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981.
The rate coefficients for the dehydrogenation of ethane, propane, and isobutane with cationic rhodium atoms Rh+ and clusters Rh+ n of up to 30 atoms were measured under single-collision conditions in a Fourier-transform ion cyclotron resonance mass spectrometer. The reaction rates are cluster size dependent and parallel for all the three alkanes. While the reactions proceed close to the theoretical collision rates for a large number of clusters, characteristic minima are observed for Rh+ (5/6/9/19/28). The degree of dehydrogenation varies with the cluster size with maxima for 10< or =n< or =15 for the three alkanes and for n=3 and 2-4 in the cases of ethane and propane, respectively. However, complete dehydrogenation is only observed for the reaction of Rh+ 11 with propane. Dehydrogenation is remarkably selective and no other neutral products than H2 are observed. The results are interpreted in terms of likely cluster geometries. 相似文献
982.
Nielsen CB Johnsen M Arnbjerg J Pittelkow M McIlroy SP Ogilby PR Jørgensen M 《The Journal of organic chemistry》2005,70(18):7065-7079
[reaction: see text] The synthesis and characterization of water-soluble singlet oxygen sensitizers with a phenylene-vinylene motif is presented. The principal motivation for this study was to better understand specific features of a water-soluble molecule that influence the photosensitized production of singlet oxygen upon nonlinear, two-photon excitation of that molecule. To achieve water solubility, sensitizers were synthesized with ionic as well as nonionic substituents. In the ionic approach, salts of N-methylated pyridine, benzothiazole, and 1-methyl-piperazine moieties were used, as were aryl-substituted sulfonic acid moieties. In the nonionic approach, aryl-substituted triethylene glycol moieties were used. Selected photophysical properties of the compounds synthesized were determined, including singlet oxygen quantum yields. Of the molecules examined, the most efficient singlet oxygen sensitizers had triethylene glycol units as the functional group that imparted water solubility. Molecules containing the ionic moieties did not make singlet oxygen in appreciable yield nor did they efficiently fluoresce. Rather, for these latter molecules, rapid charge-transfer-mediated non-radiative processes appear to dominate excited state deactivation. 相似文献
983.
Xiongyu Wu Xiaohong Liu Guangce Jiang Yongcheng Lin Willy Chan L. L. P. Vrijmoed 《Chemistry of Natural Compounds》2005,41(1):27-29
A novel metabolite 1, named xyloketal G, was isolated from cultures of marine derived mangrove fungus Xylaria sp. 2508. Its structure was elucidated by analysis of spectroscopic data.__________Published in Khimiya Prirodnykh Soedinenii, No. 1, pp. 22–23, January–February, 2005. 相似文献
984.
Rudnev AV Aleksenko SS Semenova O Hartinger CG Timerbaev AR Keppler BK 《Journal of separation science》2005,28(2):121-127
A CE method has been developed to evidence and quantitatively characterize the interaction between platinum-based antitumor drugs and human serum proteins. This method is a variant of affinity CE modified regarding both experimental setup and data treatment so as to measure the peaks (or vacancies) that correspond to the bound drug when it slowly binds to the protein. Using the formalism of the Hummel-Dreyer method and cisplatin and oxaliplatin as test compounds, a protocol for determining albumin and transferrin binding constants and stoichiometries, including (and distinguished by) 48 hours of incubation of the reaction mixture, was elaborated. Relative affinities of drugs toward different proteins in aqueous solution at physiological pH, chloride concentration, and temperature were compared in terms of overall binding constants and numbers of drug molecules attached to the protein. The results indicate that both platinum drugs bind to albumin more strongly than to transferrin, supporting the concept that the albumin fraction is a major drug supply route for chemotherapeutical needs. From a comparison with the binding parameters measured previously for cisplatin by other methods, conclusions were drawn about the validity of CE as a simple and convenient method for assaying protein-drug reactions with slow kinetics. 相似文献
985.
Marie-Noelle Avettand-Fènoël N. David G. Reumont J. -M. Fiorani M. Vilasi P. Perrot 《Journal of Thermal Analysis and Calorimetry》2007,90(2):329-332
The Fe-Sn-Zn system is of interest because Sn is one element added to the Zn galvanizing bath to overcome the drawbacks due
to the presence of Si in semi-killed steels. This work has been undertaken with the aim to understand the tin effect on the
microstructure and the layers growth in batch galvanized coatings on low alloyed steels.
Various experimental techniques such as metallography, scanning electron microscopy (SEM) coupled with X-ray energy dispersive
spectroscopy (EDX) are used in order to characterize the microstructure and the properties of such coatings elaborated in
a zinc bath enriched with tin.
Solidification phenomena and layers growth mechanisms during galvanization are explained by means of the ternary phase diagram
Fe-Sn-Zn at 450°C. The Calphad method allows to obtain this phase diagram from the three optimized binary phase diagrams Fe-Sn,
Fe-Zn and Sn-Zn and some experimental data inside the ternary Fe-Sn-Zn system. 相似文献
986.
987.
988.
A new combination of a flow/sequential injection method for the analysis of ammonia has been developed. Gaseous ammonia is selectively absorbed in a phosphoric acid coated glass tube and determined with Berthelot reagents by flow injection. The combination of the gas diffusion denuder sampler with flow injection makes this method very sensitive and selective. The limit of detection of 0.15 mug NH(3). 相似文献
989.
CE-MS has evolved into a strong alternative to LC-MS. Most of CE-MS applications deal with characterization and identification. However, quantitative aspects have gained importance in, e.g., pharmaceutical and biotechnological applications. Here we summarize and evaluate various methodological aspects in order to achieve sensitive and reproducible results. Similar to LC-MS, aspects of matrix influence on the electrospray process need to be carefully addressed when quantitative results are intended by CE-MS. Due to a more complicated coupling special emphasis needs to be put on the CE-MS interface. Generally linearity over more than three orders of magnitude can be achieved by CE-ESI-MS. Furthermore, a literature survey has been performed in order to give an overview over quantitative measurements performed by CE-MS. The precision can be doubled when changing from a structural related to an isotopically labeled internal standard. Thus a level of precision better than 5% RSD can be achieved. 相似文献
990.
Capillary reversed-phase high-performance liquid chromatography (RP-HPLC) utilizing monolithic poly(styrene-divinylbenzene) columns was optimized for the coupling to electrospray ionization mass spectrometry (ESI-MS) by the application of various temperatures and mobile phase additives during peptide and protein analysis. Peak widths at half height improved significantly upon increasing the temperature and ranged from 2.0 to 5.4 s for peptide and protein separations at 70 degrees. Selectivity of peptide elution was significantly modulated by temperature, whereas the effect on proteins was only minor. A comparison of 0.10% formic acid (FA), 0.050% trifluoroacetic acid (TFA), and 0.050% heptafluorobutyric acid (HFBA) as mobile phase additives revealed that highest chromatographic efficiency but poorest mass spectrometric detectabilities were achieved with HFBA. Clusters of HFBA, water, and acetonitrile were observed in the mass spectra at m/z values >500. Although the signal-to-noise ratios for the individual peptides diverged considerably both in the selected ion chromatograms and extracted mass spectra, the average mass spectrometric detectabilities varied only by a factor of less than 1.7 measured with the different additives. Limits of detection for peptides with 500 nl sample volumes injected onto a 60 mm x 0.20 mm monolithic column were in the 0.2-13 fmol range. In the analysis of hydrophobic membrane proteins, HFBA enabled highest separation selectivity at the cost of lower mass spectral quality. The use of 0.050% TFA as mobile phase additive turned out to be the best compromise between chromatographic and mass spectrometric performance in the analysis of peptides and proteins by RP-HPLC-ESI-MS using monolithic separation columns. 相似文献