Correspondence between Spectral-Derived and Viscosity-Derived Local Composition in Binary Liquid Mixtures Having Specific Interactions with Preferential Solvation Theory.

Local interactions between unlike molecules (1-2) in solution are commonly measured with spectroscopy and used to estimate local composition. Herein, a viscosity model based on preferential solvation (PS) theory is developed for aqueous and nonaqueous binary liquid mixtures containing a dipolar aprotic solvent that provides local composition considering the hydration or solvation shell around complex (1-2) molecules. Spectral-derived and viscosity-derived local composition distributions showed similar trends with bulk composition, and their correspondence is attributed to characteristics of the hydration or solvation shell. Viscosity-derived local compositions were consistent with literature molecular simulations, whereas spectral-derived local composition distributions contained artifacts. The PS viscosity model is also applicable to nonpolar-polar mixtures for which self-association occurs, and it can be used to estimate solvent mixture dipolarity/polarizability. Since the PS viscosity model only requires bulk viscosity, it may provide a means to estimate microviscosity or the solvent environment around biomolecules.