Volume 232, Issue 7-8 - Special Issue: Research Unit FOR 1583: Hydrogen-Bonded Liquids Subject to Interfaces of Various Hydroaffinities / Guest Editors: Gerd Buntkowsky and Michael Vogel

Effects of interfaces on hydrogen-bonded liquids play major roles in nature and technology. Despite their importance, a fundamental understanding of these effects is still lacking. In large parts, this shortcoming is due to the high complexity of these systems, leading to an interference of various interactions and effects. Therefore, it is advisable to take gradual approaches, which start from well designed and defined model systems and systematically increase the level of intricacy towards more complex mimetics. Moreover, it is necessary to combine insights from a multitude of methods, in particular, to link novel preparation strategies and comprehensive experimental characterization with inventive computational and theoretical modeling. Such concerted approach was taken by a group of preparative, experimentally, and theoretically working scientists in the framework of Research Unit FOR 1583 funded by the Deutsche Forschungsgemeinschaft (German Research Foundation). This special issue summarizes the outcome of this collaborative research. In this introductory article, we give an overview of the covered topics and the main results of the whole consortium. The following contributions are review articles or original works of individual research projects.

We investigate the effect of several nanoscale confinements on structural and dynamical properties of liquid water and binary aqueous mixtures. By means of molecular dynamics simulations based on density functional theory and atomistic force fields. Our main focus is on the dependence on the structure and the hydrogen-bonding-network of the liquids near the confinement interface at atomistic resolution. As a complementary aspect, spatially resolved profiles of the proton NMR chemical shift values are used to quantify the local strength of the hydrogen-bond-network.

We investigate liquid water confined within nanoscale cellulose slabs by means of molecular dynamics simulations. Depending on the construction of the cellulose–water interface, two different surface structures with distinct levels of hydrophilicity are exposed to the water. The different philicities are reflected in the response of the water phase to this geometric confinement, both in terms of the density profile and in the strength of the aqueous hydrogen bonding network. At the smooth surface cut along the (010) axis of the cellulose crystal, water shows typical properties of a hydrophilic confinement: the density shows fluctuations that disappear further away from the wall, the water molecules orient themselves and the coordination numbers increases at the interface. As a consequence, the water becomes “harder” at the interface, with a considerably increased local ordering. At the zigzag-shaped surface along the (111) axis, the degree of hydrophilicity is reduced, and only small effects can be seen: the density shows weak fluctuations, and the orientation of the water molecules is closer to that of bulk water than to the smooth surface. The local coordination numbers remains constant over the whole confinement. Our work shows that the nature of the exposed cellulose interface has a strong influence on how the structure of adjacent water is modified. The different ways of surface construction yield distinct degrees of hydrophilicity and spatial accessibility regarding the hydrogen bond network, resulting in a notably different interfacial water structure.

The processes of drying mesoporous silica materials and their refilling with water have been examined by magic-angle spinning (MAS) solid-state NMR, broadband dielectric spectroscopy (BDS), and differential scanning calorimetry (DSC). It is shown that different drying protocols strongly influence the amount and types of hydroxy-species inside the pores. It is found that a very good vacuum (≈10 −6 bar) is necessary to remove all H 2 O molecules from the silica matrices in order to accurately refill them with very low amounts of water such as e.g. a mono- or submonolayer coverage of the surface. Time-dependent 1 H-NMR-spectra recorded after loading the samples indicate a very specific course of water first existing in a bulk-like form inside the pores and then distributing itself through the pores by hydrogen bonding to surface silanol groups. After assuring accurate sample loading, we were able to investigate lowly hydrated samples of water confined in MCM-41 via DCS and BDS at temperatures below the freezing point of free bulk-water (0°C) and find two non-crystallizing water species with Arrhenius behavior and activation energies of 0.53 eV (51.1 kJ/mol).

We have developed a flexible experimental setup to conduct triplet solvation dynamics (TSD) experiments. The setup is capable of exciting dyes at 355, 320 and 266 nm. Phosphorescence spectra can be recorded up to a 10 ns-resolution usually covering three decades using a grating spectrograph and a CCD camera. In this contribution, we describe the experimental setup as well as first investigations on water-alcohol mixtures, microemulsions and new dyes for TSD, i.e. naphthalene derivates, which take full advantage of this experimental method sensitive to the local environment of the dyes.

Mesoporous silica MCM-41 is prepared, for which the inner surfaces are modified by 3-(aminopropyl)triethoxysilane (APTES) in a controlled manner. Nitrogen gas adsorpition yields a pore diameter of 2.2 nm for the APTES functionalized MCM-41. 2 H nuclear magnetic resonance (NMR) and broadband dielectric spectroscopy (BDS) provide detailed and consistent insights into the temperature-dependent reorientation dynamics of water in this confinement. We find that a liquid water species becomes accompanied by a solid water species when cooling through ~210 K, as indicated by an onset of bimodal 2 H spin-lattice relaxation. The reorientation of the liquid water species is governed by pronounced dynamical heterogeneity in the whole temperature range. Its temperature dependence shows a mild dynamic crossover when the solid water species emerges and, hence, the volume accessible to the liquid water species further shrinks. Therefore, we attribute this variation in the temperature dependence to a change from bulk-like behavior towards interface-dominated dynamics. Below this dynamic crossover, 2 H line-shape and stimulted-echo studies show that water reorientation becomes anisotropic upon cooling, suggesting that these NMR approaches, but also BDS measurements do no longer probe the structural ( α ) relaxation, but rather a secondary ( β ) relaxation of water at sufficiently low temperatures. Then, another dynamic crossover at ~180 K can be rationalized in terms of a change of the temperature dependence of the β relaxation in response to a glassy freezing of the α relaxation of confined water. Comparing these results for APTES modied MCM-41 with previous findings for mesoporous silica with various pore diameters, we obtain valuable information about the dependence of water dynamics in restricted geometries on the size of the nanoscopic confinements and the properties of the inner surfaces.

2 H NMR is used to ascertain dynamical behaviors of pure and mixed hydrogen-bonded liquids in bulk and in confinement. Detailed comparisons of previous and new results in broad dynamic and temperature ranges reveal that confinement effects differ for various liquids and confinements. For water, molecular reorientation strongly depends on the confinement size, with much slower and less fragile structural relaxation under more severe geometrical restriction. Moreover, a dynamical crossover occurs when a fraction of solid water forms so that the dynamics of the fraction of liquid water becomes even more restricted and, as a consequence, changes from bulk-like to interface-dominated. For glycerol, by contrast, confinement has weak effects on the reorientation dynamics. Mixed hydrogen-bonded liquids show even more complex dynamical behaviors. For aqueous solutions, the temperature dependence of the structural relaxation becomes discontinuous when the concentration changes due to a freezing of water fractions. This tendency for partial crystallization is enhanced rather than reduced by confinement, because different liquid-matrix interactions of the molecular species induce micro-phase segregation, which facilitates ice formation in water-rich regions. In addition, dynamical couplings at solvent-protein interfaces are discussed. It is shown that, on the one hand, solvent dynamics are substantially slowed down at protein surfaces and, on the other hand, protein dynamics significantly depend on the composition and, thus, the viscosity of the solvent. Furthermore, a protein dynamical transition occurs when the amplitude of water-coupled restricted backbone dynamics vanishes upon cooling.

Polyethylene glycol is water soluble and forms an eutectic system with water. The eutectic temperature is −19 °C for M =1500 g mol −1 and increases with molecular weight. The dielectric relaxation spectrum of the mixtures exhibits a strong loss maximum in ϵ ″ ( ω ) similar to pure water. Relaxation time increases with the addition of PEG. Activation energies exhibit a maximum of 0.35 eV at molar fraction χ p ≈0.2. This compares well with results on ethanol water mixtures. Adding PEG molecules to nanoscopic water droplets of inverse microemulsions has only small impact on the bending modulus κ of a non-ionic microemulsion. In AOT based microemulsions an increase or decrease of κ is found in dependence on the size of the droplets. This is in accordance with the variation of the dynamic percolation transition in the same systems.

FTIR spectroscopy has been used to reveal the effects of different types of cosolvents (TMAO, urea) as well as macromolecular crowding (using the crowding agent Ficoll) on the temperature and pressure dependent structure of poly-L-lysine, poly-D-lysine and their racemic mixture. Compared to the effects of cosolvents on the unfolding transition of proteins, their effects on the α-helix to aggregated β-sheet transition of polylysine are quite small. High hydrostatic pressure has been found to favor the α-helical state over the aggregated β-sheet structure which is reflected in a volume decrease of Δ V =−32 mL mol −1 , indicating that the packing mode is more efficient in the α-helical structure. Both, addition of urea and TMAO lead to a decrease in pressure stability of the aggregated β-sheet structure, which is accompanied by a three-fold decrease in Δ V , whereas the macromolecular crowder has little effect on the β-to-α transition. The more than 3 kbar higher β-to-α transition pressure of the racemic mixture compared with PLL confirms the drastic stabilization of β-sheet aggregates if the stereoisomers PLL and PDL are combined. Changes in hydration and packing of the polypeptide occurs upon interaction and fine packing of the polypeptide’s chains of opposed chirality, which are slightly modulated by the properties of cosolute and crowding, only. The underlying solvational and packing mechanisms observed here may be decisive factors responsible for the spontaneous protein aggregation in general and, as such, may shed additional light on the molecular basis of amyloid-associated diseases.

A series of novel functionalized mesoporous silica-based materials with well-defined pore diameters, surface functionalization and surface morphology is synthesized by co-condensation or grafting techniques and characterized by solid-state NMR spectroscopy, DNP enhanced solid state-NMR and thermodynamic techniques. These materials are employed as host-systems for small-guest molecules like water, small alcohols, carbonic acids, small aromatic molecules, binary mixtures and others. The phase-behavior of these confined guests is studied by combinations of one dimensional solid-state NMR techniques ( 1 H MAS, 2 H-line shape analysis, 13 C CPMAS) and two-dimensional correlation experiments like 1 H- 29 Si- solid-state HETCOR.

Nanoscale structuring in confined geometries using atomic layer deposition (ALD) is demonstrated for surfaces of nanochannels in track-etched polymer membranes and in mesoporous silica (SBA-15). Suitable process conditions for conformal ALD coating of polymer membranes and SBA-15 with inorganic oxides (SiO 2 , TiO 2 , Al 2 O 3 ) were developed. On the basis of the oxide-coated layers, nanochannels were further structured by a molecular-templated ALD approach, where calixarene macromolecules are covalently attached to the surface and then embedded into an Al 2 O 3 layer. The removal of calixarene by ozone treatment results in 1–2 nm wide surface nanocavities. Surfaces exposed to different process steps are analyzed by small angle X-ray scattering (SAXS) as well as by X-ray photoelectron and infrared spectroscopy. The proposed nanostructuring process increases the overall surface area, allows controlling the hydrophilicity of the channel surface, and is of interest for studying water and ion transport in confinement.

Surface enhanced solid-state NMR by dynamic nuclear polarization (DNP SENS) enables the characterization of the inner-pore surface functionalization of porous etched ion-track membranes exhibiting low specific surface areas compared to typical SBA- or MCM-type mesoporous silica materials. The membranes were conformally coated with a 5 nm thin SiO 2 layer by atomic layer deposition. This layer was subsequently modified by aminopropyl silane linkers that allow further functionalization via the terminal amine group. The results evidence that in principle DNP SENS is a capable tool to analyze more complex porous systems, e.g. bioinspired functional etched ion-track membranes down to the molecular level. These results are relevant also for single nanopore systems, for which a direct analysis of the channel surface functionalization is not feasible by classical characterization methods. The applicability of DNP SENS to complex porous systems requires the optimization of the sample preparation and measurement parameters.

Aqueous systems are omnipresent in nature and technology. They show complex behaviors, which often originate in the existence of hydrogen-bond networks. Prominent examples are the anomalies of water and the non-ideal behaviors of aqueous solutions. The phenomenology becomes even richer when aqueous liquids are subject to confinement. To this day, many properties of water and its mixtures, in particular, under confinement, are not understood. In recent years, molecular dynamics simulations developed into a powerful tool to improve our knowledge in this field. Here, our simulation results for water and aqueous mixtures in the bulk and in various confinements are reviewed and some new simulation data are added to improve our knowledge about the role of interfaces. Moreover, findings for water are compared with results for silica, exploiting that both systems form tetrahedral networks.

Controlling the synthesis of nanostructured surfaces is essential to tailor the properties of functional materials such as catalysts. We report on the synthesis of nanocavities of 1–2 nm dimension on planar Si-wafers by sacrificial nanotemplating and atomic layer deposition (ALD). It is shown that the process of nanocavity formation can be directly monitored on a monomolecular level through imaging with an atomic force microscope (AFM). In particular, by employing the AFM peak force tapping mode the simultaneous mapping of surface topography and tip-surface adhesion forces is accessible, which is useful for the assignment of topographical features and determining the orientation of the template molecules on the wafer surface. Detailed analysis based on the three-dimensional AFM topography allows for a quantification of the template and nanocavity surface coverage. The results are of importance for a detailed understanding of the processes underlying template-based nanocavity formation on oxide surfaces.

We employed FT-IR and NMR experiments to investigate the influence of a cell-mimicking crowding environment on the structure and dynamics of an elastin-like peptide (ELP) with the sequence GVG(VPGVG) 3 , which – due to a high number of hydrophobic amino acid side chains – exhibits an inverse temperature transition (ITT). As simplified crowding agent, we used 30 wt% Ficoll. The FT-IR data revealed the well-known broad ITT above ~25°C, as observed by the decrease of the relative population of random coil structures and the concomitant increase of type II β-turns. Interestingly, the addition of Ficoll leads to a destabilizing effect of type II β-turn structures. This is in contrast to the expected excluded-volume effect of the macromolecular crowder, but can be explained by weak interactions of the peptide with the polysaccharide chains of the crowding agent. Further, the crowding agent leads to the onset of a reversal of the folding transition at high temperatures. The full assignment of the ELP allowed for a residue-specific investigation of the dynamic behavior of ELP by NMR. Due to a strong change of microscopic viscosity between native/buffered conditions and crowded conditions, relaxation data remain inconclusive with respect to the observation of an ITT. Hence, no quantitative details in terms of internal conformational changes can be obtained. However, temperature dependent differences in the 13 C relaxation behavior between core and terminal parts of the peptide indicate temperature induced changes in the internal dynamics with generally higher internal mobility at chain ends: This is in full agreement with FT-IR data. In harmony with the FT-IR analysis, macromolecular crowding does not lead to significant changes in the relaxation behavior.