical for efficient stochastic simulations of cell signaling and gene regulation. To facilitate the framework, we provide a user-friendly open-source computational package, ASSISTER, that automatically performs the present framework.

IR spectroscopic characterization of the co-adsorption of CO2 and H2 onto cationic Cun+ clusters

To understand elementary reaction steps in the hydrogenation of CO2 over copper-based catalysts, we experimentally study the adsorption of CO2 and H2 onto cationic Cun+ (n = 4–7) clusters.

Elementary Reaction-based Kinetic Model for the Fate of N-nitrosodimethylamine under UV Oxidation

UV photolysis is an effective process to remove nitrosamines from contaminated water resources. Nitrosamines represent a class of compounds with high potential for carcinogenicity and, therefore, there are serious concerns...