Interfacial Water and Micro-heterogeneity in Aqueous Solutions of Ionic Liquids

In this work, aqueous solutions of two prototypical ionic liquids (ILs), [BMIM][BF4] and [BMIM][TfO], were investigated by UV Raman spectroscopy and small-angle neutron scattering (SANS) in the water-rich domain, where strong heterogeneities at mesoscopic length scales (microheterogeneity) were expected. Analyzing Raman data by a differential method, the solute-correlated (SC) spectrum was extracted from the OH stretching profiles, emphasizing specific hydration features of the anions. SC-UV Raman spectra pointed out the molecular structuring of the interfacial water in these microheterogeneous IL/water mixtures, in which IL aggregates coexist with bulk water domains. The organization of the interfacial water differs for the [BMIM][BF4] and [BMIM][TfO] solutions, being affected by specific anion−water interactions. In particular, in the case of [BMIM][BF4], which forms weaker H-bonds with water, the aggregation properties clearly depend on concentration, as reflected by local changes in the interfacial water. On the other hand, stronger water−anion hydrogen bonds and more persistent hydration layers were observed for [BMIM][TfO], which likely prevent changes in IL aggregates. The modeling of SANS profiles, extended to [BPy][BF4] and [BPy][TfO], evidences the occurrence of significant concentration fluctuations for all of the systems: this appears as a rather general phenomenon that can be ascribed to the presence of IL aggregation, mainly induced by (cation-driven) hydrophobic interactions. Nevertheless, larger concentration fluctuations were observed for [BMIM][BF4], suggesting that anion−water interactions are relevant in modulating the microheterogeneity of the mixture

Hydration Dynamics of Model Peptides with Different Hydrophobic Character

The multi-scale dynamics of aqueous solutions of the hydrophilic peptide N-acetyl-glycine-methylamide (NAGMA) have been investigated through extended frequency-range depolarized light scattering (EDLS), which enables the broad-band detection of collective polarizability anisotropy fluctuations. The results have been compared to those obtained for N-acetyl-leucinemethylamide (NALMA), an amphiphilic peptide which shares with NAGMA the same polar backbone, but also contains an apolar group. Our study indicates that the two model peptides induce similar effects on the fast translational dynamics of surrounding water. Both systems slow down the mobility of solvating water molecules by a factor 6–8, with respect to the bulk. Moreover, the two peptides cause a comparable far-reaching spatial perturbation extending to more than two hydration layers in diluted conditions. The observed concentration dependence of the hydration number is explained considering the random superposition of different hydration shells, while no indication of solute aggregation phenomena has been found. The results indicate that the effect on the dynamics of water solvating the amphiphilic peptide is dominated by the hydrophilic backbone. The minor impact of the hydrophobic moiety on hydration features is consistent with structural findings derived by Fourier transform infrared (FTIR) measurements, performed in attenuated total reflectance (ATR) configuration. Additionally, we give evidence that, for both systems, the relaxation mode in the GHz frequency range probed by EDLS is related to solute rotational dynamics. The rotation of NALMA occurs at higher timescales, with respect to the rotation of NAGMA; both processes are significantly slower than the structural dynamics of hydration water, suggesting that solute and solvent motions are uncoupled. Finally, our results do not indicate the presence of super-slow water (relaxation times in the order of tens of picoseconds) around the peptides investigated

Proceedings of the fourth Resilience Engineering Symposium

These proceedings document the various presentations at the Fourth Resilience Engineering Symposium held on June 8-10, 2011, in Sophia-Antipolis, France. The Symposium gathered participants from five continents and provided them with a forum to exchange experiences and problems, and to learn about Resilience Engineering from the latest scientific achievements to recent practical applications. The First Resilience Engineering Symposium was held in Söderköping, Sweden, on October 25-29 2004. The Second Resilience Engineering Symposium was held in Juan-les-Pins, France, on November 8-10 2006, The Third Resilience Engineering Symposium was held in Juan-les-Pins, France, on October 28-30 2008. Since the first Symposium, resilience engineering has fast become recognised as a valuable complement to the established approaches to safety. Both industry and academia have recognised that resilience engineering offers valuable conceptual and practical basis that can be used to attack the problems of interconnectedness and intractability of complex socio-technical systems. The concepts and principles of resilience engineering have been tested and refined by applications in such fields as air traffic management, offshore production, patient safety, and commercial fishing. Continued work has also made it clear that resilience is neither limited to handling threats and disturbances, nor confined to situations where something can go wrong. Today, resilience is understood as the intrinsic ability of a system to adjust its functioning prior to, during, or following changes and disturbances, so that it can sustain required operations under both expected and unexpected conditions. This definition emphasizes the ability to continue functioning, rather than simply to react and recover from disturbances and the ability to deal with diverse conditions of functioning, expected as well as unexpected. For anyone who is interested in learning more about Resilience Engineering, the books published in the Ashgate Studies in Resilience Engineering provide an excellent starting point. Another sign that Resilience Engineering is coming of age is the establishment of the Resilience Engineering Association. The goal of this association is to provide a forum for coordination and exchange of experiences, by bringing together researchers and professionals working in the Resilience Engineering domain and organisations applying or willing to apply Resilience Engineering principles in their operations. The Resilience Engineering Association held its first General Assembly during the Fourth Symposium, and will in the future play an active role in the organisation of symposia and other activities related to Resilience Engineering