Structural characterization of an ionic liquid in bulk and in nano-confined environment using data from MD simulations

This article contains data on structural characterization of the [C2Mim][NTf2] in bulk and in nano-confined environment obtained using MD simulations. These data supplement those presented in the paper “Insights from Molecular Dynamics Simulations on Structural Organization and Diffusive Dynamics of an Ionic Liquid at Solid and Vacuum Interfaces” [1], where force fields with three different charge methods and three charge scaling factors were used for the analysis of the IL in the bulk, at the interface with the vacuum and the IL film in the contact with a hydroxylated alumina surface. Here, we present details on the construction of the model systems in an extended detailed methods section. Furthermore, for best parametrization, structural and dynamic properties of IL in different environment are studied with certain features presented herein

On the Adsorption of Aspartate Derivatives to Calcite Surfaces in Aqueous Environment

In many living organisms, biomolecules interact favorably with various surfaces of calcium carbonate. In this work, we have considered the interactions of aspartate (Asp) derivatives, as models of complex biomolecules, with calcite. Using kinetic growth experiments, we have investigated the inhibition of calcite growth by Asp, Asp2 and Asp3.This entailed the determination of a step-pinning growth regime as well as the evaluation of the adsorption constants and binding free energies for the three species to calcite crystals. These latter values are compared to free energy profiles obtained from fully atomistic molecular dynamics simulations. When using a flat (104) calcite surface in the models, the measured trend of binding energies is poorly reproduced. However, a more realistic model comprised of a surface with an island containing edges and corners, yields binding energies that compare very well with experiments. Surprisingly, we find that most binding modes involve the positively charged, ammonium group. Moreover, while attachment of the negatively charged carboxylate groups is also frequently observed, it is always balanced by the aqueous solvation of an equal or greater number of carboxylates. These effects are observed on all calcite features including edges and corners, the latter being associated with dominant affinities to Asp derivatives. As these features are also precisely the active sites for crystal growth, the experimental and theoretical results point strongly to a growth inhibition mechanism whereby these sites become blocked, preventing further attachment of dissolved ions and halting further growth

Dynamic equilibria in supported ionic liquid phase (SILP) catalysis: in situ IR spectroscopy identifies [Ru(CO)x_xCly_y]n_n species in water gas shift catalysis

Ru-based supported ionic liquid phase (SILP) systems efficiently catalyze the low- temperature water-gas shift reaction (WGSR). While previous studies suggest that Ru-carbonyl species play an important role in the mechanism, detailed knowledge on the catalytically active species is still missing. To identify these carbonyl complexes, we apply in situ diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS) in combination with density functional theory (DFT). Investigations of an as-prepared [RuIJCO)3Cl2]2/ [C4C1C1Im]Cl/Al2O3 catalyst indicate splitting of the dimer induced by Cl−. Subsequently, an equilibrium between several [RuIJCO)xCly]n species is established, in which the IL serves as an effectively infinite Cl− reservoir. We find that the major species in the system freshly-prepared from [RuIJCO)3Cl2]2 is indeed [RuIJCO)3Cl3]−. A smaller amount of [RuIJCO)2Cl3]− and chloride-rich species [RuIJCO)2Cl4]2− or [RuCOCl4]2− are also found in the SILP. Similar Ru-carbonyl species are observed during carbonylation of RuCl3/ [C4C1C1Im]Cl/Al2O3, another potential WGSR catalyst. The response of [RuIJCO)3Cl2]2/[C4C1C1Im]Cl/Al2O3 to heating and/or CO dosing was probed in situ and the results confirm the presence of the equilibrium proposed above

ESPRAS Survey on Breast Reconstruction in Europe.

BACKGROUND  The European Leadership Forum (ELF) of the European Society of Plastic, Reconstructive and Aesthetic Surgery (ESPRAS) previously identified the need for harmonisation of breast reconstruction standards in Europe, in order to strengthen the role of plastic surgeons. This study aims to survey the status, current trends and potential regional differences in the practice of breast reconstruction in Europe, with emphasis on equity and access. MATERIALS AND METHODS  A largescale web-based questionnaire was sent to consultant plastic and reconstructive surgeons, who are experienced in breast reconstruction and with understanding of the national situation in their country. Suitable participants were identified via the Executive Committee (ExCo) of ESPRAS and national delegates of ESPRAS. The results were evaluated and related to evidence-based literature. RESULTS  A total of 33 participants from 29 European countries participated in this study. Overall, the incidence of breast reconstruction was reported to be relatively low across Europe, comparable to other large geographic regions, such as North America. Equity of provision and access to breast reconstruction was distributed evenly within Europe, with geographic regions potentially affecting the type of reconstruction offered. Standard practices with regard to radiotherapy differed between countries and a clear demand for European guidelines on breast reconstruction was reported. CONCLUSION  This study identified distinct lack of consistency in international practice patterns across European countries and a strong demand for consistent European guidance. Large-scale and multi-centre European clinical trials are required to further elucidate the presented areas of interest and to define European standard operating procedures