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41.
E. A. Zheligovskaya 《Journal of Structural Chemistry》2003,44(5):827-835
A computer simulation of proton-ordered ice IX and its proton-disordered analog III (768 molecules, 90 K) was carried out by the molecular dynamics method using Poltev–Malenkov's potential. For ice IX, the differences in the dynamic characteristics of molecules with O(1) and O(2) are much wider than those in the case of ice III. The libration spectrum of ice IX has a number of distinct acute peaks, and the spectrum of ice III is strongly smoothed. These peculiarities are explained by the proton ordering of ice IX and disordering of ice III. The latter is responsible for the great differences in the short- and especially long-range environment of water molecules in ice crystals and hence for the presence of many molecules with different dynamic characteristics. Thus averaging over a large number of different vibrational spectra of molecules leads to a smoothed total spectrum in the case of the proton-disordered crystal modification of ice. 相似文献
42.
Savos'kin M. V. Yaroshenko A. P. Mysyk R. D. Vaiman G. E. Vovchenko L. L. Popov A. F. 《Theoretical and Experimental Chemistry》2004,40(2):92-97
New thermally stable intercalation compounds of graphite were obtained by the further intercalation of a series of organic compounds into graphite nitrate. The stabilization is explained by the formation of hydrogen bonds between the protonated form of the modifying substance and neutral surrounding molecules. 相似文献
43.
J.?R.?Tolchard J.?E.?H.?Sansom P.?R.?SlaterEmail author M.?S.?Islam 《Journal of Solid State Electrochemistry》2004,8(9):668-673
Recently, high oxide ion conduction has been observed in the apatite-type systems La9.33+x(Si/Ge)6O26+x/2, with conductivities approaching and even exceeding that of yttria-stabilized zirconia. The Ge-based phases have been reported to suffer from Ge loss and undergo irreversible structural changes on sintering at the high temperatures required to obtain dense pellets. In this paper we discuss doping studies (Ba, Bi for La) aimed at stabilizing the hexagonal apatite lattice to high temperature, and/or lowering the synthesis and sintering temperatures. The results show that doping with Ba helps to stabilize the hexagonal lattice at high temperatures, although Ge loss appears to still be a problem. Conductivity data show that, as previously reported for the Si-based systems, non-stoichiometry in the form of cation vacancies and/or oxygen excess is required to achieve high oxide ion conduction in these Ge-based systems. Neutron diffraction structural data for the fully stoichiometric phase La8Ba2Ge6O26 shows that the channel oxygen atoms show little anisotropy in their thermal displacement parameters, consistent with the low oxide ion conductivity of this phase. Bi doping is shown to lower the synthesis and sintering temperatures, although the presence of Bi means that these samples are not stable at high temperatures under reducing conditions.Presented at the OSSEP Workshop Ionic and Mixed Conductors: Methods and Processes, Aveiro, Portugal, April 10–12, 2003 相似文献
44.
45.
Margarita Valero Silvia M. B. Costa José R. Ascenso M. Mercedes Velázquez Licesio J. Rodríguez 《Journal of inclusion phenomena and macrocyclic chemistry》1999,35(4):663-677
The inclusion of the anti-inflammatory drug, Nabumetone, in -, - and hydroxypropyl--cyclodextrin (CDs) is studied using UV-VIS absorption and steady-state fluorescence emission. Binding constants and thermodynamic parameters of complex formation are determined by spectrofluorimetry. The inclusion phenomena of Nabumetone with the three cyclodextrins is compared with that of the well known similar anti-inflammatory drug Naproxen. In the case of Nabumetone pronounced differences are observed in the complexation process with each cyclodextrin whereas the respective Naproxen complexes are nearly identical. 1H-NMR experiments show that the inclusion process in Nabumetone can occur either through the substituents in the -2 (butanone) or -6 (methoxy) positions in the naphthalene ring. 相似文献
46.
Composite membranes were prepared by (a) infiltrating NAFION with SiO2-P2O5-ZrO2 sol, and (b) recasting a film using NAFION solution containing SiO2-P2O5-ZrO2 sol. The membranes were characterized by Differential Thermal Analysis and ac-impedance spectroscopy as a function of relative humidity. The influences of the heat treatment (80°C–150°C) and cleaning on the electrical properties were investigated. The incorporation of SiO2-P2O5-ZrO2 gels into NAFION lead to improvements in its thermal stability and proton conductivity. 相似文献
47.
Hiromi Matsuhashi Masakazu Oikawa Hiromi Shibata Michiko Tanaka 《Reaction Kinetics and Catalysis Letters》1998,65(2):253-258
Reversible formation of F+-centers was observed over platinum promoted sulfated zirconia in the presence and absence of hydrogen. The intensity of ESR
signal of F+-centers was increased by treatment in He stream and it was decreased rapidly by supply of hydrogen in gas phase. This behavior
seems to be related to proton spillover. 相似文献
48.
Laura León-Reina 《Journal of solid state chemistry》2007,180(4):1250-1258
La9.75□0.25(Ge6O24)O2.62 oxy-apatite shows a phase transition from triclinic to hexagonal symmetry at approximately 1020 K that has been characterised by high-temperature synchrotron X-ray and neutron powder diffraction, and ionic conductivity measurements. The crystal structure at 1073 K has been determined from joint Rietveld refinements of synchrotron X-ray and neutron powder diffraction data. The study shows that hexagonal-La9.75□0.25(Ge6O24)O2.62 contains interstitial oxygen at the position previously reported for other oxy-germanates. Changes in the oxide conductivity associated with this structural transition are discussed. The thermal analyses showed a weight loss on heating close to 600 K very likely due to water release. The synchrotron thermodiffractometric study shows an anomaly in the cell parameters evolution at that temperature, which indicates that this residual water is located into the apatite channels. The electrical characterisation under different atmospheres (dry and wet synthetic air) indicates that there is a significant proton contribution to the overall conductivity below 600 K, mainly under wet atmosphere. 相似文献
49.
Gostev F. E. Petrukhin A. N. Titov A. A. Shienok A. I. Marevtsev V. S. Sarkisov O. M. 《Russian Chemical Bulletin》2003,52(3):557-561
Intramolecular processes in electronic-excited states of 2,4,5-triarylimidazole molecules were studied by femtosecond laser spectroscopy. Experiments were carried out with two types of compounds, namely, those experiencing intramolecular proton transfer and two model compounds in which it is impossible. Schemes of the processes studied were proposed and the characteristic rate constants were determined. The excited-state intramolecular proton transfer (ESIPT) in the molecules with planar structure of the reaction center is a very fast process (100 fs). If the reaction center has a nonplanar structure and, hence, the intramolecular hydrogen bond is weakened, the ESIPT time is determined by the time of conformational rearrangement of the molecule. 相似文献
50.
The experimental values of the gas-phase proton affinities for a variety of 4-substituted benzonitriles, 4-substitutedN, N-dimethylanilines, and 4-substituted benzaldehydes have been examined by means of correlation analysis techniques and by ab initio quantum mechanical methods (MP2/ 6-31G(d) level). From this study it is concluded that in the gas phase, 4-(dimethylamino)-benzonitrile essentially protonates on the dimethylamino group, while protonated 4-cyanobenzaldehyde is very nearly a 21 mixture of the carbonyl- and cyano-protonated forms.This work is dedicatedin memoriam to Professor Robert W. Taft. 相似文献