Homomorphic Feller Cocycles on a C*-Algebra

When a Fock-adapted Feller cocycle on a C*-algebra is regular,completely positive and contractive, it possesses a stochasticgenerator that is necessarily completely bounded. Necessaryand sufficient conditions are given, in the form of a sequenceof identities, for a completely bounded map to generate a weaklymultiplicative cocycle. These are derived from a product formulafor iterated quantum stochastic integrals. Under two alternativeassumptions, one of which covers all previously considered cases,the first identity in the sequence is shown to imply the rest.     

Temperature Dependence for the Relative Raman Cross Section of the Ammonia/Water Complex

The Raman spectra of aqueous ammonia solutions have been obtained between -40 and 25 degrees C. The Raman spectrum of neat water was also obtained at 25 degrees C and is characterized by two broad peaks observed at 3200 and 3400 cm(-1). The spectrum due to water is subtracted to determine the NH(3) spectrum at all temperatures. In ammonia-water solutions, the spectrum shows three features at measured displacements of 3250, 3316, and 3400 cm(-1). The feature at 3316 cm(-1) is assigned to the Q branch of the symmetric stretch. The broad, weak features at 3250 and 3400 cm(-1), previously assigned to rotational bands, are assigned to combination bands. The NH(3) combination bands are assigned by comparing with sum frequency generation (SFG) experiments, monitoring changes with temperature, and analyzing the polarization data. The rotational structure of the Q band is also discussed. As the temperature is lowered from 25 to -40 degrees C, an increase in the Raman intensity is observed for all bands. The relative Raman scattering cross section is determined from the numerically integrated area of the NH(3) Q branch at each temperature. Copyright 2001 Academic Press.     

Studies on thermionic ionisation detection in comprehensive two-dimensional gas chromatography

This study explores the application of specific thermionic ionisation detection in comprehensive 2-D GC (GC x GC) and represents the first report of GC x GC with nitrogen phosphorus detection (GC x GC-NPD). Of particular interest is the performance of the NPD with respect to peak parameters of asymmetry and sensitivity. Since GC x GC produces much narrower peaks than obtained with fast GC (e.g. 100 ms vs. <1 s) the effect of detector response time and any lack of symmetry arising from the detection step is important if peak separation (resolution) is to be maintained. It was observed that detector gas flows had a significant impact on peak asymmetry and peak magnitude, and that optimisation of the detector was critical, particularly for complex sample analysis by GC x GC-NPD. Peak asymmetries ranging from As = 1.8 to 8.0 were observed under different conditions of detector gas flows. Comparison of GC x GC-NPD with GC x GC-flame ionisation detection (FID) showed the former to be approximately 20 times more sensitive for the detection of nitrogen-containing methoxypyrazines analytes, and GC x GC-NPD had a larger linear detection range compared to GC x GC-FID. Furthermore, comparison of GC x GC-NPD and GC x GC-TOFMS chromatograms for the analysis of coffee head-space demonstrated the benefits of selective detection, ultimately realised in a comparatively simplified contour plot.     

Short Total Synthesis of Ajoene

We describe a short total synthesis of ajoene, a major biologically active constituent of garlic. The instability of allicin as the only other known alternative starting material has led to the development of a reliable procedure for the synthesis of ajoene from simple building blocks that is also suitable for upscale operations.     

Copolymerization of ethylene and non-conjugated diene using homogenous catalyst

Ethylene and different amounts of 1,7-octadiene were copolymerized using the metallocene catalyst system ethylidene-bis(fluorenyl) zirconium dichloride and methylaluminoxane (MAO) at both 50 and 90 °C. The catalyst activity has slightly increased with the addition of low amounts of the diene in relation to the homopolymerization of ethylene. The obtained polymers were characterized according to their melting temperature (T_m) and crystallinity degree (x_c) by differential scanning calorimetry (DSC). Weight-average molecular weight (M_w) and polydispersity were determined by gel permeation chromatography (GPC). Diene contents in the copolymer were obtained through the FTIR spectroscopy. The results indicated that at polymerization temperature of 90 °C, crosslinking bonds in the obtained copolymers were low, differently from what was observed at 50 °C. The diene content in the copolymer achieved more than 3 mol% and the comonomer conversion was around 15%. Moreover, the obtained copolymers have M_w around 100,000 and large polydispersity.     

Synthesis,crystal structure and magnetic properties of the helical oxalate-bridged copper(II) chain {[(CH3)4N]2[Cu(C2O4)2] · H2O}n

The preparation, crystal structure and magnetic properties of a new oxalate-containing copper(II) chain of formula {[(CH₃)₄N]₂[Cu(C₂O₄)₂] · H₂O}_n (1) [(CH₃)₄N⁺ = tetramethylammonium cation] are reported. The structure of 1 consists of anionic oxalate-bridged copper(II) chains, tetramethylammoniun cations and crystallization water molecules. Each copper(II) ion in 1 is surrounded by three oxalate ligands, one being bidentate and the other two exhibiting bis-bidenate coordination modes. Although all the tris-chelated copper(II) units from a given chain exhibit the same helicity, adjacent chains have opposite helicities and then an achiral structure results. Variable-temperature magnetic susceptibility measurements of 1 show the occurrence of a weak ferromagnetic interaction through the oxalate bridge [J = +1.14(1) cm⁻¹, the Hamiltonian being defined as H = –J ∑_nmS_i · S_j]. This value is analyzed and discussed in the light of available magneto-structural data for oxalate-bridged copper(II) complexes with the same out-of-plane exchange pathway.     

Flow-induced noise of a wall-mounted finite airfoil at low-to-moderate Reynolds number

This paper presents an experimental investigation of the flow-induced noise created by a wall-mounted finite airfoil at low-to-moderate Reynolds number and zero angle of attack. Far-field noise measurements have been taken at a single observer location and with two perpendicular microphone arrays in an anechoic wind tunnel at Reynolds numbers of _Rec=9.2×10⁴–1.6×10⁵${\mathit{Re}}_c=9.2\times {10}^4–1.6\times {10}^5$, based on chord, and for a variety of airfoil aspect ratios (length to chord ratio of L/C=0.2–2$L/C=0.2–2$, corresponding to length to thickness ratio of L/T=1.7–16.7$L/T=1.7–16.7$). Additionally, surface oil-film visualisation images and unsteady velocity measurements taken in the near trailing edge wake are related to far-field noise measurements to determine the flow mechanisms responsible for noise generation. The results show that the wall-mounted finite airfoil radiates noise similar to a two-dimensional airfoil when L/T>8.3$L/T>8.3$. Despite the incoming boundary layer height at the junction being 1.30≤δ/T≤1.46$1.30\le \delta /T\le 1.46$, junction and tip flow suppresses tonal noise production for airfoil?s up to L/T=8.3$L/T=8.3$ at _Rec=9.2×10⁴–1.2×10⁵${\mathit{Re}}_c=9.2\times {10}^4–1.2\times {10}^5$. Trailing edge noise is found to be the dominant airfoil noise generation mechanism at frequencies above 1 kHz with the position of the noise source along the trailing edge determined by the proportion of the airfoil span influenced by flow at the airfoil–wall junction.     

Ethynyl and Propynylpyrene Inhibitors of Cytochrome P450

Abstract  

The single-crystal X-ray structures and in vivo activities of three aryl acetylenic inhibitors of cytochromes P450 1A1, 1A2, 2A6, and 2B1 have been determined and are reported herein. These are 1-ethynylpyrene, 1-propynylpyrene, and 4-propynylpyrene. To investigate electronic influences on the mechanism of enzyme inhibition, the experimental electron density distribution of 1-ethynylpyrene has been determined using low-temperature X-ray diffraction measurements, and the resulting net atomic charges compared with various theoretical calculations. A total of 82,390 reflections were measured with Mo Kα radiation to a (sinθ/λ)_max = 0.985 Å⁻¹. Averaging symmetry equivalent reflections yielded 8,889 unique reflections. A least squares refinement procedure was used in which multipole parameters were added to describe the distortions of the atomic electron distributions from spherical symmetry. A map of the model electron density distribution of 1-ethynylpyrene was obtained. Net atomic charges calculated from refined monopole population parameters yielded charges that showed that the terminal acetylenic carbon atom (C18) is more negative than the internal carbon (C17). Net atomic charges calculated by ab initio, density functional theory, and semi-empirical methods are consistent with this trend suggesting that the terminal acetylenic carbon atom is more likely to be the site of oxidation. This is consistent with the inhibition mechanism pathway that results in the formation of a reactive ketene intermediate. This is also consistent with assay results that determined that 1-ethynylpyrene acts as a mechanism-based inhibitor of P450s 1A1 and 1A2 and as a reversible inhibitor of P450 2B1. Crystallographic data: 1-ethynylpyrene, C₁₈H₁₀, P2₁/c, a = 14.571(2) Å, b = 3.9094(5) Å, c = 20.242(3) Å, β = 105.042(2)°, V = 1,113.5(2) Å³; 1-propynylpyrene, C₁₉H₁₂, P2₁/n, a = 8.970(2) Å, b = 10.136(1) Å, c = 14.080(3) Å, β = 99.77(2)°, V = 1,261.5(4) Å³; 4-propynylpyrene, C₁₉H₁₂, Pbca, a = 9.904(1) Å, b = 13.174(2) Å, c = 19.401(1) Å, V = 2,531.4(5) Å³.