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The influence of the polar, aprotic solvent propylene carbonate on the interfacial structure of the ionic liquid (IL) 1-butyl-1-methylpyrrolidinium tris(pentafluoroethyl)trifluorophosphate on sapphire was investigated by high-energy x-ray reflectivity. Experiments at solvent concentrations between 17 mol.% and 83 mol.% bridge the gap between diluted electrolytes described by the classical Gouy- Chapman theory and pure ionic liquids. Analysis of our experimental data revealed interfacial profiles comprised of alternating anion and cation enriched regions decaying gradually into the bulk liquid. With increasing solvent concentration, we observed a decrease in correlation length of the interfacial layering structure. At high ion concentrations, solvent molecules were found to accumulate laterally within the layers. By separating like-charged ions, they reduce their Coulomb repulsion. The results are compared with the bulk structure of IL/solvent blends probed by x-ray scattering and predictions from fundamental fluid theory. [ABSTRACT FROM AUTHOR]

The development of simple, primitive model descriptions for electrolyte solutions is usually carried out by fitting the system parameters to reproduce some experimental data. We propose an alternative method, that allows one to derive implicit solvent models of electrolyte solutions from all-atom descriptions. We obtain analytic expressions for the thermodynamic and structural properties of the ions, which are in good agreement with the underlying explicit solvent representation, provided that ion association is taken into account. Effective ion-ion potentials are derived from molecular dynamics simulations and are used within a first-order perturbation theory to derive the best possible description in terms of charged hard-spheres. We show that our model provides a valid description for a series of 1-1 electrolytes. [ABSTRACT FROM AUTHOR]

The ASEP/MD method has been employed for studying the solvent effect on the conformational equilibrium of the alanine dipeptide in water solution. MP2 and density functional theory (DFT) levels of theory were used and results were compared. While in gas phase cyclic structures showing intramolecular hydrogen bonds were found to be the most stable, the stability order is reversed in water solution. Intermolecular interaction with the solvent causes the predominance of extended structures as the stabilizing contacts dipeptide-water are favoured. Free-energy differences in solution were calculated and PPII, αR, and C5 conformers were identified as the most stable at MP2 level. Experimental data from Raman and IR techniques show discrepancies about the relative abundance of αR y C5, our results support the Raman data. The DFT level of theory agrees with MP2 in the location and stability of PPII and αR forms but fails in the location of C5. MP2 results suggest the possibility of finding traces of C7eq conformer in water solution, in agreement with recent experiments. [ABSTRACT FROM AUTHOR]

Co-solvents such as glycerol and sorbitol are small organic molecules solvated in the cellular solutions that can have profound effects on the protein structures. Here, the molecular dynamics simulations and comparative structural analysis of magainin, as a peptide model, in pure water, 2,2,2-trifluoroethanol/water, glycerol/water, and sorbitol/water are reported. Our results show that the peptide NMR structure is largely maintained its native structure in osmolytes-water mixtures. The simulation data indicates that the stabilizing effect of glycerol and sorbitol is induced by preferential accumulation of glycerol and sorbitol molecules around the nonpolar and aromatic residues. Thus, the presence of glycerol and sorbitol molecules decreases the interactions of water molecules with the hydrophobic residues of the peptide, and the alpha helical structure is stabilized. [ABSTRACT FROM AUTHOR]

The presence of a chiral surface can alter the characteristics of nearby solvent molecules such that, on average, these molecules become chiral. The extent of this induced chirality and its dependence on the surface and solvent characteristics are explored in this article. Three surfaces employed in chiral chromatography are examined: The Whelk-O1 interface, a phenylglycine-derived chiral stationary phase (CSP), and a leucine-derived CSP. All three interfaces are “brush type” in that the chiral molecules are attached to the underlying substrate via an achiral tether. The solvents consist of ethanol, a binary n-hexane/ethanol solvent, 2-propanol, and a binary n-hexane/2-propanol solvent. Molecular dynamics simulations of the solvated chiral interfaces form the basis of the analysis. The chirality induced in the solvent is assessed based on a chirality index originally proposed by Osipov et al. [Mol. Phys. 84, 1193 (1995)]. Solvent chirality will depend on the solvent position relative to the surface. For this reason, a position-dependent chirality index is analyzed in detail. [ABSTRACT FROM AUTHOR]

We have performed measurements of the thermal diffusion coefficient DT in the dilute limit on polystyrene in cyclo-octane, cyclohexane, benzene, toluene, tetrahydrofuran, ethyl acetate, and methyl ethyl ketone and of poly(dimethyl-siloxane) in toluene. These data have been combined with literature data to test various theoretical predictions. The viscosity is identified as the dominating and only relevant solvent parameter. On the polymer side, the size or mass of an effective correlated segment determines the strength of the Soret effect. Large and heavy effective segments, as found in stiffer chains, lead to higher DT. [ABSTRACT FROM AUTHOR]

We use first-principles quantum-chemical approaches to study absorption and emission properties of recently synthesized distyrylbenzene (DSB) derivative chromophores and their dimers (two DSB molecules linked through a [2.2]paracyclophane moiety). Several solvent models are applied to model experimentally observed shifts and radiative lifetimes in Stokes nonpolar organic solvents (toluene) and water. The molecular environment is simulated using the implicit solvation models, as well as explicit water molecules and counterions. Calculations show that neither implicit nor explicit solvent models are sufficient to reproduce experimental observations. The contact pair between the chromophore and counterion, on the other hand, is able to reproduce the experimental data when a partial screening effect of the solvent is taken into account. Based on our simulations we suggest two mechanisms for the excited-state lifetime increase in aqueous solutions. These findings may have a number of implications for organic light-emitting devices, electronic functionalities of soluble polymers and molecular fluorescent labels, and their possible applications as biosensors and charge/energy conduits in nanoassemblies. [ABSTRACT FROM AUTHOR]

This study modifies the authors' previously reported directed self-assembly (DSA) process of polystyrene-block-poly(methyl methacrylate) (PS-b-PMMA) in order to meet the throughput and material-related requirements of a semiconductor manufacturing environment. It is demonstrated that all of the bottleneck steps in the authors' DSA process, including the deposition of the cross-linkable mat and the deposition of the brush layer, can be done in minutes on a hot plate in an N2 atmosphere, which simulates the processing environment of a lithography track module. A 25-nm-pitch pattern resulting from a 4:1 density multiplication was demonstrated with a manufacturing-compatible organic solvent. A preliminary uniformity study on 300 mm wafers was also presented. The modified DSA process presents a viable solution to some of the anticipated throughput-related challenges to DSA commercialization and thus, brings integration of DSA within reach of the semiconductor manufacturing industry. [ABSTRACT FROM AUTHOR]

A simple and reliable method for preparing tips coated with poly(dimethylsiloxane) (PDMS) for scanning tunneling microscopy (STM) in aqueous solutions is reported. Au STM tips were dip-coated with PDMS and subsequently cured. The coated tips were characterized by scanning electron microscopy, energy dispersive x-ray spectroscopy, and voltammetry. We show that the PDMS layer smoothly covers the tip surface except for its very apex. These tips enable atomically resolved imaging of a sample surface and measurement of single-molecule conductance below 1.0 nS with STM in aqueous solutions. Because of the superior compatibility of PDMS with organic solvents, the PDMS-coated tips would be useful for preparing molecular tips via their chemical modification in such solvents, enabling chemically selective imaging of a single molecule in water. [ABSTRACT FROM AUTHOR]

Ultrafast carrier dynamics and saturable absorption of few-layered graphene oxide, well-dispersed in organic solvent, are studied using femtosecond pump-probe and Z-scan techniques. The results demonstrate that few-layered graphene oxide has a fast energy relaxation of hot carriers and strong saturable absorption, which is comparable with that of reduced graphene oxide. Fast carrier relaxation combined with well solution processing capability arises from the large fraction of sp2 carbon atom inside the few-layered graphene oxide sheet together with oxidation mainly existing at the edge areas. This superiority of few-layered graphene oxide will facilitate potential applications of graphene for ultrafast photonics. [ABSTRACT FROM AUTHOR]

We present a procedure to reconfigure microring resonators based on liquid surface adhesion. Droplets of organic solvents were deposited over Si3N4/SiO2 strip- and slot-waveguide ring resonators, and the transmission spectra were measured several hours after the evaporation of the droplets at room temperature. Our measurements show that the optical properties of the microrings are significantly modified by liquid adhered to the waveguides, persisting even 96 h after bulk evaporation. Liquid-solid interfacial forces slow down liquid evaporation at the nanoscale, enabling permanent photonic configurations. Rewriteability is achieved by removing the adhered liquid with heat. [ABSTRACT FROM AUTHOR]