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121.
First, we evaluated the complete electric dipole moment matrixeZ using a multi- AO basis on Cr, C, and O centers fortheimportant, parent organometallic molecule -C6H6Cr(CO)3. Second, we generated ground state LCAO-MO eigenvectors employing five commonly used semi-empirical procedures for molecules of this size which contain transition metals. Transformation of operator matrixeZ into the MO space of each of the five methods then leads us to conclude that the empirical input of Basch, Viste and Gray is most suitable. Finally, we compare the merits of several single- basis orbitals with the multi- metal orbitals.[/p] 相似文献
122.
Narayani Ramakrishnan Marian E. Clay Liang-YAN Xue Helen H. Evans Antonio Rodriguez-Antunez Nancy L. Oleinick 《Photochemistry and photobiology》1988,48(3):297-303
Abstract— Chloroaluminum phthalocyanine (CAPC) is an efficient photosensitizer for the inactivation of Chinese hamster V79 cells. In order to investigate possible molecular mechanisms in the photo-dynamic action of CAPC and visible light, the induction and repair rate of two classes of DNA lesions have been determined, i.e. DNA single-strand breaks and DNA-protein cross-links. In cells pretreated with 1 μ.M CAPC, a fluence of 12 kJ/m2 of red light (>600 nm) kills approximately 50% of the cells and induces 3 to 3.5 Gy-equivalents of single-strand breaks. The repair of these breaks was slower than the repair of single-strand breaks induced by -irradiation. The photodynamic action of CAPC also induces a large number of DNA-protein cross-links which, in contrast to -radiation-induced DNA-protein cross-links, do not appear to be repaired during 4 h of post-treatment incubation in fresh medium. These studies suggest that DNA may be an important target for the cytotoxicity of CAPC + red light. 相似文献
123.
Deacon GB Evans DJ Junk PC Lork E Mews R Zemva B 《Dalton transactions (Cambridge, England : 2003)》2005,(13):2237-2238
Addition of 15-crown-5 to [GdF(AsF6)2], both dissolved in liquid SO2, and crystallisation at -30 degrees C has led to the isolation of the tetranuclear ionic complex [Gd4F7(15-crown-5)4][AsF6]5.6 SO2 which is stable up to--10 degrees C where SO2 loss leads to loss of crystallinity. 相似文献
124.
Isotachophoretic zone formation of serum albumin in different free fluid electrophoresis instruments
The isotachophoretic behavior of a model protein, serum albumin, was examined (i) by computer simulation, (ii) by capillary isotachophoresis in HPE 100 and Tachophor 2127, (iii) by continuous flow isotachophoresis in Elphor VaP 22 and the BIO-STREAM Separator and (iv) by recycling isotachophoresis in an apparatus of our own design. Variations in monitored zone shapes can be explained by differences in engineering aspects and fluid stabilization principles of the instruments. 相似文献
125.
Treatment of meso-substituted metalloporphyrins [meso -substituent = OCOCF3, OCOCH3, OMe, CHO, CN, Cl; metal = Zn(II) or Cd(II)] with thallium(III) trifluoroacetate, followed by an acidic work-up, gives the corresponding β-substituted α-oxophlorins which were either characterised as such or else further derivatised. In all cases the major (or only) disubstitution product has the αβ orientation at the meso positions, indicating that the existing meso substituent directs the incoming one (trifluoroacetate) into the flanking, rather than opposite, meso position of the intermediate π-cation radical or π-dication. In contradistinction, meso substituted zinc(II) porphyrins which are able to lose protons (e.g. α-oxophlorins or α-aminoporphyrins) react with thallium(III) trifluoroacetate, and after a work-up with HCl the corresponding γ-chloro-α-oxophlorin or γ-chloro-α-aminoporphyrin is obtained. 相似文献
126.
The direct reaction of europium with 2-propanol and phenols has been investigated under a variety of conditions. The reaction of europium metal with 2,6-dimethylphenol and 2,6-diisopropylphenol in 2-propanol at reflux revealed that polymetallic europium complexes could be generated by this method. Hx[Eu8O6(OC6H3Me2-2,6)12(OiPr)8], 1, and H5[Eu5O5(OC6H3iPr2-2,6)6(NCCH3)8], 2, were isolated by recrystallization in the presence of hexanes and acetonitrile, respectively, and characterized by X-ray crystallography. Complex 1 has a cubic arrangement of europium ions with face-bridging mu 4-O donor atoms, edge-bridging mu-O(phenoxide/phenol) ligands, and terminal O(isopropoxide/2-propanol) ligands. Complex 2 is mixed valent and has a square pyramidal europium core with four Eu(II) ions at the basal positions and one Eu(III) ion at the apex. Since these reactions gave complicated mixtures of products from which 1 and 2 could only be obtained in low yields, direct reactions under less forcing reaction conditions were investigated. Europium reacts slowly at room temperature to form arene-soluble divalent [Eu(OiPr)2(THF)x]n, 3. Complex 3 reacts with 2,6-dimethylphenol to form the arene-insoluble complex (H[Eu(OC6H3Me2)2(OiPr)])n, 4. Recrystallization of 4 in the presence of THF results in the crystallographically characterizable divalent trimetallic complex [Eu(OC6H3Me2-2,6)2(THF)2]3, 5, which has an unusual linear metal geometry. In the presence of HOiPr at ambient conditions in the glovebox, crystals of 5 slowly convert to the mixed valent H10[Eu8O8(OC6H3Me2-2,6)10(OiPr)2(THF)6], 6, which was found to have a cubic arrangement of europium atoms similar to 1 by X-ray crystallography. Complex 4, upon heating under vacuum, followed by reaction with THF, forms the arene-soluble divalent complex H18([Eu9O8(OC6H3Me2-2,6)10(THF)7][Eu9O9(OC6H3Me2-2,6)10(THF)6]), 7, which contains two types of capped cubic arrangements of europium ions in the solid state. 相似文献
127.
Summary Inverse gas chromatography with sulphurated olefinic stationary phases and air as carrier gas has been found to yield characteristic
shifts of retention data. The resulting plots of retention index versus reaction time obtained for a range of squalene vulcanizates
have been found to be similar to those given by oxygen absorption measurements. Furthermore the chromatographic oxidation
curves have been found to be consistent with the known oxidation behaviour of the various sulphur networks formed on vulcanization.
This paper is dedicated to the memory of Dr.Graham Moore (1924–1968). 相似文献
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