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951.
Frank C. De Lucia Jr. Jennifer L. Gottfried Chase A. Munson Andrzej W. Miziolek 《Spectrochimica Acta Part B: Atomic Spectroscopy》2007,62(12):1399-1404
Detecting trace explosive residues at standoff distances in real-time is a difficult problem. One method ideally suited for real-time standoff detection is laser-induced breakdown spectroscopy (LIBS). However, atmospheric oxygen and nitrogen contributes to the LIBS signal from the oxygen- and nitrogen-containing explosive compounds, complicating the discrimination of explosives from other organic materials. While bathing the sample in an inert gas will remove atmospheric oxygen and nitrogen interference, it cannot practically be applied for standoff LIBS. Alternatively, we have investigated the potential of double pulse LIBS to improve the discrimination of explosives by diminishing the contribution of atmospheric oxygen and nitrogen to the LIBS signal. These initial studies compare the close-contact (< 1 m) LIBS spectra of explosives using single pulse LIBS in argon with double pulse LIBS in atmosphere. We have demonstrated improved discrimination of an explosive and an organic interferent using double pulse LIBS to reduce the air entrained in the analytical plasma. 相似文献
952.
P. Bracco 《Polymer Degradation and Stability》2007,92(12):2155-2162
Ultra-high molecular weight polyethylene (UHMWPE) has been the material of choice for load-bearing articular components used in total joint arthroplasty in the past 30 years. However, the durability of the whole implant has often been compromised by oxidation of UHMWPE components. Since the use of a suitable, biocompatible stabilizer would minimize this inconvenience, the possibility of adding synthetic Vitamin E to medical grade UHMWPE is currently under investigation.In the present work, medical grade UHMWPE was blended with 0.05, 0.1 or 0.5 w/w% of α-tocopherol and consolidated by compression moulding. Small blocks of reference UHMWPE and of each blend were then gamma irradiated to 30 or 100 kGy. FTIR spectroscopy was used to monitor changes in both the polymer and the additive. Thin sections of virgin and α-tocopherol doped UHMWPE irradiated and unirradiated were aged in a ventilated oven at 90 °C and the kinetic of oxidation was followed by FTIR. In addition, CL-imaging curves were recorded at 180 °C on both irradiated and unirradiated samples.Phenol loss is observed in all the α-tocopherol doped samples upon irradiation. Hypotheses on the rearrangements of the additive structure include the formation of quinonoid products. Nevertheless, all the additive-containing samples exhibit better oxidation resistance compared to the virgin material, indicating stabilizing activity of the α-tocopherol derivatives. 相似文献
953.
Abohachem Laguecir Serge Ulrich Jérôme Labille Nicolas Fatin-Rouge Serge Stoll Jacques Buffle 《European Polymer Journal》2006,42(5):1135-1144
Monte Carlo simulations, experimental titrations and fluorescence correlation spectroscopy experiments were used to investigate the conformational and electrical properties of polyacrylic acids (PAA). On the one hand, titration curves were calculated to get an insight into the role of pH on the degree of ionization and conformation of PAA chains. On the other hand, experimental potentiometric titrations of PAA were also achieved for different PAA molecular weights and compared to the calculated titration curves obtained by Monte Carlo coarse grained simulations. It was found that for a large range at intermediate PAA ionizations, a good correlation is obtained between experimental and simulations data thanks to the prominence of electrostatic interactions in this domain. The effect of ionic concentration and PAA molecular weight on the titration curves was also investigated. In order to get a better understanding of PAA conformational behavior, we also investigated PAA diffusion properties in aqueous solutions as a function of pH and ionic strength by fluorescence correlation spectroscopy (FCS), thanks to its high sensitivity to measure diffusion coefficients of tracer solutes. Good qualitative agreements were observed between experimental diffusivities and polymer properties calculated from MC simulations. It was shown that the high molecular weight PAA chains display more significant changes in diffusivity in agreement with the ionization degrees and conformational changes observed in the simulations. 相似文献
954.
G.K. Liu 《Journal of solid state chemistry》2005,178(2):489-498
Systematic behaviors of free-ion and crystal-field interactions are elucidated as a function of N, the number of f electrons in a lanthanide or actinide ion. Experimentally determined values of the free-ion interaction parameters are compared with those calculated based on Hartree-Fock theory. Comparison is also made between the lanthanide series in 4fN configurations and the actinide series in 5fN configurations. Variation in intra-ionic electrostatic interaction, spin-orbit coupling, and ion-ligand interaction is analyzed in comparison between the iso-f-electron lanthanide and actinide ions. Based on an exchange-charge model of crystal-field theory, crystal-field parameters of the f-element ions in various crystals are summarized in terms of point charge contribution and covalence effect. A systematic correlation is found between the free-ion parameters and the crystal-field strength. Increase of the crystal-field interaction results in a reduction in the free-ion parameters. 相似文献
955.
《Journal of Molecular Structure》2002,616(1-3):259-264
The molecular structure of the title complex [ZnBr2(C7H6N2)2] was investigated by X-ray diffraction and IR spectroscopy methods. Molecules of zinc(II) complex crystallize in the triclinic crystal system with cell constants a=7.526(2) Å, b=7.8971(8) Å, c=13.431(1) Å, Z=2 and V=791.3(2) Å3. In the molecular structure, the Zn atom is coordinated tetrahedrally by two Br− anions and two benzimidazole ligands. Intramolecular steric repulsions between Br− anions and benzimidazole groups have been caused to cis configuration around the central metal atom. 相似文献
956.
Mészáros Szécsényi K. Leovac V. M. Jaćimović Ž. K. Češljević V. I. Kovács A. Pokol G. 《Journal of Thermal Analysis and Calorimetry》2001,66(2):573-581
The synthesis of copper(II) chloride complexes with 3,5-dimethylpyrazole, 1-carboxamidine-3,5-dimethylpyrazole, 5-amino-4-carboxamide-1-phenylpyrazole
and 4-acetyl-3-amino-5-methylpyrazole is described. The compounds are characterized by elemental analysis, FT-IR spectroscopy,
thermal methods, magnetic moment and molar conductivity measurements. Thermal decomposition of the dichloro-(3,5-dimethylpyrazole)-copper(II)
complex results in an unstable intermediate with a stochiometric composition. The decomposition of the other compounds is
continuous.
This revised version was published online in August 2006 with corrections to the Cover Date. 相似文献
957.
Dyke JM Levita G Morris A Ogden JS Dias AA Algarra M Santos JP Costa ML Rodrigues P Andrade MM Barros MT 《Chemistry (Weinheim an der Bergstrasse, Germany)》2005,11(5):1665-1676
The thermal decompositions of methyl azidoformate (N3COOMe), ethyl azidoformate (N3COOEt) and 2-azido-N,N-dimethylacetamide (N3CH2CONMe2) have been studied by matrix isolation infrared spectroscopy and real-time ultraviolet photoelectron spectroscopy. N2 appears as an initial pyrolysis product in all systems, and the principal interest lies in the fate of the accompanying organic fragment. For methyl azidoformate, four accompanying products were observed: HNCO, H2CO, CH2NH and CO2, and these are believed to arise as a result of two competing decomposition routes of a four-membered cyclic intermediate. Ethyl azidoformate pyrolysis yields four corresponding products: HNCO, MeCHO, MeCHNH and CO2, together with the five-membered-ring compound 2-oxazolidone. In contrast, the initial pyrolysis of 2-azido-N,N-dimethyl acetamide, yields the novel imine intermediate Me2NCOCH=NH, which subsequently decomposes into dimethyl formamide (HCONMe2), CO, Me2NH and HCN. This intermediate was detected by matrix isolation IR spectroscopy, and its identity confirmed both by a molecular orbital calculation of its IR spectrum, and by the temperature dependence and distribution of products in the PES and IR studies. Mechanisms are proposed for the formation and decomposition of all the products observed in these three systems, based on the experimental evidence and the results of supporting molecular orbital calculations. 相似文献
958.
EPR, UV/Vis and FTIR spectroscopy as well as thermal analysis (TA/MS) were applied to study the influence of sulfate species present in the anatase support on the specific nature of VOx species in supported VOx/TiO2 catalysts. Those sulfate species modify the local structure of the supported vanadyl species and lead to the formation of two types of VO2+ sites instead of only one type being formed on sulfate‐free anatase. EPR and FTIR spectroscopic measurements revealed that a part of the VO2+ species are directly bound to the surface sulfate species. By TA/MS it was found that SO2 is released at lower temperature from VOx/TiO2 in comparison to the vanadium‐free support. The direct bonding between sulfate and VOx species stabilizes the latter on the surface of VOx/TiO2 resulting in three effects: 1) a higher V site dispersion in comparison to sulfate‐free TiO2, 2) a better resistance of surface vanadyls against diffusion into the bulk of the support and 3) a much faster reoxidation of reduced V sites than observed on sulfate‐free TiO2. 相似文献
959.
Maria Ochsenkühn-Petropulu Petros Tarantilis John Tsarouchis Klaus Ochsenkühn George Parissakis 《Mikrochimica acta》1998,129(3-4):233-238
Large area coatings (>10cm2) of the high temperature superconductor YBa2Cu3O7–x (x = 0.1 – 0.2) (YBCO) have been prepared by scale up an electrophoretic deposition technique using silver sheets and Si-wafers coated with Ag or Au as substrates. Several parameters, like the kind of the solvent, the applied voltage, the distance between the electrodes, the initial concentration of the suspension and the temperature during the electrophoresis were investigated in order to attain high deposition rates, as well as uniform YBCO coatings with the proper stoichiometry. To obtain a strongly adherent and dense coating a subsequent appropriate sintering and annealing procedure has been developed. The coatings obtained were characterized for their stoichiometry and superconducting properties by X-ray diffraction (XRD), Raman spectroscopy and magnetic measurements. The homogeneity and thickness of the films and the average grain size of the deposited particles have been investigated by optical and scanning electron microscopy (SEM). 相似文献
960.
Wenzel TJ Freeman BE Sek DC Zopf JJ Nakamura T Yongzhu J Hirose K Tobe Y 《Analytical and bioanalytical chemistry》2004,378(6):1536-1547
Chiral crown ethers 1 and 5 are useful enantiomeric discriminating agents in 1H NMR spectroscopy for neutral and protonated primary amines, amino acids, and amino alcohols. The presence of the carboxylic acid groups in 1 and 5 provide sites at which ytterbium(III) can bind. Adding ytterbium(III) nitrate to crown–substrate mixtures in methanol-d4 causes shifts in the spectra of substrates and often enhances the chiral discrimination in the 1H NMR spectrum. The enhancement in enantiomeric discrimination that occurs in the presence of ytterbium(III) allows lower concentrations of the crown ether to be used in chiral recognition studies. Several amide derivatives of 1 were prepared and evaluated as chiral NMR discriminating agents, although except for 1e, these were less effective than 1. 相似文献