Crystal and molecular structure of (−)-1,2-O-isopropylidene-3-O-methyl-7,8-dideoxy-β-l-glycero-d-gluco-non-7-enofuranurono-9,6-lactone,C13H18O7

The crystal structure of the title lactone, C₁₃H₁₈O₇, has been determined by single crystal diffraction methods. The compound crystallizes in the monoclinic space groupP2₁ witha=13.231(2),b=10.248(2),c=5.348(1) Å,=96.66(2)°, andZ=2. A total of 1055 reflection intensities were recorded on a Siemens AED single-crystal diffractometer (CuK radiation) at room temperature. The structure was solved by direct methods and electron density calculations. Full-matrix least-squares refinement gaveR=0.055 for 946 unique reflections above 2(I). The absolute configuration of the six chiral carbon atoms was deduced as 4S, 5R, 6R, 7S, 9R, 10R (crystallographic numbering corresponds to C-6, 5, 4, 3, 2, 1 in the title compound). An intermolecular O-HO hydrogen bond joins the molecules in chains which run along the twofold screw axis.     

Search for high energy γ-rays emission in28Si,32S+64Ni dissipative reactions at about 5 MeV/amu incident energy

Photons emitted in the²⁸ Si+⁶⁴ Ni and³² S+⁶⁴ Ni reactions at 143 MeV and 156 MeV incident energy respectively, have been detected in coincidence with the ejected charged fragments. An array of 48 BaF₂ -rays detector and 6 solid state silicon detector telescopes have been used. Photon energy spectra measured in the energy range from 2 to 20 MeV in coincidence with ejectiles coming from deep inelastic reactions, are consistent with statistical emission from the reaction products.Thanks are due to Dr.T.Noorman for the suggestions in the statistical calculations and to Mr.C.Marchetta for the preparation of high quality targets.     

Generalized Lyapunov exponents in high-dimensional chaotic dynamics and products of large random matrices

We study the behavior of the generalized Lyapunov exponents for chaotic symplectic dynamical systems and products of random matrices in the limit of large dimensionsD. For products of random matrices without any particular structure the generalized Lyapunov exponents become equal in this limit and the value of one of the generalized Lyapunov exponents is obtained by simple arguments. On the contrary, for random symplectic matrices with peculiar structures and for chaotic symplectic maps the generalized Lyapunov exponents remains different forD , indicating that high dimensionality cannot always destroy intermittency.     

Binding affinity studies of 1,2,3-triazole copper(II) complexes to human serum albumin

Abstract

Two copper(II) complexes with tetradentate 1,4-disubstituted-1,2,3-triazole ligands, [CuL(MeCN)](ClO₄)₂ (1) and [CuL′](ClO₄)₂ (2), have been prepared and characterized by different techniques, including X-ray structure determination, spectroscopic, and electrochemical measurements, as reported elsewhere. Herein, we report the interactions of these complexes, and corresponding free ligands, with human serum albumin (HSA) verifying their relative thermodynamic stability and differences in binding to this protein. Interactions with HSA were verified by CD measurements monitored at 564?nm, up to stoichiometric ratio 2:1 [Complex]:[protein], according to competitive equilibria involving the insertion of copper at the selective N-terminal metal binding site in HSA, and additionally at a secondary nonselective site. Further interactions of these complexes with L-tryptophan residues, and probable supplementary site(s) for the binding, were followed by fluorescence measurements. Analogous experiments with the free L and L′ indicated much weaker interactions. Protein oxidation damage was observed for both complexes, monitored by carbonyl groups formation in the presence of H₂O₂, probably with the participation of reactive oxygen species. Density functional theory calculations exhibit metal-ligand binding interaction energies similar to [Cu(HSA-N_terminal)]⁺, and reinforced the experimental results, showing clearly that such triazole ligands are competitive toward copper(II) in biological medium.     

A new reverse mode light shutter from silica-dispersed liquid crystals

Nanoparticle dispersions in liquid crystalline materials at low concentrations allow both investigating the formation of defects in liquid crystal (LC) and enhancing the light-scattering properties of LC optical devices. Reverse mode LC dispersions are LC devices, which look like transparent in their OFF state, when no electric field is applied, and opaque in their ON state. In this paper, a new reverse mode device, formed by a dispersion of a LC mixture in a silica nanoparticle crosslinked network, is presented. The morphology and the electro-optical properties of these silica nanoparticle/LC composites were investigated for two different LC mixtures with a negative dielectric anisotropy. The observed transmittances and relaxation times were found to depend strongly on the silica amount and chemical–physical properties of LC used in the sample preparation.     

程序升温汽化大体积进样气相色谱法同时测定空气中的甲醛及其他10种羰基污染物（英文）

Long-term indoor-air limit for formaldehyde stipulated by the European Commission is 1 μg/m3,while the World Health Organization has set a threshold of 100 μg/m3 that should not be exceeded for more than 30 min. To date,however,only a few analytical techniques have been developed that can be used to detect formaldehyde at these very restrictive limits. Thus,there is a need to develop for comprehensive methods for analyzing airborne formaldehyde and other carbonyl pollutants in the ambient environment. The aim of this study is to develop a highly sensitive online automated preconcentration gas chromatographic method using large-volume injection with a programmed temperature vaporization injector for the analysis of airborne formaldehyde and ten other carbonyl compounds. The influence of several parameters,such as the maximum volume injected,programmed temperature vaporization transfer time and temperature,carrier gas flow rate,and type of packing material was investigated. After optimization,highly satisfactory results in terms of the absolute and methodological detection limits were achieved,i. e. as low as the μg/m3 level for all the carbonyl pollutants studied. A commercially available sampler,originally designed for active sampling,was evaluated as a passive sampling device;this optimized technique was applied to monitor the concentrations of carbonyl pollutants in the indoor air of ten public buildings in Florence. The strength of this methodology lies both in the low detection limits reached in the simultaneous analysis of a wide group of 2,4-dinitrophenylhydrazine derivatives,and the potential adaptability of this method to other gas chromatographic applications to achieve lower sensitivity.     

The safety assessment of herbals with a new and ethical approach

The increasing use of plant medicines (herbals) in Europe needs a shared methodology to determine the toxicity and the daily exposure level to these drugs. For this reason, the European regulatory agencies have undertaken a study that could meet popular uses and toxicological research in different countries of the Union. Here we list some examples of the most used herbal drug classes and we propose a decision-making process based on their characteristics, their content in active principles and on the basis of the present scientific pharmacological and toxicological literature. The proposed decision tree actually makes easier for the assessor to quickly and accurately evaluate the accredited indexes for risk and toxicity assessment based on the preclinical literature data and using the correct classification that some of them may have because they are already present in medicinal products or used as food.     

Tandem Mass Spectrometry and Ion Mobility Reveals Structural Insight into Eicosanoid Product Ion Formation

Ion mobility measurements of product ions were used to characterize the collisional cross section (CCS) of various complex lipid [M-H]^? ions using traveling wave ion mobility mass spectrometry (TWIMS). TWIMS analysis of various product ions derived after collisional activation of mono- and dihydroxy arachidonate metabolites was found to be more complex than the analysis of intact molecular ions and provided some insight into molecular mechanisms involved in product ion formation. The CCS observed for the molecular ion [M-H]^? and certain product ions were consistent with a folded ion structure, the latter predicted by the proposed mechanisms of product ion formation. Unexpectedly, product ions from [M-H-H₂O-CO₂]^? and [M-H-H₂O]^? displayed complex ion mobility profiles suggesting multiple mechanisms of ion formation. The [M-H-H₂O]^? ion from LTB₄ was studied in more detail using both nitrogen and helium as the drift gas in the ion mobility cell. One population of [M-H-H₂O]^? product ions from LTB₄ was consistent with formation of covalent ring structures, while the ions displaying a higher CCS were consistent with a more open-chain structure. Using molecular dynamics and theoretical CCS calculations, energy minimized structures of those product ions with the open-chain structures were found to have a higher CCS than a folded molecular ion structure. The measurement of product ion mobility can be an additional and unique signature of eicosanoids measured by LC-MS/MS techniques.

Open image in new window

Graphical Abstract ?

     

Bimetallic Ag‐Pt Sub‐nanometer Supported Clusters as Highly Efficient and Robust Oxidation Catalysts

A combined experimental and theoretical investigation of Ag‐Pt sub‐nanometer clusters as heterogeneous catalysts in the CO→CO₂ reaction (COox) is presented. Ag₉Pt₂ and Ag₉Pt₃ clusters are size‐selected in the gas phase, deposited on an ultrathin amorphous alumina support, and tested as catalysts experimentally under realistic conditions and by first‐principles simulations at realistic coverage. In situ GISAXS/TPRx demonstrates that the clusters do not sinter or deactivate even after prolonged exposure to reactants at high temperature, and present comparable, extremely high COox catalytic efficiency. Such high activity and stability are ascribed to a synergic role of Ag and Pt in ultranano‐aggregates, in which Pt anchors the clusters to the support and binds and activates two CO molecules, while Ag binds and activates O₂, and Ag/Pt surface proximity disfavors poisoning by CO or oxidized species.     

Multivariate Normal Approximation on the Wiener Space: New Bounds in the Convex Distance

Journal of Theoretical Probability - We establish explicit bounds on the convex distance between the distribution of a vector of smooth functionals of a Gaussian field and that of a normal vector...