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This review gives an overview of current trends in the investigation of confined molecules such as water, small and higher alcohols, carbonic acids, ethylene glycol, and non-ionic surfactants, such as polyethylene glycol or Triton-X, as guest molecules in neat and functionalized mesoporous silica materials employing solid-state NMR spectroscopy, supported by calorimetry and molecular dynamics simulations. The combination of steric interactions, hydrogen bonds, and hydrophobic and hydrophilic interactions results in a fascinating phase behavior in the confinement. Combining solid-state NMR and relaxometry, DNP hyperpolarization, molecular dynamics simulations, and general physicochemical techniques, it is possible to monitor these confined molecules and gain deep insights into this phase behavior and the underlying molecular arrangements. In many cases, the competition between hydrogen bonding and electrostatic interactions between polar and non-polar moieties of the guests and the host leads to the formation of ordered structures, despite the cramped surroundings inside the pores. 

Polyethylene glycol (PEG) is one of the environmentally benign solvent options for green chemistry. It readily absorbs water when exposed to the atmosphere. The Molecular Dynamics (MD) simulations of PEG200, a commercial mixture of low molecular weight polyethyelene glycol oligomers, as well as di-, tetra-, and hexaethylene glycol are presented to study the effect of added water impurities up to a weight fraction of 0.020, which covers the typical range of water impurities due to water absorption from the atmosphere. Each system was simulated a total of four times using different combinations of two force fields for the water (SPC/E and TIP4P/2005) and two force fields for the PEG and oligomer (OPLS-AA and modified OPLS-AA). The observed trends in the effects of water addition were qualitatively quite robust with respect to these force field combinations and showed that the water does not aggregate but forms hydrogen bonds at most between two water molecules. In general, the added water causes overall either no or very small and nuanced effects in the simulation results. Specifically, the obtained water RDFs are mostly identical regardless of the water content. The added water reduces oligomer hydrogen bonding interactions overall as it competes and forms hydrogen bonds with the oligomers. The loss of intramolecular oligomer hydrogen bonding is in part compensated by oligomers switching from inter- to intramolecular hydrogen bonding. The interplay of the competing hydrogen bonding interactions leads to the presence of shallow extrema with respect to the water weight fraction dependencies for densities, viscosities, and self-diffusion coefficients, in contrast to experimental measurements, which show monotonous dependencies. However, these trends are very small in magnitude and thus confirm the experimentally observed insensitivity of these physical properties to the presence of water impurities.