Use of solid-phase microextraction-capillary-gas chromatography (SPME-CGC) for the varietal characterization of wines by means of chemometrical methods

The extraction of wine aroma compounds was studied by direct-SPME (DI/SPME), headspace-SPME (HS/SPME) and multiple-headspace-extraction-SPME (MHE/SPME). The aromagrams obtained by HS/SPME-CGC were evaluated with chemometrical methods for the varietal classification of wines. Received: 25 July 1997 / Revised: 24 September 1997 / Accepted: 7 October 1997     

Theoretical investigations of Fe porphyrins. V. Low-lying electronic states of bisammineporphinatoiron(III)

Ab initio CI calculations are reported on the lowest doublet, quartet, and sextet states of [Fe^III(P)(NH₃)₂]⁺. The low-spin ground state is calculated as (d_xy² (d_π)³ with d_xy(d_π)⁴ higher by 0.15 eV. The near-ir bands at ～1 eV observed in low-spin ferriheme proteins are attributed to (π → d_π) transitions. The lowest high-spin state is ⁶A_1g, and the near-ir transitions of the high-spin ferriheme proteins observed at ～1.2 eV are attributed to higher ⁶[tripsextet] excited states [i.e., ring triplet, metal sextet]. The 30-ps “triplet” transient populated with low quantum yield observed in laser-flash studies on Fe^III(TPP)CI [TPP = tetrapbenylporphyrin] may be an ¹[tripsextet] state.     

Rhodopsin exhibits a preference for solvation by polyunsaturated docosohexaenoic acid

An all-atom molecular dynamics simulation of rhodopsin in a membrane environment has been carried out with lipid composition similar to that of the retinal membrane. The initial conformation of the protein was taken from the X-ray crystallographic structure (1F88), while those of the lipids came from a previous molecular dynamics simulation. During the course of the 12.5 ns simulation, the initially randomly placed lipids adopt an anisotropic solvation structure around the protein. The lipids, having one saturated stearic acid chain and one polyunsaturated docosohexaenoic acid chain with a zwitterionic phosphatidylcholine headgroup, arrange themselves to maximize contact between the polyunsaturated chain and the protein surface. This organization is driven by energetically favorable interactions between the transmembrance helices and the docosohexaenoyl chains that are largely of the van der Waals type. These observations are consistent with various experimental studies on rhodopsin and other G-protein coupled receptors and with the picture of extreme flexibility in polyunsaturated fatty acid chains that has arisen from recent NMR and computational work.     

Simple technique for the simultaneous determination of solvent diffusion coefficient in polymer by Quantum Resistive Sensors and FT‐IR spectroscopy

A simple, quick and novel method for the determination of diffusion properties through polymer films, based on Quantum Resistive Sensors made of Conductive Polymer nanoComposites is presented. The integral time lag method is employed for the calculation of diffusion coefficient, and the results are compared simultaneously with that of Fourier transform infrared spectroscopy and sorption method. Two model polymers, a semi‐crystalline poly(lactic acid) and an amorphous poly(isobutylene‐co‐isoprene), are used to validate the study. A good correlation is established between the diffusion coefficient values derived from all techniques demonstrating the interest of such reliable, simple and cheap nanosensors for the quick determination (several minutes) of diffusion properties in polymer films. Our first results suggest that this technique is meaningful for the determination of barrier properties in nanocomposite membranes filled with platelets of graphene or clay. Copyright © 2013 John Wiley & Sons, Ltd.     

Synthesis and Characterization of the New Copper Indium Phosphate Cu8In8P4O30

The system CuO/In₂O₃/P₂O₅ has been investigated using solid state reaction between CuO, In₂O₃ and (NH₄)₂HPO₄ in silica glass crucibles at 900 °C. The powder samples were characterized by X‐ray diffraction, thermal analysis and FT‐IR spectroscopy. Orange single crystals of the new quaternary phase were achieved by the process of crystallization with mineralizers in sealed silica glass ampoules. They were then analyzed with EDX and single‐crystal X‐ray analysis in which the composition Cu₈In₈P₄O₃₀ with the triclinic space group P$\bar{1}$ (No 2) with a = 7,2429(14) Å, b = 8,8002(18) Å, c = 10,069(2) Å, α = 103,62(3)°, β = 106,31(3)°, γ = 101,55(3)° and Z = 1 was found. The three‐dimensional framework consists of [InO₆] octahedra and distorted [CuO₆] octahedra, overcaped [InO₇] prisms and [PO₄] tetrahedra, also trigonal [(CuIn)O₅] bipyramids and distorted [(CuIn)O₆] octahedra, where copper and indium are partly exchanged against each other. Cu₈In₈P₄O₃₀ exhibits an incongruent melting point at 1023 °C.     

Extended defects in CdZnTe crystals: Effects on device performance

We explored some unique defects in a batch of cadmium zinc telluride (CdZnTe) crystals, along with dislocations and Te-rich decorated features, revealed by chemical etching. We extensively investigated these distinctive imperfections in the crystals to identify their origin, dimensions, and distribution in the bulk material. We estimated that these features ranged from 50 to 500 μm in diameter, and their depth was about ∼300 μm. The density of these features ranged between 2×10² and 1×10³ per cm³. We elaborated a model of them and projected their effect on charge collection and spectral response. In addition, we fabricated detectors with these defective crystals and acquired fine details of charge-transport phenomena over the detectors’ volume using a high-spatial resolution (25 μm) X-ray response mapping technique. We related the results to better understand the defects and their influence on the charge-transport properties of the devices. The role of the defects was identified by correlating their signatures with the findings from our theoretical model and our experimental data.     

Atomic-scale structure of dislocations revealed by scanning tunneling microscopy and molecular dynamics

The intersection between dislocations and a Ag(111) surface has been studied using an interplay of scanning tunneling microscopy (STM) and molecular dynamics. Whereas the STM provides atomically resolved information about the surface structure and Burgers vectors of the dislocations, the simulations can be used to determine dislocation structure and orientation in the near-surface region. In a similar way, the subsurface structure of other extended defects can be studied. The simulations show dislocations to reorient the partials in the surface region leading to an increased splitting width at the surface, in agreement with the STM observations. Implications for surface-induced cross slip are discussed.