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81.
Reactions of organo(trichloromcthyl)silanes RMc2SiCCl3 (R = Me, Ph, Mc3Si) with aluminum chloride have been studied. The interaction of trimetltyl(tricltlorometltyl)silane with AlCl3 carried out in cyclohexane or in benzene leads to Me3SiCHCI2 (in 75 % yield) or ClMe2SiCPh2Me (in 70 % yield), respectively; whereas no conversions are observed inn-hexane and methylene chloride. Treatment of dimetltyl(phenyl)(ricltloromethyl)silane with aluminum chloride in an-C5H12/CH2CI2 mixture gives an aromatic cross-linked insoluble polymer. The reaction of pentamethyl(trichloromcthyl)disilane (R = Mc3Si) with AICl3 in pentane affords the rearrangement product, Me3SiCCl2SiMc2Cl, in 65 % yield. In methylene chloride the further cleavage of the disilane occurs to yield Me2SiCl2 and CH2=CHMe2SiCl.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 6, pp. 1511-1515, June, 1996. 相似文献
82.
Yoshihara T Druzhinin SI Zachariasse KA 《Journal of the American Chemical Society》2004,126(27):8535-8539
The planar rigidized molecule fluorazene (FPP) undergoes fast reversible intramolecular charge transfer (ICT) in the excited state, with a reaction time of 12 ps in the polar solvent ethyl cyanide at -45 degrees C. The ICT state of FPP has a dipole moment mu(e)(ICT) of 13 D, much larger than that of the locally excited state LE (1 D). The ICT behavior of FPP is similar to that of its flexible counterpart N-phenylpyrrole (PP), for which mu(e)(ICT) = 12 D. These results show that intramolecular charge transfer to a planar ICT state can occur efficiently. In designing ICT systems capable of rapid switching, it is therefore important to realize that large amplitude motions such as those necessary for the formation of a twisted intramolecular charge transfer (TICT) state are not required. 相似文献
83.
Sergey Y. Savinov Hwaung Lee Hyung Keun Song Byung-Ki Na 《Plasma Chemistry and Plasma Processing》2003,23(1):159-173
An experimental study of plasmachemical reaction involving CH4 and N2 molecules in rf discharge was studied in order to know the effect of vibrational excitation of N2 molecules. When the relative nitrogen concentration was greater than 0.8, the main product of CH4 decomposition was HCN, and the rate of methane decomposition at this condition was faster than that one in pure methane. These results could be confirmed through the mass spectroscopic method. The reason for these results is the vibrational energy of N2 excited by rf discharge. The chain reaction mechanisms of producing HCN by vibrational excitation of N2 were examined closely through numerical simulation. The rate-controlling step was the dissociation reaction of excited nitrogen molecule to the atomic nitrogen, so the process of HCN synthesis was limited by the value of reaction constant, kN. 相似文献
84.
Aleksandr A. Zirka Sergey I. Reshetnikov 《Reaction Kinetics and Catalysis Letters》2006,88(2):399-404
Summary Gas-phase hydrofluorination of perchloroethylene to pentafluoroethane in the presence of a chromium-magnesium catalyst at
0.4 MPa and 330-390°C has been studied. А reaction scheme taking into account the formation of by-products is suggested.
An erratum to this article is available at . 相似文献
85.
Yarovenko V. N. Semenov S. L. Zavarzin I. V. Ignatenko A. V. Krayushkin M. M. 《Russian Chemical Bulletin》2003,52(2):451-456
The influence of catalysts, acid chlorides, and solvents on the acylation of methyl 2-methyl-4H-thieno[3,2-b]pyrrole-5-carboxylate was studied. The use of AlCl3 allows the regioselective introduction of the acyl group into position 3 to be performed, whereas the acyl group is regioselectively introduced into position 6 of thienopyrrole when SnCl4 is used. 相似文献
86.
Buneva VN Kanyshkova TG Vlassov AV Semenov DV Khlimankov DYu Breusova LR Nevinsky GA 《Applied biochemistry and biotechnology》1998,75(1):63-76
Various catalytically active antibodies (Abs), or abzymes, have been detected recently in the sera of patients with autoimmune
pathologies, in whom their presence is probably associated with autoimmunization. Normal humans are generally not considered
to have abzymes, since no obvious immunizing factors are present. Here is shown by different methods that IgG from the milk
of normal females possesses both DNase and RNase activities. The activities were also present in the IgG F(ab′)2 and Fab fragments.
Affinity modification of IgG by the chemically reactive derivative of an oligonucleotide led to preferential modification
of the L chain of IgG. After separation of the subunits by sodium dodecyl sulfate electrophoresis in a gel containing DNA,
an in-gel assay showed DNase activity in the L chain. The L chain separated by affinity chromatography on DNA-cellulose was
catalytically active. These findings speak in favor of the generation of cat alytic Abs by the immune system of healthy mothers.
It is known that the treatment of adults with DNases and RNases offers protection from viral and bacterial diseases. Since
breast milk protects the infants from infec tions until the immune system is developed, this raises the possibility that catalytic
Abs like nucleases, may possess a protective role. 相似文献
87.
A. T. Baryshnikov V. I. Erashko N. I. Zubanova B. I. Ugrak S. A. Shevelev A. A. Fainzilberg V. V. Semenov 《Russian Chemical Bulletin》1992,41(9):1657-1664
The condensation of dinitromethane with glyoxal has been investigated and it has been demonstrated that 1,1,4,4-tetranitro-2,3-butandiol, -hydroxy-,-dinitropropionic acid or their mixture may be formed. Interaction of 1,1,4,4-tetranitro-2,3-butandiol or 1,4-dibromo-1,1,4,4-tetranitro-2,3-butanediol diacetates with sodium azide leads to bis(5-nitro-1,2,3-triazol-4-yl) via intermediate 1,1,4,4-tetranitro-1,3-butadiene.For communication 3, see [1].N. D. Zelinskii Institute of Organic Chemistry, Russian Academy of Sciences, 117913 Moscow. Translated from Izvestiya Akademii Nauk, Seriya Khimicheskaya, No. 9, pp. 2123–2131, September, 1992. 相似文献
88.
Donna C Arnold Olga Kazakova Guillaume Audoit Joseph M Tobin Jaideep S Kulkarni Sergey Nikitenko Michael A Morris Justin D Holmes 《Chemphyschem》2007,8(11):1694-1700
The synthesis of marokite CaMn(2)O(4) nanowires using a hydrothermal method is reported. Transmission electron microscopy and electron diffraction measurements show that the nanowires are polycrystalline in nature with diameters between 10 and 20 nm and lengths ranging from approximately 100 to 500 nm. Most interestingly, in contrast with the bulk material, magnetization measurements show that these nanowires exhibit ferromagnetic ordering with a Curie temperature (T(C)) of approximately 40 K. 相似文献
89.
Elena V. Piletska Maria Romero-Guerra Iva Chianella Kal Karim Anthony P.F. Turner Sergey A. Piletsky 《Analytica chimica acta》2005,542(1):111-117
The synthetic receptors for cocaine, deoxyephedrine, methadone and morphine were computationally designed and produced using molecular imprinting. The structure and energy of the molecular complexes were analysed by computational techniques. The possible structures of the binding sites in the synthetic receptors have been compared with those of corresponding natural receptors. The composition of imprinted polymers was optimised to allow adequate performance under the same experimental conditions. All selected molecular imprinting polymers (MIPs) demonstrated stronger affinity in comparison with corresponding blank polymers resulting in imprinted factors (I) equal to 1.2 (cocaine), 2.5 (deoxyephedrine), 3.5 (methadone) and 3 (morphine) which suggested that the specific binding site for each molecule was successfully created. The polymers studied possessed good selectivity and affinity towards their templates and could be recommended for the integration with sensor devices. From a practical point of view, especially for multisensor requirements, the synthetic receptors based on imprinted polymers could be superior to natural receptors due to their stability, robustness and compatibility with automation processes required for sensor fabrication. 相似文献
90.
G M Rodchenkov A N Vedenin V P Uralets V A Semenov 《Journal of chromatography. A》1991,565(1-2):45-51
Human urinary metabolites of the synthetic corticosteroids prednisone and prednisolone were detected in the course of gas chromatographic steroid profiling as methoxime-trimethylsilyl derivatives. Metabolites were provisionaly identified by combined gas chromatography-mass spectrometry. The major metabolites were 11-keto/11-hydroxy conversion products, 20-hydroxy and 4,5-dihydro analogues of the parent drugs. Cortisone, 6-hydroxy and fully saturated A-ring compounds were minor metabolites. Retention indices and mass spectral data are presented. 相似文献