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51.
Jennifer S. Forrester Jennifer S. Zobec Erich H. Kisi 《Journal of solid state chemistry》2004,177(10):3553-3559
The pressure-less sintering behavior of PbTiO3 powders synthesized by mechanical alloying TiO2 and PbO was investigated using dilatometry and Rietveld refinements of X-ray diffraction patterns. As-synthesized, the powders are nanocrystalline with a mean particle size of 20 nm. Pressure-less sintering in the range 500-1050°C gives single phase ceramics with densities of 85-90% and crystallite sizes in the range 80-400 nm. Cracking due to the paraelectric-ferroelectric phase transition was not observed in samples sintered below 700°C due to the small crystallite size whereas macroscopic cracks formed in samples sintered above 700°C. Rietveld analysis indicates the formation of Pb vacancies in samples sintered and held for 24 h at intermediate temperatures (600-1000°C) which gives some insight into the mechanism of Pb loss and second phase formation in this system. 相似文献
52.
Jäntti introduced a method to reduce the time required for the stepwise measurement of adsorption isotherms (Jäntti et al., Progress in Vacuum Microbalance Techniques, Vol. 1, Heyden, London, pp. 345–353, 1972). After a pressure change he measured the adsorbed mass three times and calculated its equilibrium value for the new pressure. In the present paper we discuss the applicability of this method in a broader scope (without starting from a single combination of gas and solid adsorbent) and also discuss the influence of measurement inaccuracies. It is shown that the method can serve as an early warning system, which decides whether an improvement of the adsorption model is necessary. 相似文献
53.
Rahul S. Pawar Erich Grundel Eugene Mazzola Kevin D. White Alexander J. Krynitsky Jeanne I. Rader 《Journal of separation science》2010,33(2):200-205
Enantioseparation of the pyrrolizidine alkaloid isomers intermedine and lycopsamine, isolated from Symphytum uplandicum, is discussed. The separatory power of two immobilized carbohydrate‐based chiral HPLC columns, Chiralpak IA and IC, in different chromatographic conditions is compared. The study demonstrated the importance of solvent and column selection while developing such chiral HPLC separation methods. The baseline HPLC separation of the two alkaloid isomers in preparatory scale is reported for the first time. The optimized separations were achieved on a Chiralpak IA column with mobile phases of ACN/methanol (80:20) and methanol/methyl‐t‐butyl ether (90:10), both containing 0.1% diethylamine. 相似文献
54.
The push-pull characters of a large series of donor-acceptor substituted azo dyes—71 structures in all—have been quantified by the NN double bond lengths, dNN, the 15N NMR chemical shift differences, Δδ15N, of the two nitrogen atoms and the quotient, π∗/π, of the occupations of the antibonding π∗, and bonding π orbitals of this partial NN double bond. The excellent correlation of the occupation quotients with the bond lengths strongly infers that both π∗/π and dNN are excellent parameters for quantifying charge alternation in the push-pull chromophore and the molecular hyperpolarizability, β0, of these compounds. By this approach, selected compounds can be appropriately considered as viable candidates for nonlinear optical (NLO) applications. 相似文献
55.
The through space NMR shieldings (TSNMRS) of dodecahedrane C20H20, of the isomeric hydrocarbons C20H12, of the ions C20H122+ and C20H122?, of the fluxional fullerene C20 and of its dication C202+ have been ab initio calculated employing the NICS concept on basis of MP2/6-31G1 geometries and visualized as iso-chemical-shielding/deshielding surfaces (ICSSs). TSNMRS values were employed to study the exohedral magnetic properties of the compounds studied. Hereby, the curved π-conjugation in the compounds studied could be quantified. 相似文献
56.
Erich Hellemann Dr. Rubens R. Teles Prof. Dr. Fernando Hallwass Prof. Dr. W. Barros Jr. Dr. Armando Navarro‐Vázquez Prof. Dr. Roberto R. Gil 《Chemistry (Weinheim an der Bergstrasse, Germany)》2016,22(46):16632-16635
Anisotropic NMR parameters, such as residual dipolar couplings (RDCs), residual chemical shift anisotropies (RCSAs) and residual quadrupolar couplings (RQCs or ΔνQ), appear in solution‐state NMR when the molecules under study are subjected to a degree of order. The tunable alignment by reversible compression/relaxation of gels (PMMA and p‐HEMA) is an easy, user‐friendly, and very affordable method to measure them. When using this method, a fraction of isotropic NMR signals is observed in the NMR spectra, even at a maximum degree of compression. To explain the origin of these isotropic signals we decided to investigate their physical location inside the NMR tube using deuterium 1D imaging and MRI micro‐imaging experiments. It was observed that after a certain degree of compression the gels start to buckle and they generate pockets of isotropic solvent, which are never eliminated. The amount of buckling depends on the amount of cross‐linker and the length of the gel. 相似文献
57.
Christian Erich Zybill Mahmoud Abdel-Hafiez Sami Allam Tharwat El Sherbini 《Progress in Solid State Chemistry》2007,35(2-4):469-480
Ferroelectric thin films form an equilibrium domain structure compatible with their respective crystallographic symmetry. In tetragonal (111) PZT, 90° domains prevail; in (pseudo-tetragonal) (100) SBT both 90° and 180° domains are present. The size of 90° domains has been measured for e.g., PZT as slabs of 15 nm width. Domain size is a result of stress minimization in the film during the paraelectric (PE) → ferroelectric (FE) transition. A precise and regular domain pattern for (111) PZT and (100) SBT films has been investigated in detail by TMSFM. Single domains can be addressed mechanically with the tip of an AFM. Such single domain switching corresponds to a data storage density of 200 Gbit/inch2. Applications of ferroelectric and high- paraelectric materials for e.g., non-volatile data storage replacing DRAM devices or as sensors in infrared cameras are increasingly becoming popular. 相似文献
58.
59.
Bagrat A. Shainyan Igor A. Ushakov Uwe Schilde Erich Kleinpeter 《Tetrahedron》2007,63(48):11828-11837
Multinuclear dynamic NMR spectroscopy of 3,5-bis(trifluoromethylsulfonyl)-1,3,5-oxadiazinane (3) revealed the existence of two conformers with differently oriented CF3 groups with respect to the ring, and two dynamic processes: ring inversion and restricted rotation about the N-S bond. Two transition states connecting the two conformers and corresponding to clockwise and counterclockwise rotations about the N-S bond were found; the calculated activation barriers of about 12 kcal/mol are in excellent agreement with those measured experimentally for the related molecule 1,3,5-tris(trifluoromethylsulfonyl)-1,3,5-triazinane (1). X-ray analysis proved the existence of the symmetric isomer of 3, which is the minor isomer in solutions but the only one in the crystal due to packing effects. The normal Perlin effect (JCHax<JCHeq) was observed for 2(6)-CH2 in 3, whereas the reversed Perlin effect was found for the 4-CH2 group in 3 as well as for all CH2 groups in 1 both experimentally and theoretically. The latter effect in compounds 1, 3, and 1-(methylsulfonyl)-3,5-bis(trifluoromethylsulfonyl)-1,3,5-triazinane (2) can be considered as a genuine reverse Perlin effect since larger values of 1JCH are observed for longer C-H bonds. 相似文献
60.
Zellner M Winkler W Hayden H Diestinger M Eliasen M Gesslbauer B Miller I Chang M Kungl A Roth E Oehler R 《Electrophoresis》2005,26(12):2481-2489
For the preparation of proteins for proteome analysis, precipitation is frequently used to concentrate proteins and to remove interfering compounds. Various methods for protein precipitation are applied, which rely on different chemical principles. This study compares the changes in the protein composition of human blood platelet extracts after precipitation with ethanol (EtOH) or trichloroacetic acid (TCA). Both methods yielded the same amount of proteins from the platelet preparations. However, the EtOH-precipitated samples had to be dialyzed because of the considerable salt content. To characterize single platelet proteins, samples were analyzed by two-dimensional fluorescence differential gel electrophoresis. More than 90% of all the spots were equally present in the EtOH- and TCA-precipitated samples. However, both precipitation methods showed a smaller correlation with nonprecipitated samples (EtOH 74.9%, TCA 79.2%). Several proteins were either reduced or relatively enriched in the precipitated samples. The proteins varied randomly in molecular weight and isoelectric point. This study shows that protein precipitation leads to specific changes in the protein composition of proteomics samples. This depends more on the specific structure of the protein than on the precipitating agent used in the experiment. 相似文献