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911.
912.
The catalytic mechanism of molybdenum containing CO dehydrogenase has been studied using hybrid DFT methods with quite large chemical models. The recent high-resolution X-ray structure, showing the surprising presence of copper linked to molybdenum, was used as a starting point. A pathway was initially found with a low barrier for C-O bond formation and CO2 release. However, this pathway did not include the formation of any S-CO2 species, which had been suggested by experiments with an n-butylisocyanide inhibitor. When these SCO2 structures were studied they were found to lead to deep minima, making CO2 release much more difficult. A large effort was spent, including investigations of other spin states, varying the number of protons and electrons, adding water, etc., until a plausible pathway for S-C bond cleavage was found. In this pathway a water molecule is inserted in between molybdenum and the SCO2 group. Full catalytic cycles, including electron and proton transfers, are constructed both with and without S-C bond formation. When these pathways are extended to two full catalytic cycles it can be understood why the formation of the S-C bond actually makes catalysis faster, even though the individual step of CO2 release becomes much more difficult. These results agree well with experimental findings. 相似文献
913.
The semiconductor properties of the interface TiO2/electrolyte in high organized porous oxide structures were analyzed by means of impedance spectroscopy near the flat band
potential. The impedance and capacitance studies performed on the as-anodized and thermally treated samples (anatase) indicate
the presence of a duplex structure formed by (1) the oxide at the bottom of the pores and (2) the walls of pores with different
donor densities and surface state concentrations. 相似文献
914.
This study aims to clarify the effects of carbon activation type and physical form on the extent of adsorption capacity and
desorption capacity of a bi-solute mixture of phenol and 2-chlorophenol (2-CP). For this purpose, two different PACs; thermally
activated Norit SA4 and chemically activated Norit CA1, and their granular countertypes with similar physical characteristics,
thermally activated Norit PKDA and chemically activated Norit CAgran, were used. The thermally activated carbons were better
adsorbers for phenol and 2-CP compared with chemically activated carbons, but adsorption was more reversible in the latter
case. 2-CP was adsorbed preferentially by each type of activated carbon, but adsorption of phenol was strongly suppressed
in the presence of 2-CP. The simplified ideal adsorbed solution (SIAS) model underestimated the 2-CP loadings and overestimated
the phenol loadings. However, the improved and modified forms of the SIAS model could better predict the competitive adsorption.
The type of carbon activation was decisive in the application of these models. For each activated carbon type, phenol was
desorbed more readily in the bi-solute case, but desorption of 2-CP was less compared with single-solute. This was attributed
to higher energies of 2-CP adsorption. 相似文献
915.
S. N. Dmitrieva N. I. Sidorenko A. I. Vedernikov L. G. Kuz’mina J. A. K. Howard T. M. Buslaeva S. P. Gromov 《Russian Chemical Bulletin》2007,56(5):993-1002
The condensation reaction of 1,2-bis(2-haloethoxy)-4-nitrobenzenes with acyclic α,ω-(oxa)alkanedithiols in the presence of
alkali metal carbonates produced a series of nitrobenzodithiacrown ethers with macrocycles of different size. The structures
of three ethers were established by X-ray diffraction. A new method was developed for the synthesis of nitrobenzomonothia-15-crown-5
ether. Nitro derivatives of benzodithiacrown ethers were tested as reagents for extraction of palladium(II), platinum(IV), and rhodium(III) from hydrochloric acid solutions. Extraction of PdII salts was found to be highly selective compared to that of PtIV and RhIII salts. Benzodithia-15-crown-5 ether is the most efficient extractant for palladium(II). Reduction of nitrobenzothiacrown ethers with hydrazine hydrate in the presence of a platinum catalyst afforded their amino
derivatives.
Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 5, pp. 958–966, May, 2007. 相似文献
916.
Uwe EilitzChristoph Böttcher Lothar HennigAlois Haas Cecile BoyerKlaus Burger 《Journal of fluorine chemistry》2002,115(2):149-154
Homochiral 2-C-perfluoroalkyl substituted d- and l-riboses were synthesized via Barbier, Grignard and Ruppert type reactions. The influence of the size of the perfluoroalkyl groups, attached to C-2, on the furanose/pyranose as well as on the α-furanose/β-furanose and α-pyranose/β-pyranose ratio in solution was studied. 相似文献
917.
A. S. Golubev N. D. Chkanikov M. Yu. Antipin Yu. T. Struchkov A. F. Kolomiets A. V. Fokin 《Russian Chemical Bulletin》1992,41(8):1425-1429
Condensation of methyl trifluoropyruvate with 2-(3,4-dimethoxyphenyl)ethylamine, tryptamine, and (D, L)-tryptophan yielded 1-methoxycarbonyl-1-trifluoromethyl-6,7-dimethoxy-1,2,3,4-tetrahydroisoquinoline, 1-methoxycarbonyl-1-trifluoromethyl-1,2,3,4-tetrahydro-9H-pyrido[3,4-b]indole, and Z-1-methoxycarbonyl-1-trifluoromethyl-3-carboxy-1,2,3,4-tetrahydro-9H-pyrido[3,4-b]indole, respectively. The Z configuration of the latter was determined by x-ray structural analysis.A. N. Nesmayanov Institute of Organoelemental Compounds, Russian Academy of Sciences, 117813 Moscow, Russia. Translated from Izvestiya Akademii Nauk, Seriya Khimicheskaya, No. 8, pp. 1831–1836, August, 1992. 相似文献
918.
The polarographic behaviour of salicylaldehyde-2-pyridylhydrazone (SAPH) has been studied in aqueous buffer solution containing 40% ethanol using DC and DP polarographic methods. In the pH range 1.8–7.5 the observed single irreversible reduction wave is assigned to the splitting of the N-N bond and reduction of C=N centre. In alkaline medium, a second wave appears at a more negative potential due to the reduction of the salicylaldehyde which is formed by hydrolytic decomposition of the SAPH molecule. The effect of pH on the limiting current andE
1/2 as well as the reduction mechanism are discussed and compared with similar compounds. The kinetic parameters of the electrode reaction have been calculated.The analytical properties of the copper(II)-SAPH system is described. The complex gave rise to a single irreversible well-defined wave (E
1/2=–0.58 V at pH=5.2). The reaction process is diffusion controlled. A method is suggested for the determination of Cu(II) in presence of different metal ions as the difference in theirE
1/2 values is sufficient for the purpose.This work is taken partly from the M. Sc. Thesis of Jamal S. Shalabi 相似文献
919.
U. K. Chakrabarti S. J. Pearton W. S. Hobson C. R. Abernathy 《Plasma Chemistry and Plasma Processing》1993,13(2):333-350
Vinyl iodide (C2H3I) microwave discharges with additions of H2 and Ar are found to provide faster etch rates than conventional CH4/H2/Ar discharges for InP, InGaAs, GaAs, and AlGaAs. This is a result of the relatively high volatilities of indium, gallium, and aluminum iodide species. The etched features are smooth and anisotropic over a wide range of do self-biases (–150 to –350 V), process pressures (1–20mTorr), and microwave powers (150–500 W). The polymer that forms on the mask during the plasma exposure can be readily removed in O2 discharges. Electron spectroscopy for chemical analysis (ESCA) showed that the etched surfaces are slightly deficient in the group V elements under most conditions, but changes to the optical properties of the semiconductors are minimal. No defects are visible by transmission electron microscopy (TEM) in GaAs or InP samples etched at dc biases –250 V. 相似文献
920.
The root of Carlina acanthifolia All. (Asteraceae) contained 1.0% of essential oil (expressed in g per 100 g of dried plant material). Using GC and GC/MS,
nine components were identified (100% of total oil). The structure of benzyl 2-furylacetylene (carlina oxide), which is the
principal component of the oil (91.5%), was spectrometrically identified.
__________
Published in Khimiya Prirodnykh Soedinenii, No. 4, pp. 331–332, July–August, 2005. 相似文献