Liquids

This study investigates the formation of hydroxyl radicals (OH radicals) in cavitation bubble plasma-treated water (CBPTW) using a chemical probe method. CBPTW samples were prepared with different electrode materials (W, Fe, Cu, and Ag), and the chemical scavenger was added two minutes after the completion of cavitation and plasma treatments. The concentrations of metal ions and hydrogen peroxide (H₂O₂) generated in the CBPTW were also measured over time. This study reveals a novel mechanism whereby metal nanoparticles and ions released from electrodes catalyze the continuous generation of hydroxyl radicals in CBPTW, which has not been fully addressed in previous studies. The results suggest a continuous generation of OH radicals in CBPTW prepared with W, Fe, and Cu electrodes, with the amount of OH radicals produced in the order Cu > Fe > W. The study reveals a correlation between OH radical production and electrode wear, suggesting that the continuous generation of OH radicals in CBPTW results from the catalytic decomposition of H₂O₂ by metal nanoparticles or ions released from the electrodes. It should be noted that cavitation bubble plasma (CBP) is fundamentally different from sonochemistry. While sonochemistry utilizes ultrasound-induced cavitation to generate radicals, CBP relies on plasma discharge generated inside cavitation bubbles. No ultrasound was applied in this study; therefore, all observed radical formation is attributable exclusively to plasma processes rather than sonochemical effects. However, the precise mechanism of continuous OH radical formation in CBPTW remains unclear and requires further investigation. These findings provide new insights into the role of electrode materials in continuous OH radical generation in cavitation bubble plasma treated water, offering potential applications in water purification and sterilization technologies.

A new method is presented for the estimation of contributions to solvation free energy from dispersion, polar, and hydrogen-bonding (HB) intermolecular interactions. COSMO-type quantum chemical solvation calculations are used for the development of four new molecular descriptors of solutes for their electrostatic interactions. The new model needs one to three solvent-specific parameters for the prediction of solvation free energies. The widely used Abraham’s LSER model is used for providing the reference solvation free energy data for the determination of the solvent-specific parameters. Extensive calculations in 80 solvent systems have verified the good performance of the model. The very same molecular descriptors are used for the calculation of solvation enthalpies. The advantages of the present model over Abraham’s LSER model are discussed along with the complementary character of the two models. Enthalpy and free-energy solvation information for pure solvents is translated into partial solvation parameters (PSP) analogous to the widely used Hansen solubility parameters and enlarge significantly their range of applications. The potential and the perspectives of the new approach for further molecular thermodynamic developments are discussed.

Experimental data on the folding and unfolding of small globular proteins are often well described assuming a two-state equilibrium process. It means that after careful analysis by a combination of experimental techniques, only folded and unfolded states of the protein are found to be populated under various external conditions with no detectable intermediates. One of the consequences of the two-state behavior is that the equilibrium ratio of the folded to unfolded protein states follows a simple thermodynamic relation, and the enthalpy difference between states can be obtained from the temperature dependence of the equilibrium constant. In this paper, we theoretically investigate the criteria for the two-state equilibrium behavior and discuss the thermodynamic constraint on the properties of the “hidden” folding intermediates. The literature data on the folding mechanism of lysozyme in water and glycerol, which follows a two-state equilibrium behavior but includes kinetic intermediates, is analysed in light of this constraint.