Calculation of the glory scattering with anisotropic molecule-atom interactions in sudden approximation

For specified rotational states glory phenomena are investigated in sudden approximation under influence of angle dependent terms in the intermolecular potential. The distance at which the intermolecular potential is probed by the anisotropic glory undulation is R ≈ 0.96 R_m, for LJ 12-6 potentials, i.e. the well defined probing distance nearly coincides with the classical turning point of the glory ray. For a specific choice of the ratio of anisotropy parameters, q_2,12/q_2,6, ≈ 1.5, the anisotropic glory changes sign. Quenching of the state averaged glories practically disappears for q_2,12/q_2,6 ≈ 2 (e.g. for NO-Ar). The method of calculation is tested against a full partial wave treatment.     

The Berry-Esseen theorem for functions of uniform spacings

Summary A Berry-Esseen bound of order is established for suitably normalized sums of nonlinear measurable functions of uniform spacings under the natural moment assumptions.Some of this study was carried out at the Mathematical Centre, Amsterdam, and some of it when the second author was a member of the Mathematical Sciences Research Institute, Berkeley     

Polyol-Komplexe. VIII. R,R-trans-1,2-Diaminocyclohexan-κN,N′-(methyl-β-D-xylopyranosid-2,3-ato-κO2,O3)-aqua-kupfer-Dihydrat, [(R,R-chxn)(H2O)Cu(Me-β-D-Xylp2,3 H−2)] · 2 H2O, — ein Kupferkomplex mit einem doppelt deprotonierten D-Xylosederivat als Ligand

Polyol Metal Complexes. VIII. R,R-trans-Diaminocyclohexane-κN,N′ Methyl-β-D-xylopyranosid-2,3-ato-κO²,O³ Aqua Copper Dihydrate, [(R,R-chxn)(H₂O)Cu(Me-β-D-Xylp2,3 H_?2)] · 2 H₂O, — a Copper Complex with a Twofold Deprotonated Xylose Derivative as a Ligand Methyl β-D-xylopyranoside forms a chelate complex with copper(II) ions in aqueous, alkaline solution after deprotonation at O-2 and O-3. In the blue crystals, Cu^II is further coordinated by R,R-trans-1,2-diaminocyclohexane and water; P2₁, a = 982.9(3), b = 705.8(5), c = 1 292.1(6) pm, β = 96.74(4)°, V = 890.2(8) · 10⁶ pm³. The alkoxide-O-atoms act as acceptors in a hydrogen bond system, a typical feature of which is a homodromic helix of water molecules.     

High-performance liquid chromatographic analysis of glutathione and its thiol and disulfide degradation products

A rapid and sensitive high-performance liquid chromatographic method for quantitation of picomole levels of glutathione, glutathione disulfide, cysteine, cystine, cysteinylglycine, cysteinylglycine disulfide and cysteine glutathione-mixed disulfide in biological samples is described. The compounds were separated isocratically on a reversed-phase column by ion-pair chromatography. The mobile phase consisted of an aqueous buffer containing 0.1 M monochloroacetic acid and 3.3 mM 1-heptanesulfonic acid (pH 2.60)-methanol-N,N-dimethylformamide (96.5:3.0:0.5). After chromatographic separation, the disulfides were reduced by a potential (-1.0 V) from a battery, with subsequent detection of all thiols by electrochemical oxidation (+0.15 V) with a dual gold-mercury electrode. Thiol and disulfide concentrations were determined in tissue extracts (liver and kidney) and fluids (bile and plasma) from control rats and rats treated with acivicin, an inhibitor of gamma-glutamyltranspeptidase. A marked increase in biliary glutathione concentration was observed in treated animals with a corresponding decrease in cysteine and cysteinylglycine concentrations. The results demonstrate that this method is useful for measuring glutathione and its degradation products in tissues and fluids.     

The <Emphasis Type="Italic">r</Emphasis><Subscript>0</Subscript> structural parameters of equatorial and axial chlorocyclobutane,conformational stability from temperature dependent infrared spectra of xenon solutions,and vibrational assignments

Variable temperature (?55 to ?100 °C) studies of the infrared spectra (4,000–400 cm^?1) of chlorocyclobutane, c-C₄H₇Cl, dissolved in liquid xenon have been carried out. The infrared spectrum (4,000–100 cm^–1) of the gas has also been recorded. For this puckered ring molecule the enthalpy difference between the more stable equatorial conformer and the axial form, has been determined to be 361 ± 17 cm^?1 (4.32 ± 0.20 kJ/mol). This stability order is consistent with that predicted by ab initio calculations but the ?H is much lower than the average energy value of 646 ± 73 cm^?1 obtained from the MP2 ab initio calculations or 611 ± 28 cm^?1 from the B3LYP density functional theory calculations. The percentage of the axial conformer present at ambient temperature is estimated to be 15 ± 1%. By utilizing previously reported microwave rotational constants for both conformers combined with ab initio MP2(full)/6–311+G(d,p) predicted structural values, adjusted r ₀ parameters have been obtained. The determined heavy atom structural parameters for the equatorial conformer are: the distances C–Cl = 1.783(5), C₁–C₄ = 1.539(3), C₄–C₆ = 1.558(3) Å, and angles ∠C₆C₄C₁ = 86.9(5), ∠C₄C₁C₅ = 89.7(5)°, and for the axial conformer are: the distances C–Cl = 1.803(5), C₁–C₄ = 1.547(3), C₄–C₆ = 1.557(3) Å, and angles ∠C₆C₄C₁ = 86.3(5), ∠C₄C₁C₅ = 88.9(5) and the puckering angles for the equatorial and axial conformers are 30.7(5)° and 22.3(5)°, respectively. The conformational stabilities, harmonic force fields, infrared intensities, Raman activities, depolarization ratios and vibrational frequencies have been obtained for both conformers from MP2(full)/6-31G(d) ab initio calculations and compared to experimental values where available. The results are discussed and compared to the corresponding properties of some similar molecules.     

Cost-effective sulphur emission reduction under uncertainty

The problem of reducing SO₂ emissions in Europe is considered. The costs of reduction are assumed to be uncertain and are modeled by a set of possible scenarios. A mean-variance model of the problem is formulated and a specialized computational procedure is developed. The approach is applied to the trans-boundary air pollution model with real-world data.     

A High-Conversion-Factor, Double-Resonance Structure for High-Field Dynamic Nuclear Polarization

This contribution presents a novel design of a double-resonance structure for high-field dynamic nuclear polarization operating at 95 GHz and 144 MHz, in which a miniaturized radiofrequency coil is integrated within a single-mode nonradiative dielectric resonator. After a detailed discussion of the design principles, the conversion factors of this system are determined by means of microwave and radiofrequency measurements. The obtained results, 1.68 mT/W^1/2 for the microwave conversion factor and 0.8 mT/W^1/2 for the radiofrequency conversion factor, represent the state-of-the-art among the double-resonance structures. Simultaneous electron paramagnetic resonance and liquid-state ¹H nuclear magnetic resonance experiments are performed on samples of nitroxide radical 2,2,6,6-tetramethylpiperidine-1-oxyl dissolved in a mixture of water and dioxane. A maximum dynamic nuclear polarization enhancement of about ?16 is obtained at a microwave power of 70 mW with a radical concentration of 10 mM in nanoliter-sized sample volumes. These results are discussed in view of further improvements and applications of the proposed double-resonance structure.     

The configuration of the hydrogen atoms in HfV2Hx compounds at low temperatures: A NMR study

The ⁵¹V nuclear electric quadrupole interaction and the shape of the proton resonance line in the low temperature phase of the HfV₂H_x (0≤x≤4) compounds has been studied by NMR. The data yield information about the hydrogen arrangement in the low temperature phase. They confirm the results of recent neutron diffraction studies that for x=4 and ordered super lattice of the hydrogen atoms exists, with the hydrogen atoms occupying only tetrahedral interstitial sites formed by two Hf and two V atoms. Our results show that in the lower concentration compound the hydrogen atoms most probably also occupy the same type of interstices, but without crystallographic order.     

Conformational,vibrational, and structural studies of 2,2,3,3,3‐pentafluoropropylamine from Raman and infrared spectra of gas,liquid, xenon solutions,and solid supported by ab initio calculations

The Raman and infrared spectra (3500–50 cm⁻¹) of the gas, liquid or solution, and solid were recorded of 2,2,3,3,3‐pentafluoropropylamine (CF₃CF₂CH₂NH₂) and the ND₂ isotopomer. Variable temperature (−55 to − 100 °C) studies of the infrared spectra (3600–400 cm⁻¹) of samples dissolved in liquid xenon have been carried out. From these data, two of the five possible conformers have been identified and their relative stabilities obtained. The enthalpy difference was determined between the more stable Tt conformer and the less stable Tg form to be 280 ± 14 cm⁻¹ (3.35 ± 0.17 kJ/mol). The first indicator is the NCCC dihedral angle (G = gauche or T = trans), and the second one (g = gauche or t = trans) is the relative position of the lone pair of electrons on nitrogen with respect to the β‐carbon. The percentage of the Tg conformer at ambient temperature is estimated to be 34 ± 2%. The conformational stabilities have been predicted from ab initio calculations utilizing several different basis sets up to aug‐cc‐pVTZ for both MP2(full) and density functional theory calculations by the B3LYP method. Vibrational assignments have been provided for most of the observed bands for both isotopomers, supported by MP2(full)/6‐31G(d) ab initio calculations to predict the harmonic force fields, wavenumbers, infrared intensities, Raman activities, and depolarization ratios for both conformers. Estimated r₀ structural parameters were obtained from adjusted MP2(full)/6‐311 + G(d,p) calculations. The results are discussed and compared with the corresponding properties of some related molecules. Copyright © 2011 John Wiley & Sons, Ltd.