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991.
E.B. Lobkovskii G.L. Soloveichik A.I. Sisov B.M. Bulychev A.I. Gusev N.I. Kirillova 《Journal of organometallic chemistry》1984,265(2):167-173
The structure of a titanium aluminium hydride complex of composition [(C5H5)2TiAlH4]2(CH3)2NC2H4N(CH3)2C6H6 has been determined by X-ray diffraction. The complex forms triclinic crystals with unit cell dimensions a = 8.406(2), b = 10.117(2), c = 11.269(3) Å; α = 112.01(2)°, β = 109.25(2)°, γ = 87.04(2)°, space group P, Z = 2 and density d = 1.21 g/cm3. The structure was refined to give a discrepancy index R = 0.056. The crystals are composed of centrosymmetric molecules of (Cp2TiAlH4)2TMEDA (Cp = η5-cyclopentadienyl) and molecules of crystal benzene. Two moieties of Cp2TiH2AlH2 are linked by a tetramethylethylenediamine molecule (rAlN 2.11 Å). The aluminium atom is bonded to a titanium atom by a double hydride bridge (rAlH b = 1.8, 1.6 Å, rTiH b = 1.6 Å), and has trigonal bipyramidal stereochemistry, [H4N] (rAlH t = 1.6 Å). 相似文献
992.
Isobaric vapor–liquid equilibrium data at 95.96 kPa for the three binary systems of 2,2,4-trimethylpentane with methyl tert-butyl ether, di-isopropyl ether and dimethoxymethane are determined. A Swietoslawski type ebulliometer is used for the measurements. The experimental T–x data are used to estimate Wilson parameters and the parameters, in turn, are used to calculate vapor phase compositions and activity coefficients. All the systems studied here do not exhibit azeotropes and behave like non-ideal solutions. 相似文献
993.
Selective laser-induced phototautomerism of free-base porphin in different n-alkanes (n-hexane, n-heptane, n-octane, nnonane, n-decane, n-undecane and n-dodecane) has been used to identify tautomer splittings in a number of sites in polycrystalline samples at 2 K. Pairs or lines arising from the two molecular orientations in each site can be reversibly transformed into each other. In the odd n-alkanes the occupation of different sites was not dependent on the rate at which the samples were frozen, but in the even n-alkanes metastable sites were only occupied following rapid quenching. 相似文献
994.
The polymer reference interaction site model (PRISM) integral equation theory was used to describe the structure and thermodynamic properties of atactic polystyrene (aPS) melt, in which the monomer of aPS is represented with an eight-site model to characterize its microstructure. The intramolecular structure factors needed in the PRISM calculations were obtained from single chain MD simulations. The calculated results indicate that the results by the integral equation method agrees well with experiments, and can reflect the fine microscopic structure of real aPS melt. This work shows that the PRISM theory is a powerful tool for investigating the structure and properties of complex polymers. 相似文献
995.
Ab initio calculations ofp-dichlorobenzene molecule were carried out using the Hartree-Fock method in the 6–31 G* valence-split basis set. The molecule was also calculated by the MNDO method in the valence sp-basis set for comparison. The populations of the valent p-orbitals of the C and CI atoms were analyzed. The optimized geometry of the molecule as well as its35Cl NQR frequency and the asymmetry parameter of the electric field gradient at the35CI nuclei calculated using the populations of the less diffuse components of the valent p-orbitals of the Cl atoms are in agreement with the corresponding experimental values for the -modification of 1,4-Cl2C6H4.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 9, pp. 2177–2179, September, 1996. 相似文献
996.
A. L. Chistyakov I. V. Stankevich N. P. Gambaryan I. A. Tikhonova V. B. Shur 《Russian Chemical Bulletin》1995,44(6):997-1004
Geometries and electronic structures of the complexes of halide anions with cyclic trimerico-phenylenemercury, (o-C6H4Hg)3, perfluoro-o-phenylenemercury, (o-C6F4Hg)3, vinylenemercury, (C2H2Hg)3, and perfluorovinylenemercury, (C2F2Hg)3, were modelled by the MNDO method. Calculations were performed for [L-X]– semisandwich complexes, [X-L-X]2– bipyramidal complexes, and [L-X-L]– sandwich complexes (where X=Hal,L is a mercury-containing macrocycle). Based on the results of calculations, we concluded that it was advantageous to describe the chemical bonding between halide anions and mercury-containing macrocycles in terms of generalized chemical bonds, which were successfully used for -complexes of transition metals. In the [L-X]– semisandwich complexes, the halide anion and the metallacycle are involved in the formation of three generalized chemical bonds: one headlight-shaped -bond and two two-lobe -bonds. In the [X-L-X]2– bipyramidal complexes, each halide anion forms three generalized chemical bonds with the macrocycle. It is possible because the macrocycleL has unoccupied molecular orbitals suitable for the formation of such bonds; these MOs consist mainly of the orbitals of mercury atoms directed toward both the upper and lower halogen atoms. In the [L-X-L]– sandwich complexes, the halide anion cannot be bonded to each ringvia three bonds, and, hence, an unsymmetrical structure is formed, in which the rings are located at different distances from the central atom: the [L-X]– semisandwich complex solvated by macrocycleL.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 6, pp. 1035–1042, June, 1995.The authors are grateful to V. I. Faustov for valuable remarks.This work was supported by the Russian Foundation for Basic Research (Project No. 93-03-18342). 相似文献
997.
Navzer D. Sachinvala Ruei F. Ju Morton H. Litt Walter P. Niemczura 《Journal of polymer science. Part A, Polymer chemistry》1995,33(1):15-29
A series of methyl methacrylate polymers have been prepared containing sucrose-based crosslinkers and additives. Thermogravimetry and long-term aging studies at 200°C show that sucrose-based alkyl and allyl ethers provide unprecedented thermal stability to linear, as well as crosslinked, poly (methyl methacrylate) or PMMA. Linear PMMA and PMMA crosslinked with trimethylolpropane trimethacrylate (TMPTMA) both degrade at 284°C. PMMA containing octa-O-crotylsucrose (1 mol %) degraded at 322°C. Depending on concentration, PMMA containing octa-O-allylsucrose (0.1-1.0 mol % and higher) degraded between 334 and 354°C, and PMMA containing 1′,6,6′-trimethacryloyl-2,3,3′,4,4′-penta-O-methylsucrose (0.1-1.0 mol %) degraded between 309 and 320°C. PMMA containing (1 mol % each) sucrose-based esters, ester-ether derivatives, all degraded at or below the degradation temperature of pure PMMA. Long-term air aging studies revealed that PMMA containing penta-O-methylsucrose trimethacrylate, octa-O-allylsucrose, and octa-O-crotylsucrose did not flow or sag after heating for 24 h at 200°C, but the polymers did show yellowing. While linear and crosslinked samples of PMMA containing compounds other than sucrose ethers lost more than 50% of their original weight within 15 h at 200°C, PMMA containing sucrose-based ethers lost about 8 and 20% of their original weight after 1 and 8.5 days, respectively. Herein we propose a unique mechanism by which saccharide ethers may be imparting this unprecedented thermal stabilization to PMMA. While tertiary hydrogens alpha to oxygens in saccharide ethers are stable to chain transfer during normal polymerization temperatures, they readily chain transfer at 200°C where PMMA is unstable. Chain transfer of these hydrogens is followed by fragmentation to produce alkyl, allyl or crotyl radicals, which combine with the macroradicals and terminate depropagation. © 1995 John Wiley & Sons, Inc. 相似文献
998.
多色蓝在核酸分子上的Langmuir聚集吸附 总被引:4,自引:0,他引:4
用微相吸附-光谱修正(MPASC)新技术研究核酸与多色蓝(PCB)探针分子间的相互作用,分析核酸分子内双静电膜的形成与Langmuir吸附的关联性.通过pH 7.24的介质核酸-PCB反应的光谱研究,测定了结合产物的物理化学参数:结合比1PCB:2DNA-PCB、1PCB:3RNA-PCB, 平衡常数KDNA-PCB=5.42×104, KRNA-PCB=2.82×104,摩尔吸收系数ε(DNA-PCB, 625 nm)=5.65×103(mo1-1•L )•cm-1, ε(RNA-PCB, 625 nm)=3.85×103 (mol-1•L)•cm-1.结果表明, RNA分子仅形成约60%双螺旋结构链,核酸双螺旋每一周期的负静电沟最大聚集10个PCB分子.该吸附反应用于核酸样品测定,结果良好. 相似文献
999.
微量元素锌与反复呼吸道感染的相关性 总被引:2,自引:1,他引:2
陈洁 《广东微量元素科学》1996,3(1):22-23
对28例反复呼吸道感染患儿(下称复感儿)及26例健康儿进行微量元素发锌测定。发现前者发锌平均值为(92.3±14.7)×10~(-6),后者为(132.5±21.5)×10~(-6),P<0.01,差异非常显著。对复感儿进行口服锌治疗,观察其疗效及治疗前后发锌变化。治疗前发锌平均值为(92.3±14.7)×10~(-6),治疗后为(137.5±20.2)×10~(-6),P<0.01差异非常显著。有效率达85.7%。故缺锌可能是复感儿患病的影响因素之一,锌治疗小儿反复呼吸道感染是十分必要的。 相似文献
1000.
Brian J. Brisdon 《Journal of organometallic chemistry》1977,125(2):225-230
Compounds of the type [XM(CO)2(ν-allyl)L2] (where X = Cl and Br; M = Mo and W; L2 = Ph2PCH2PPh2 and Ph2 PCH2CH2PPh2) have been prepard from the corersponding MeCN complexes. The spectral properties of these compounds and the effects of chelate rign size on 31P coordination shifts and J(183W—31P) have been investigated. 相似文献