Features of solvation of phenolic acids in supercritical carbon dioxide modified by methanol and acetone

The study of solvation of three phenolic acids, 3,4,5-trihydroxybenzoic acid (gallic acid), 3,4-dihydroxybenzoic acid (protocatechuic acid), and 4-hydroxy-3,5-dimethoxybenzoic acid (syringic acid), in pure, methanol-modified and acetone-modified (0.03 and 0.06 mol fraction) supercritical (SC) carbon dioxide has been carried out by computational methods. Structural features of hydrogen-bonded complexes formation in modified SC media have been researched by using classical molecular dynamics at different densities corresponding to the experimental pressures 20 and 30 MPa and temperatures from 313 to 333 K. The results obtained have revealed that an increase of fluid density and cosolvent concentration provide increasing the average number of hydrogen bonds formed by the solute with cosolvent. Ab initio calculations of formation energy of hydrogen-bonded complexes solute - cosolvent have been performed. Solvation free energy of the phenolic acids in SC CO2 with and without cosolvents was evaluated by means of the Bennett's acceptance ratio method. The solvation free energy has been found to be strongly dependent on the number of hydrogen bonds solute - cosolvent. Cosolvent-induceci solubility enhancement values were also calculated. The results indicate that the increase in solubility of the phenolic acids is observed by passing from the pure SC CO2 through acetone-modified to methanol-modified solvent. Moreover the order of cosolvent-induced solubility enhancement magnitude depends on the number of hydrogen bonds solute - cosolvent and greatly on the concentration of the latter. (C) 2017 Elsevier B.V. All rights reserved.