Publication Date: 2008.
We present results from molecular dynamics simulations performed on reverse micelles immersed in cyclohexane. Three different inner polar phases are considered: water (W), formamide (FM), and an equimolar mixture of the two solvents. In all cases, the surfactant was sodium bis(2-ethylhexyl) sulfosuccinate (usually known as AOT). The initial radii of the micelles were R∼15 Å, while the corresponding polar solvent-to-surfactant molar ratios were intermediate between w0 =4.3 for FM and w0 =7 for W. The resulting overall shapes of the micelles resemble distorted ellipsoids, with average eccentricities of the order of ∼0.75. Moreover, the pattern of the surfactant layer separating the inner pool from the non-polar phase looks highly irregular, with a roughness characterized by length scales comparable to the micelle radii. Solvent dipole orientation polarization along radial directions exhibit steady growths as one moves from central positions toward head group locations. Local density correlations within the micelles indicate preferential solvation of sodium ionic species by water, in contrast to the behavior found in bulk equimolar mixtures. Still, a sizable fraction of ∼90% of Na+ remains associated with the head groups. Compared to bulk results, the translational and rotational modes of the confined solvents exhibit important retardations, most notably those operated in rotational motions where the characteristic time scales may be up to 50 times larger. Modifications of the intramolecular connectivity expressed in terms of the average number of hydrogen bonds and their lifetimes are also discussed. © 2008 American Institute of Physics.
Author affiliation: Pomata, M.H.H. Universidad de Buenos Aires. Facultad de Ciencias Exactas y Naturales; Argentina.
Author affiliation: Laria, D. Universidad de Buenos Aires. Facultad de Ciencias Exactas y Naturales; Argentina.
Author affiliation: Elola, M.D. Universidad de Buenos Aires. Facultad de Ciencias Exactas y Naturales; Argentina.
Keywords: Amides; Colloids; Dynamics; Hydrogen; Hydrogen bonds; Ionization of liquids; Molecular dynamics; Quantum chemistry; Sodium; Solvents; Surface active agents; Average numbers; Characteristic times; Dipole orientations; Dynamical properties; Equimolar mixtures; Head groups; Ionic species; Length scales; Life-times; Local densities; Molar ratios; Molecular dynamics simulations; Polar phasis; Polar solvents; Preferential solvations; Radial directions; Reverse micelles; Rotational modes; Rotational motions; Sulfosuccinate; Surfactant layers; Micelles.
Repository: Biblioteca Digital (UBA-FCEN). Universidad Nacional de Buenos Aires. Facultad de Ciencias Exactas y Naturales
Authors: Fernandez, Ariel
Publication Date: 2012.
Nanoscale solvent confinement at the protein-water interface promotes dipole orientations that are not aligned with the internal electrostatic field of a protein, yielding what we term epistructural polarization. To quantify this effect, an equation is derived from first principles relating epistructural polarization with the magnitude of local distortions in water coordination causative of interfacial tension. The equation defines a nanoscale electrostatic model of water and enables an estimation of protein denaturation free energies and the inference of hot spots for protein associations. The theoretical results are validated vis-à-vis calorimetric data, revealing the destabilizing effect of epistructural polarization and its molecular origin.
Author affiliation: Fernandez, Ariel. Consejo Nacional de Investigaciones Científicas y Técnicas. Oficina de Coordinación Administrativa Saavedra 15. Instituto Argentino de Matemática Alberto Calderon; Argentina. Collegium Basilea; Suiza
Repository: CONICET Digital (CONICET). Consejo Nacional de Investigaciones Científicas y Técnicas