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91.
As a step toward deeper insight on the "hydrogen bonding" in supercritical ethanol (scEtOH), we carried out NVT molecular dynamics simulations of the fluid over a wide range of temperatures and pressures. The fluid was studied at SC conditions for which thermodynamic and spectroscopic (NMR, infrared, Raman, dielectric) data are available. The various site-site pair distribution functions (pdf's) were calculated, and their temperature and pressure dependence was obtained. It was found that over the thermodynamic conditions investigated here, scEtOH remains highly structured. Moreover, the characteristic behavior of the first peaks in H-H, O-O, and H-O pdf's reveals that hydrogen bonds still exist in scEtOH. The analysis focuses also on the reorientational dynamics of the bond unit vectors O-H, C-O, and of the permanent dipole moment of the molecules as well as the total dipole moment of the sample. The corresponding Legendre time correlation functions were discussed in connection to the "hydrogen bonding" in the fluid and in the context of experimental results. Specifically, the behavior of the O-H dynamics exhibits the well-known associative nature of the molecules in the system. A further analysis of the hydrogen bonds was carried out, and the degree of aggregation (average number of H-bonds per molecule) was obtained and compared with results from NMR chemical shift studies. Also the estimated monomer and free O-H groups in the fluid were compared with results from IR and Raman vibrational spectroscopy. The percentage analysis fi of the liquid and scEtOH molecules, with i = 0, 1, 2, 3, ... hydrogen bonds per molecule, has been obtained. The results show the existence of small, linear-chain oligomers formed mainly by two molecules, whereas the number of the three body oligomers, and specifically that of four body oligomers in the sample, is relatively small. 相似文献
92.
Summary Carbon disulphide reacts with bis(-mercaptopropylamine)nickel(II) by insertion into the Ni-N bond to yield a planar dithiocarbamate complex, in which the Ni-S bond is broken and a sulphydryl group is formed. 相似文献
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First measurement of the left-right cross section asymmetry in Z boson production by e+e- collisions
Abe K Abt I Acton PD Adolphsen CE Agnew G Alber C Alzofon DF Antilogus P Arroyo C Ash WW Ashford V Astbury A Aston D Au Y Axen DA Bacchetta N Baird KG Baker W Baltay C Band HR Baranko G Bardon O Barrera F Battiston R Bazarko AO Bean A Beer G Belcinski RJ Bell RA Ben-David R Benvenuti AC Berger R Berridge SC Bethke S Biasini M Bienz T Bilei GM Bird F Bisello D Blaylock G Blumberg R Bogart JR Bolton T Bougerolle S Bower GR Boyce RF Brau JE Breidenbach M Browder TE Bugg WM Burgess B Burke D 《Physical review letters》1993,70(17):2515-2520
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Barrera C Herrera AP Bezares N Fachini E Olayo-Valles R Hinestroza JP Rinaldi C 《Journal of colloid and interface science》2012,377(1):40-50
The size, charge, and stability of colloidal suspensions of magnetic nanoparticles with narrow size distribution and grafted with poly(ethylene glycol)-silane of different molecular weights were studied in water, biological buffers, and cell culture media. X-ray photoelectron spectroscopy provided information on the chemical nature of the nanoparticle surface, indicating the particle surfaces consisted of a mixture of amine groups and grafted polymer. The results indicate that the exposure of the amine groups on the surface decreased as the molecular weight of the polymer increased. The hydrodynamic diameters correlated with PEG graft molecular weight and were in agreement with a distributed density model for the thickness of a polymer shell end-grafted to a particle core. This indicates that the particles obtained consist of single iron oxide cores coated with a polymer brush. Particle surface charge and hydrodynamic diameter were measured as a function of pH, ionic strength, and in biological buffers and cell culture media. DLVO theory was used to analyze the particle stability considering electrostatic, magnetic, steric, and van der Waals interactions. Experimental results and colloidal stability theory indicated that stability changes from electrostatically mediated for a graft molecular weight of 750 g/mol to sterically mediated at molecular weights of 1000 g/mol and above. These results indicate that a graft molecular weight above 1000 g/mol is needed to produce particles that are stable in a wide range of pH and ionic strength, and in cell culture media. 相似文献
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A. Barrera J.A. Montoya P. del Angel J. Navarrete M.E. Cano F. Tzompantzi A. López-Gaona 《Journal of Physics and Chemistry of Solids》2012,73(8):1017-1025
The surface properties of Pd and Pd–Pt catalysts supported on binary ZrO2–WOx and ternary ZrO2–Al2O3–WOx oxides prepared by the sol–gel method were studied. Special attention was paid to the study of the texture of the catalysts as well as the chemical state of tungstated zirconia and tungstated zirconia promoted with alumina in the palladium catalysts. The catalysts were tested in the isomerization of n-hexane and were characterized by N2 physisorption, XRD, TPR, Raman spectroscopy, XPS and FT-IR of adsorbed pyridine. The catalysts had bimodal pore size distributions with mesopores in the range 55–70 Å and macropores of 1000 Å in diameter. The catalysts had a surface WOx coverage (4.4–6.0 W nm?2) lower than that of the theoretical monolayer (7.0 W nm?2). A lower acidity of the ternary ZrO2–Al2O3–WOx oxide as compared to the binary ZrO2–WOx oxide was found. Higher activity in the isomerisation of n-hexane was obtained in the Pd–Pt catalysts supported on ternary ZrAlW oxides prepared by sol–gel that is correlated with the coexistence on the surface of W4+ (WO2) or W0 and W6+ (Al2(WO4)3) species, ZrO2 in the tetragonal phase and a high amount of ZrOx suboxides species in a low oxidation state (Zr3+ and Zr2+). 相似文献