The structural and diffusive properties of an ethanol-water mixture under hydrophilic nanoscale confinement are investigated by means of molecular dynamics simulations based on the CHARMM force field. The resulting density profiles illustrate that demixing of solvents occurs at the pore wall region, which is composed of silanol molecules in our case. Ethanol molecules are more likely to attach to the wall via hydrogen bonds than water molecules. A noticeable O-H bond orientation is observed for the ethanol molecules in this region, which can be explained by the formation of two specific hydrogen bonds between ethanol and silanol. Water, in contrast, resides mostly outside the interfacial region and is in favor of forming small hydrogen bonded strings and clusters with other water molecules. This phenomenon is corroborated by both the orientation of ethanol hydroxyl groups and the radial distribution functions of the solvent oxygen atom to the silanol hydrogen atom. Ethanol selectively attaches to the wall and forms a layer close to the wall. The hydrophobic headgroups of these ethanol molecules lead to an internal hydrophobic interface layer, which in turn yields cluster structures in the adjacent water. The self-diffusion of water in the confined ethanol-water mixture at the center of the pore is faster than that of water in the bulk ethanol-water mixture; ethanol, on the other hand, diffuses slower when it is confined.

Mesoporous carbon materials were synthesized employing polymers and silica gels as structure directing templates. The basic physico-chemical properties of the synthetic mesoporous materials were characterized by (1)H and (13)C MAS solid-state NMR, X-ray diffraction, transmission electron microscopy (TEM) and nitrogen adsorption measurements. The confinement effects on small guest molecules such as water, benzene and pyridine and their interactions with the pore surface were probed by a combination of variable temperature (1)H-MAS NMR and quantum chemical calculations of the magnetic shielding effect of the surface on the solvent molecules. The interactions of the guest molecules depend strongly on the carbonization temperature and the pathway of the synthesis. All the guest-molecules, water, benzene and pyridine, exhibited high-field shifts by the interaction with the surface of carbon materials. The geometric confinement imposed by the surface causes a strong depression of the melting point of the surface phase of water and benzene. The theoretical calculation of (1)H NICS maps shows that the observed proton chemical shifts towards high-field values can be explained as the result of electronic ring currents localized in aromatic groups on the surface. The dependence on the distance between the proton and the aromatic surface can be exploited to estimate the average diameter of the confinement structures.

Carbon nanotubes as one-dimensional nanostructures are ideal model systems to study relaxation channels of excited charged carriers. The understanding of the ultrafast scattering processes is the key for exploiting the huge application potential that nanotubes offer, e.g., for light-emitting and detecting nanoscale electronic devices. In a joint study of two-color pump-probe experiments and microscopic calculations based on the density matrix formalism, we extract, both experimentally and theoretically, a picosecond carrier relaxation dynamics, and ascribe it to the intraband scattering of excited carriers with acoustic phonons. The calculated picosecond relaxation times show a decrease for smaller tube diameters. The best agreement between experiment and theory is obtained for the (8,7) nanotubes with the largest investigated diameter and chiral angle for which the applied zone-folded tight-binding wave functions are a good approximation.

In this work, we present atomic parameters of perfluoroalkanes for use within the CHARMM force field. Perfluorinated alkanes represent a special class of molecules. On the one hand, they are considerably more hydrophobic than lipids, but on the other hand, they are not lipophilic either. Instead, they represent an independent class of philicity, enabling a whole portfolio of applications within both materials science and biochemistry. We performed a thorough parametrization of all bonded and nonbonded parameters with a particular focus on van der Waals parameters. Here, the general framework of the CHARMM and CGenFF force fields has been followed. The van der Waals parameters have been fitted to experimental densities over a wide range of temperatures and pressures. This newly parametrized class of molecules will open the gate for a variety of simulations of biologically relevant systems within the CHARMM force field. A particular perspective for the present work is the influence of polyphilic transmembrane molecules on membrane properties, aggregation phenomena, and transmembrane channels.

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