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51.
Semi-empirical molecular orbital calculations were carried out for the compounds (C2H5)3As, (C2H5)3Ga and RAsH2 (R = C2H5, i-C3H7, i-C4H9, and t-C4H9) by using the CNDO/2-U program, and their capability of β-elimination reaction is compared on the basis of the torsion energy to the transition state, electrostatic interactions and orbital overlapping between the central atom and the β-hydrogen, and bond order of the metal-carbon, and carbon-hydrogen bond. In the comparison of (C2H5)3As with (C2H5)3Ga, we found that the β-elimination of (C2H5)3As could hardly be expected to take place in the thermal decomposition. The capability of β-elimination would be smaller in C2H5AsH2 than that in (C2H5)3As. Moreover when the ethyl group is replaced by a t-butyl group in RAsH2, the β-elimination reaction appears to become more difficult and a large possibility for a radical process is suggested. 相似文献
52.
The response to Hg(II) of a thin all-solid-state Te-doped silver chalcogenide membrane, described by the general formula Ag2 + δSe1 − xTex, which has been electrochemically prepared following a previously proposed approach, has been investigated. The kinetics of formation of the membrane's secondary dynamic response to Hg(II) has been successfully combined with the precise timing and transient signal, typical for flow-injection (FI) measurements, in developing a sensitive and reliable mercury FI detector. Under optimized stream conditions it exhibits a linear Nernstian response, with a double slope of the calibration graph of 59 mV dec−1, over the mercury(II) concentration range 10−6 − 10−3 M, the typical sample throughput amounting to about 70 samples per hour. The observed chemical amplification of the signal is due to the specificity of the processes dominating the initial step in formation of the steady-state signal of the membrane to mercury. The analytical performance of the Hg(II) FI detector, as regards sensitivity, reproducibility, selectivity and long-term stability has been thoroughly investigated. The exact procedure for membrane electrodeposition is given and the potential of the proposed approach as a cost-effective way for preparing chalcogenides of unique structure and properties has been outlined in the above context. 相似文献
53.
LI Zi-jian LIU Ning LIU Zhi-qiang LIU Shu-ying HAN Qi-de ZHANG You-yi . Institute of Vascular Medicine Peking University Third Hospital Key Laboratory of Molecular Cardiovascular Sciences Ministry of Education Beijing P. R. China . Changchun Institute of Applied Chemistry Chinese Academy of Sciences Changchun P. R. China 《高等学校化学研究》2006,22(3):319-323
Introduction Adrenoceptors(ARs),membersofthesuperfami lyofG proteincoupledreceptors,arethemostimpor tantreceptorsinvolvedincardiacregulation[1].ARsin cardiacmuscleincludebothαARsandβARssub types,whileinmostmammalianheart,βARsarethe predominantsubtypes.… 相似文献
54.
A. B. Vasil’eva A. A. Plotnikov 《Computational Mathematics and Mathematical Physics》2006,46(5):762-767
A singularly perturbed parabolic equation with a nonlinear right-hand side of a special form is examined. A numerical analytical study of such equations is performed. 相似文献
55.
Cobalt antidot arrays with different thicknesses are fabricated by rf magnetron sputtering onto porous alumina substrates. Scanning electron microscopy and grazing incidence x-ray diffraction are employed to characterize the morphology and crystal structure of the antidot array, respectively. The temperature dependence of magnetic properties shows that in the temperature range 5K--300K, coercivity and squareness increase firstly, reach their maximum values, then decrease. The anomalous temperature dependences of coercivity and squareness are discussed by considering the pinning effect of the antidot and the magnetocrystalline anisotropy. 相似文献
56.
Nanocomposites (NC) were formed using cationic poly(L ‐lysine) (PLL), a semicrystalline polypeptide, that was reinforced by sodium montmorillonite (MMT) clay via solution intercalation technique. By varying solution conditions such as pH, temperature, and polypeptide concentration in the presence of clay platelets, the secondary structure of PLL was controllably altered into α‐helical, β‐sheet, and random coil. The high molecular weight polypeptide shows a strong propensity to fold into the β‐sheet structure when cast as films, irrespective of the initial secondary structure in solution. Nanocomposite local morphology confirms intercalated MMT platelets with PLL over a wide range of compositions. © 2006 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 45: 239–252, 2007. 相似文献
57.
Adam Kiersnowski Jochen S. Gutmann Jacek Pigłowski 《Journal of Polymer Science.Polymer Physics》2007,45(17):2350-2367
ε‐caprolactone was polymerized in the presence of neat montmorillonite or organomontmorillonites to obtain a variety of poly(ε‐caprolactone) (PCL)‐based systems loaded with 10 wt % of the silicates. The materials were thoroughly investigated by different X‐ray scattering techniques to determine factors affecting structure of the systems. For one of the nanocomposites it was found that varying the temperature in the range corresponding to crystallization of PCL causes reversible changes in the interlayer distance of the organoclay. Extensive experimental and literature studies on this phenomenon provided clues indicating that this effect might be a result of two‐dimensional ordering of PCL chains inside the galleries of the silicate. Small angle X‐ray scattering and wide angle X‐ray scattering investigation of filaments oriented above melting point of PCL revealed that polymer lamellae were oriented perpendicularly to particles of unmodified silicate, while in PCL/organoclay systems they were found parallel to clay tactoids. Calorimetric and microscopic studies shown that clay particles are effective nucleating agents. In the nanocomposites, PCL crystallized 20‐fold faster than in the neat polymer. The crystallization rate in nanocomposites was also significantly higher than in microcomposite. Further research provided an insight how the presence of the filler affects crystalline fraction and spherulitic structure of the polymer matrix in the investigated systems. © 2007 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 45: 2350–2367, 2007 相似文献
58.
59.
The magnetocrystalline anisotropy of thin magnetic wires of iron and cobalt is quite different from the bulk phases. The spin moment of monatomic Fe wire may be as high as 3.4 μB, while the orbital moment as high as 0.5 μB. The magnetocrystalline anisotropy energy (MAE) was calculated for wires up to 0.6 nm in diameter starting from monatomic wire and adding consecutive shells for thicker wires. I observe that Fe wires exhibit the change sign with the stress applied along the wire. It means that easy axis may change from the direction along the wire to perpendicular to the wire. We find that ballistic conductance of the wire depends on the direction of the applied magnetic field, i.e. shows anisotropic ballistic magnetoresistance. This effect occurs due to the symmetry dependence of the splitting of degenerate bands in the applied field which changes the number of bands crossing the Fermi level. We find that the ballistic conductance changes with applied stress. Even for thicker wires the ballistic conductance changes by factor 2 on moderate tensile stain in our 5×4 model wire. Thus, the ballistic conductance of magnetic wires changes in the applied field due to the magnetostriction. This effect can be observed as large anisotropic BMR in the experiment. 相似文献
60.