Thermodynamics of organic chemical hydration: QSPR models using physicochemical HYBOT descriptors

摘要

Stable and predictive quantitative structure-property relationship (QSPR) models of thermodynamics of chemical hydration (changes in Gibbs energy, Gair/water, enthalpy, Hair/water and entropy Sair/water) were obtained on the basis of physicochemical descriptors calculated by the HYBOT program. The structurally diverse training set (n = 151) and test set (n = 37) included 13 mono-functional chemical classes. The applied HYBOT descriptors comprise molecular polarizability (as a volume-related term), the sum of partial negative charges on all atoms in a molecule Sigma Q- (as an electrostatic term) and the sum of H-bond acceptor and donor factors Sigma Ca and Sigma Cd (as H-bond terms). Final equations for changes in Gibbs energy and enthalpy provided good statistical criteria and standard deviations on the level of errors of experimental determinations. All four above-mentioned terms essentially contribute to hydration enthalpy and each of them increases negative values of enthalpy. Hydration Gibbs energy predominantly depends on hydrogen bonding between solute and water molecules. Steric and electrostatic terms act in opposite directions and partly compensate each other. Changes in entropy correlate with increasing H-bond acceptor ability, whereas the other three descriptors exhibit inverse correlations.