The surface catalytic mechanism: a comparative study with square-wave and staircase cyclic voltammetry

A pseudo-first-order catalytic mechanism in which both reactant and product of a redox reaction are strongly immobilized on an electrode surface is theoretically analysed under conditions of square-wave (SWV) and staircase cyclic voltammetry (SCV). A mathematical procedure is developed under diffusionless conditions. The relationships between the properties of the voltammetric response and both the kinetic parameters of the redox reaction and the parameters of the excitation signal are studied. The phenomenon of the quasi-reversible maximum is discussed. A comparative study between SWV and SCV is presented and the limitations and advantages of both techniques, from analytical and kinetic points of view, are discussed. The theoretical predictions are experimentally confirmed by the redox reaction of azobenzene in the presence of hydrogen peroxide as an oxidizing agent. Electronic Publication     

Spin waves in ultracold gases with exchange and spin-orbit interactions

The dynamics of spin waves in ultracold gases is investigated with allowance for exchange and spin-orbit interaction. The exact basis of atomic states is used taking into account all rotational quantum numbers of the atom. The dispersion relation for spin waves is obtained for fermions and bosons in the hydro-dynamic approximation.     

Theoretical Aspects of a Surface Electrode Reaction Coupled with Preceding and Regenerative Chemical Steps: Square‐wave Voltammetry of a Surface CEC’ Mechanism

Large number of lipophilic substances, whose electrochemical transformation takes place from adsorbed state, belong to the class of so‐called “surface‐redox reactions”. Of these, especially important are the enzymatic redox reactions. With the technique named “protein‐film voltammetry” we can get insight into the chemical features of many lipophilic redox enzymes. Electrochemical processes of many redox adsorbates, occurring at a surface of working electrode, are very often coupled with chemical reactions. In this work, we focus on the application of square‐wave voltammetry (SWV) to study the theoretical features of a surface electrode reaction coupled with two chemical steps. The starting electroactive form Ox_(ads) in this mechanism gets initially generated via preceding chemical reaction. After undergoing redox transformation at the working electrode, Ox_(ads) species got additionally regenerated via chemical reaction of electrochemically generated product Red_(ads) with a given substrate Y. The theory of this so‐called surface CEC’ mechanism is presented for the first time under conditions of square‐wave voltammetry. While we present plenty of calculated voltammograms of this complex electrode mechanism, we focus on the effect of rate of regenerative (catalytic) step to simulated voltammograms. We consider both, electrochemical reactions featuring moderate and fast electron transfer. The obtained voltammetric patterns are very specific, having sometime hybrid‐like features of voltammograms as typical for CE, EC and EC’ mechanisms. We give diagnostic criteria to recognize this complex mechanism in SWV, but we also present hints to access the kinetic and thermodynamic parameters relevant to both chemical steps, and the electrochemical reaction, too. Indeed, the results presented in this work can help experimentalists to design proper experiments to study chemical features of important lipophilic systems.     

Pseudotargeted screening and determination of constituents in Qishen granule based on compound biosynthetic correlation using UHPLC coupled with high‐resolution MS

Detection and determination of many known/unknown compounds in traditional Chinese medicines have always been challenging. To comprehensively identify compounds in Qishen granule, which is a widely prescribed herbal formula for treating chronic heart failure, a pseudotargeted screening method was proposed based on compound biosynthetic correlation using ultra high‐performance liquid chromatography coupled with high‐resolution mass spectrometry. Firstly, all possible compounds of Qishen granule were classified into nine types according to their core skeletons, and potential analogue molecular formulas were predicted according to core compound‐related biosynthetic correlations, such as methylation, hydroxylation, and glucosidation. Secondly, nine pseudocompound databases consisting of core compounds, deduced biosynthetic correlations, and predicted analogue molecular formulas were established. Then, compounds of interest were directly located by pseudotargeted screening of high resolution mass spectrometry data and further verified by target tandem mass spectrometry. As a result, 213 constituents were identified and 21 of them were determined as potential new compounds. This demonstrated that pseudotargeted screening based on compound biosynthetic correlations significantly facilitated the processing of extremely large information data and improved the efficiency of compound identification. This research provided essential data for exploration of effective substances in Qishen granule and enriched the methodology for comprehensive characterization of constituents in complex traditional Chinese medicines.