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41.
Hubertus Appler Lutz W. Gross Bernd Mayer Wilhelm P. Neumann 《Journal of organometallic chemistry》1985,291(1):9-23
Factors governing the ease and mechanism of 7-silabicyclo[2.2.1]heptadienes thermolysis in order to generate free silylenes and the corresponding benzene derivatives are investigated. For this purpose, 29 new compounds of the types VII–X have been prepared. No indications for a polar mechanism or an intermediate biradical could be found. The degradation is exactly of first order in all cases investigated sofar, and is enhanced by phenyl groups at the bridgehead C atoms, if a conformation coplanar with the basic ring is allowed by the neighbouring substituents, but is not enhanced by phenyl groups at the Si. The X-ray structure of two typical derivatives is discussed with this respect. A special mechanism is operating in the easy thermolysis of carbomethoxy-substituted compounds leading to cyclic sila enolether intermediates. 相似文献
42.
Na2Mg(SO3)2 · 2H2O. A New Ternary Magnesium Sulfite. Crystal Structure, Thermoanalytical, I.R., and Raman Data Single crystals of the hitherto unknown Na2Mg(SO3)2 · 2 H2O have been obtained by crystallization from Mg(HSO3)2 solutions saturated with NaCl and with the technique of gel crystallization. The crystal structure of the triclinic Na2Mg(SO3)2 · 2 H2O (P1 , Z = 1, a = 752.4(1), b = 590.3(1), c = 517.8(1) pm, α = 106.25(1), β = 109.80(1), and γ = 101.49(1)°) has been determined using single crystal X-ray diffraction data. The Mg? O distances of the nearly regular MgO6 octahedra are between 206.6 and 210.5 pm. The MgO6 octahedra are connected by sulfite bridges forming chains in [001], which are held together by strong hydrogen bridges. The SO32? ions have nearly C3v symmetry. The results of thermoanalytical and I.R. and Raman spectroscopic measurements are reported and discussed. The O? D stretching modes of HDO molecules in partially deuterated samples show that the water molecules differ strongly from C2v symmetry. 相似文献
43.
Improving the catalytic activity of Candida antarctica lipase B by circular permutation 总被引:3,自引:0,他引:3
Lipases (EC 3.1.1.3) play an important role in asymmetric biocatalysis. Tailoring these enzymes to novel, unnatural substrates is one of the primary challenges of protein engineering. We have used circular permutation, the intramolecular relocation of a protein's N- and C-termini, to explore the effects of altered active site accessibility and protein backbone flexibility on the catalytic performance of lipase B from Candida antarctica (CALB). Our combinatorial approach identified 63 unique functional protein permutants of CALB, and kinetic analysis of selected candidates indicated that a majority of enzyme variants either retained or surpassed wild-type CALB activity on a series of standard substrates. Beyond the potential benefits of these tailor-made lipases as new catalysts for unnatural substrates, our study validates circular permutation as a promising general method for lipase engineering. 相似文献
44.
Novel Fast Ion Conductors of the Type M MIIICl6 (MI = Li, Na, Ag; MIII = In, Y) The ternary chlorides Li3InCl6, Na3InCl6, Ag3InCl6, and Li3YCl6 have been studied by difference scanning calorimetry, high-temperature X-ray, infrared, and high-temperature Raman methods. Impedance spectroscopic measurements exhibit fast ionic conductivity increasing in the sequence Na3InCl6 < Li3YCl6 < Ag3InCl6 < Li3InCl6. In the range of 300°C, Li3InCl6 is the best lithium ion conductor known so far (σ = 0,2 Ω?1 cm?1 at 300°C). With the exception of Na3InCl6, the chlorides exhibit complicated order-disorder phase transitions. 相似文献
45.
In applying non-destructive neutron-activation analysis for gold and uranium in spiked low-grade ore samples, the following extrapolated unspiked concentrations were measured: 0.278 ± 0.015 ppm gold (chemical assay: 0.202 ± 0.020 ppm gold); 25.1 ± 1.1 ppm uranium (chemical assay value: 19.5 ±2.0 ppm uranium). Different approaches to the fitting of results, and the influence of spiking non-uniformity, are discussed. 相似文献
46.
47.
Dynamical Behaviour of Linear Molecular Anions in the Hydrogensulfides of Sodium, Potassium and Rubidium: Differential Scanning Calorimetry, X-ray and Neutron Diffraction Hydrogensulfides of the alkali metals M ? Na, K, Rb were prepared in autoclaves by the reaction of the corresponding metals with H2S and D2S, respectively, in the temperature range from 50°C to 150°C. Differential scanning calorimetry, X-ray and neutron diffraction methods reveal that both, the HS?-and DS?-compounds occur in three crystalline modifications with HT ? high-, MT ? medium- and LT ? low-temperature form: The temperatures and enthalpies for the changes of modifications of the H- and D-compounds are given and the atomic arrangements revealed mainly by neutron diffraction data are discussed, in relation to, for example, size of cations. 相似文献
48.
49.
X-ray, I.R., and Raman Data of Strontium Polysulfides The strontium polysulfides SrS2, SrS3A, and SrS3B were studied in terms of preparation, thermal decomposition, and phase transition. The i.r. and Raman spectra of the strontium polysulfides as well as the normal coordinates of the phonon modes are presented and discussed in comparison with the respective barium compounds. From the spectra it is shown that S32? entities are present in SrS3A as in SrS3B. 相似文献
50.
Mulligan A Lane I Rousseau GB Hecht L Johnston SM Lennon D Kadodwala M 《Chemical communications (Cambridge, England)》2004,(21):2492-2493
Using a novel non-linear optical technique enantiomeric excess within a translationally disordered overlayer on a metal surface has been monitored for the first time. 相似文献