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51.
V. A. Mamedov A. A. Kalinin V. V. Yanilkin N. V. Nastapova V. I. Morozov A. A. Balandina A. T. Gubaidullin O. G. Isaikina A. V. Chernova Sh. K. Latypov I. A. Litvinov 《Russian Chemical Bulletin》2007,56(10):2060-2073
The oxidative dehydrocyclization of the 3-(indolizin-2′-yl)-2-oxoquinoxaline monopodand performed either electrochemically
or under the action of molecular iodine affords new redox-active heterocyclophane consisting of the redox-switchable biindolizine
fragment combined with the polyether-bridged π-deficient quinoxaline systems. The single-crystal X-ray diffraction study showed
that the trioxaundecane chain of heterocyclophane adopts an extended conformation, and one of the phenyl substituents of the
molecule closes the pseudocavity formed by the spacer from one of the sides. The cyclic voltammetric study of heterocyclophane
in MeCN and DMF showed the three-step oxidation of the indolizine fragments accompanied by the single-electron transfer in
each step. The first and third steps are reversible, and the second step is irreversible. The oxidation at potentials of the
first peak gives rise to stable radical cations detected by the ESR method (g = 2.0024, a
2N = 0.26 mT).
Dedicated to Professor E. A. Berdnikov on the occasion of his 70th birthday.
Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 10, pp. 1991–2003, October, 2007. 相似文献
52.
A differential microcalorimetric study of whey proteins and their behaviour in oil-in-water emulsions 总被引:1,自引:0,他引:1
Oil-in-water emulsions (20% soya oil, 1% protein) have been prepared containing lysozyme or isolates of -lactalbumin and β-lactoglobulin from whey protein. The structural characteristics of these proteins adsorbed at an oil/water interface were determined by following their thermal transitions using differential scanning microcalorimetry. Thermograms of the proteins in the adsorbed state differed markedly from the corresponding transitions seen for the proteins in solution. This suggests that the proteins underwent substantial changes in secondary and tertiary structure upon adsorption. In general, for all the proteins studied, a net decrease in the total energy absorbed during denaturation was found when the proteins were in an adsorbed state. Both lysozyme and -lactalbumin were in part “surface denatured”, and they showed a certain degree of reversibility between solution and the adsorbed state. β-Lactoglobulin showed the highest degree of denaturation upon adsorption and the conformational change was irreversible. 相似文献
53.
IR lattice vibration spectra were used to monitor the changes in the structure of zeolite Na-Y upon its dealumination with ethylenediaminetetraacetic acid (EDTA) or with HCl. The terminal Si-O(H,Na) bonds thus formed (which are detectable by characteristic absorbance at v 900–950 cm–1) are energetically less uniform when EDTA has been used as the dealuminating agent. This inhomogeneity is connected with the local deformations of zeolite structure which result in lowering the symmetry of silicon-oxygen tetrahedra. As a consequence, two novel bands appear at v 1090 cm–1 and 1200 cm–1 in addition to the fundamental absorption bands, vas (TO4) (T = Si, Al), at 1030 cm–1 and 1145 cm–1. A mechanism of dealumination is proposed, which takes into account the topochemical peculiarities involved in the chelation of the framework aluminum ions with EDTA.Translated fromIzyestiya Akademii Nauk. Seriya Khimicheskay, No. 2, pp. 284–287, February, 1993. 相似文献
54.
A computational study is made of the effect of basis set upon the energy, properties and inversion barrier of the phosphine molecule. The calculations are performed at both the SCF and CI level. The flexibility of the double zeta basis is discussed in the light of the results. 相似文献
55.
The structure and the relative stability of isomers of molecules X2H2F2 (X=Si, Ge, Sn) have been studied using the density functional theory (DFT). We have determined the optimised structures of the substituted isomers. The XX bond have been studied and compared to that of the parent molecules: X2H4. It appears that, for the planar and trans ethylenic systems, the double bond character of the XX decreases when the hydrogen atoms are substituted by fluorine atoms. The most stable structure is shown to be the one where the two fluorine atoms are fixed on the same atom. The bridged structures are also studied. 相似文献
56.
The reaction of imidazole with benzoyl chloride in pyridine affordedcis-1,2-bis(benzoyl-amino)ethylene (1) rather than 2-benzoylimidazole, as has been suggested previously. The structure of1 was confirmed by1H NMR spectroscopy and X-ray diffraction study.
Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 8, pp. 1593–1595, August, 1998. 相似文献
57.
In a comparative study the in vitro corrosion behavior of a selection of nickel- and cobalt-based alloys for application in
dentistry containing no noble metals was studied with slow scan cyclic voltammetry. The obtained breakthrough potentials,
the repassivation behavior and further typical features of the cyclic voltamograms are correlated with the chemical composition
as measured with electron beam microanalysis. Surface inhomogenities detected with the latter method are discussed with respect
to the electrochemical behavior. For all alloys stabilities in terms of breakthrough potential superior to previously reported
data for nickel-base alloys are found. 相似文献
58.
Pyrolysis study of fluorinated sol-gel silica 总被引:1,自引:0,他引:1
Fluorinated silica gels at various fluorine content were prepared via sol-gel by hydrolysis of 3,3,3-trifluoropropyltrimethoxysilane
and tetraethoxysilane mixtures. The gels, of nominal stoichiometry Si(CH2CH2CF3)XO(2-X/2)(X=0.1-1), were characterized by FT-IR, X-ray photoelectron spectroscopy (XPS) and N2 adsorption analysis. The thermal stability of the fluorinated samples was investigated by coupling thermogravimetric measurements
with mass spectrometric and gas chromatographic analyses of the evolved gaseous species. The chemical reactions occurring
in the gel matrices during heating were siloxane chain rearrangements involving condensation between residual hydroxyl and
ethoxyl groups in the 100-350°C temperature range, whereas the thermal decomposition of the fluoroalkyl groups were observed
at higher temperatures (450-600°C). The release of the fluoroalkyl moieties also involved C-F/Si-O bond exchanges inside the
siloxane chains, with gas-phase evolution of different fluorinated silicon units.
This revised version was published online in July 2006 with corrections to the Cover Date. 相似文献
59.
A. N. Bilyachenko A. A. Korlyukov M. M. Levitskii M. Yu. Antipin B. G. Zavin 《Russian Chemical Bulletin》2007,56(3):543-545
The first cage-like ferrophenyl siloxane containing FeIII ions in different coordination spheres (four iron ions have a trigonal-bipyramidal coordination and two iron ions have a
distorted octahedral coordination) was synthesized by the exchange reaction of sodium phenylsilanolate with FeIII chloride. An exotic lantern-like structure is formed with the involvement of two metal oxide fragments Fe—O—Fe. The structure
of this compound was established by X-ray diffraction.
Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 3, pp. 522–524, March, 2007. 相似文献
60.
Single nucleotide polymorphisms (SNPs) are currently being mapped and databased at a remarkable pace, providing a viable means for understanding disease susceptibility, differential drug response and human evolution. Consequently, there is an increasing demand for SNP genotyping technologies that are simple, rapid, cost effective and readily amenable to automation for high-throughput analyses. In this study, we improved the Survivor Assay, a SNP detection method based on electrospray ionization mass spectrometry (ESI-MS), with several developments. One improvement is the development of a one-well assay, requiring no off-line purification of the polymerase chain reaction product, achieved by simple addition of reagent solution into a single well. Another is the on-line separation of magnesium and dideoxynucleotides using an in-house made monolithic metal chelating column, eliminating any off-line sample preparation prior to mass spectrometric analysis. Here the Survivor Assay is extended from a proof-of-principle concept to a validated method by genotyping six SNPs from five different regions of human genomic DNA in 55 individual samples with 100% accuracy. This improved Survivor Assay eliminates the tedious and time-consuming steps of sample preparation, minimizes sample handing and offers a high-throughput analysis of SNPs by ESI-MS. The current combined preparation and analysis time is 2 min per sample. The simplicity of this method has potential for full automation and parallel chromatography and, thus, reduced analysis time. In addition, we have adapted the Survivor Assay for quantitative SNP analysis in pooled DNA samples. The capabilities and sensitivity of this approach were evaluated. We demonstrate that an allele occurring at a frequency of 2% can consistently be quantitated. 相似文献