Disassembling solvation free energies into local contributions—Toward a microscopic understanding of solvation processes

Abstract

Solvation free energies contribute to the driving force of molecular processes in solution and play a significant role for the relative stability of biomolecular conformations or the formation of complexes. Changes in solvation free energy are the origin of solvent‐mediated interactions such as the hydrophobic effect in water. However, an accurate description of solvation free energies, specifically in aqueous solution, without explicit representation of the solvent is a challenging task in computer simulations. To improve existing models detailed microscopic information on solute–solvent interactions is required, which is not directly accessible from experiments. Explicit solvent simulations include solvent‐mediated effects, however, at a considerable computational cost. Computational tools have been proposed in recent years to extract information on solvation free energies and solute–solvent interactions from explicit solvent simulations. The latter includes spatial decompositions of the solvation enthalpy and entropy, which may eventually lead to an improved theoretical understanding of solvation thermodynamics. This article is categorized under: Molecular and Statistical Mechanics> Free Energy Methods Theoretical and Physical Chemistry > Statistical Mechanics Structure and Mechanism > Computational Biochemistry and Biophysics

Solvent‐mediated forces in protein dielectrophoresis

“…Several recent methods allow for detailed insights into the solvation of biomolecules from equilibrium MD simulations in explicit solvents [18, 19, 33–36]. Local contributions to the total solvation free energy, enthalpy and entropy in the biomolecular environment can be spatially resolved for additional insight.…”

“…Gradients of the solvation free energy in the presence of inhomogeneous electric fields create a solvent‐mediated DEP force, which has not been included in previous theoretical considerations. A spatially resolved analysis of local solvation free energy contributions [17–19] and their field‐induced changes allows us to further obtain direct microscopic insights into the molecular origins of solvent‐mediated DEP forces. While the solvent‐mediated DEP forces are found to play a minor role for the studied systems, we predict scenarios in which solvent‐mediated contributions may become a dominant factor for protein DEP.…”

The Partner Does Matter: The Structure of Heteroaggregates of Acridine Orange in Water

“…These water molecules are the integral part of the charged aggregates. This fact significantly complicates any modelling of the structure of such aggregates [45].…”

Advances and challenges in modeling solvated reaction mechanisms for renewable fuels and chemicals

“…Continuum solvation models have been used for many decades and there are many detailed reviews in the literature explaining the theory and the applications . We only briefly overview how continuum solvation models work and how they are used to describe renewable energy catalysis.…”

“…Continuum solvation models have been used for many decades and there are many detailed reviews in the literature explaining the theory and the applications. [69][70][71][72][73][74] We only briefly overview how continuum solvation models work and how they are used to describe renewable energy catalysis. Figure 3 shows a cartoon model representation of implicit solvation of a methanol molecule with cluster and surface calculations.…”