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991.
I. V. Rogachevskii M. L. MacKey B. F. Shchegolev B. V. Krylov 《Russian Journal of General Chemistry》2002,72(3):472-479
The molecular geometries of a series of steroid hormones including cortisol, 9-fluorocortisol, 6-fluorocortisol, and 9-chlorocortisol were optimized by 3-21G and 6-31G* ab initio calculations. The results of calculations on both levels are well consistent with each other and with the experiment. The conformational changes and electron density redistribution occurring in going from cortisol to its 6- and 9-halo derivatives were discussed. A conclusion was made that the O and F atoms can participate in hydrogen bonding with the corresponding structural groups of glucocorticoid receptors. 相似文献
992.
Denifl S Ptasińska S Sonnweber B Scheier P Liu D Hagelberg F Mack J Scott LT Märk TD 《The Journal of chemical physics》2005,123(10):104308
Electron attachment to the polyaromatic hydrocarbons coronene and corannulene is studied in the electron energy range of about 0-14 eV using a high-resolution crossed electron-neutral beam setup. The major anions observed are the parent anions peaking at about 0 eV with cross sections of 3.8 x 10(-20) and 1 x 10(-19) m(2), respectively. The only fragment anions formed in coronene and corannulene are the dehydrogenated coronene and corannulene anions. Other anions observed in the negative mass spectra at about 0 eV can be ascribed to impurities of the sample. High-level quantum-mechanical studies are carried out for the determination of electron affinities, hydrogen binding energies, and structures of both molecules. The behavior of coronene and corannulene upon electron attachment is compared with that of other polyaromatic hydrocarbons studied previously. 相似文献
993.
Felderhof BU 《The Journal of chemical physics》2005,123(4):044902
It is shown on the basis of the linearized Navier-Stokes equations that a sphere set in motion by a sudden impulse, and slowing down in a viscous compressible fluid, can temporarily reverse its velocity at a late stage of the motion before finally slowing down with a positive velocity. For the effect to occur, the fluid needs to be sufficiently compressible, and the bulk viscosity needs to be sufficiently small relative to the shear viscosity. More generally, the velocity decays nonmonotonically, without necessarily passing through zero. The results are derived from the frequency-dependent friction coefficient, and hold for general boundary condition on the surface of the sphere. 相似文献
994.
Three syntheses of the hitherto unknown (±)-Δ6-3,4-cis-THC 4a and the first total synthesis of optically active Δ1- and Δ6-cis-THC's are described. These syntheses utilize a stereospecific intramolecular epoxide opening by phenolate anion; an acid catalyzed equilibration of Δ1- and Δ6-cis-THC acetates; and a kinetically controlled dehydration. The use of HPLC, GLC and NMR for the separation and identification of closely related THC's is discussed. 相似文献
995.
An emission spectrographic method is described for determination of 20 elements present as impurities in telluric acid. Samples are excited in a 12-A. d.c. arc with the use of NaCl-KCl as a spectrographic buffer and germanium as internal standard. The limit of determination lies between 10(-5) and 10(-2)%. The precision of the method calculated as relative standard deviation is 10-25%. 相似文献
996.
A. B. Sannigrahi 《International journal of quantum chemistry》1972,6(2):281-287
A simple semi-theoretical expression for β, the core resonance integral as used in the semi-empirical π-èlectron calculations has been proposed. β's for some standard C ? C and C ? 0 lengths have been evaluated with the proposed formula and the calculated values are compared with those obtained by other semi-theoretical and empirical methods. Electronic spectra of ethylene, formaldehyde, trans-butadiene and benzene have been calculated by a Pariser-Parr-like semi-empirical method with the values of β thus obtained. The calculated spectra are found to be in good agreement with the observed ones. 相似文献
997.
With an excess of dithizone over tellurium, the extraction of Te(IV) from 1 M perchloric acid solutions into a carbon tetrachloride solution (o) of dithixone follows the relation When the acidity is varied, again with a sufficiently large excess of dithissone, the following relation seems to be approached; (μ=1.0). 相似文献
998.
Bourosh P. N. Koropchanu E. B. Bologa O. A. Gdaniec M. Simonov Yu. A. Gerbeleu N. V. 《Russian Journal of Coordination Chemistry》2004,30(6):375-381
Anhydrous compound [Co(NioxH)2(Thio)2]2[SiF6] (I) was synthesized. Its structure was determined by X-ray diffraction analysis. The structures and character of intramolecular and intermolecular hydrogen bonds of complex Iand the previously studied [Co(NioxH)2(Thio)2]2[SiF6] · 3H2O complex were compared. 相似文献
999.
A new, highly sensitive, fast responding and stable potentiometric biosensor for creatinine determination is developed. The biosensor is based on an ammonium ion-selective electrode. Creatinine deiminase (EC 3.5.4.21) is chemically immobilized on the surface of the polymeric ion-sensitive membrane in the form of monomolecular layer using a simple, one-step carbodiimide covalent attachment method. The resulting enzyme electrodes are useful for measurement under flow injection analysis (FIA) conditions. The biosensors exhibit excellent operational and storage stability. The enzyme electrodes retain over 70% of initial sensitivity after ten weeks of work under FIA conditions. The storage stability at 4 °C is longer than half a year without loss of sensitivity. Under optimized conditions near 30 samples per hour can be analyzed and the determination range (0.02-20.0 mmol l−1) fully covers creatinine concentrations important from clinical and biomedical point of view. The simple biosensor/FIA system has been successfully used for determination of creatinine in urine, serum and posthemodialysate samples. 相似文献
1000.
The oxidation of iron(II) with tert-butyl hydroperoxide was investigated in the absence of oxygen in water, methanol, and the dichloromethane—methanol solvent
mixture (φr = 2:1). The oxidation rate depends on solvent polarity; measured in the presence of SCN− at constant 0.8 mmol dm−3 HCl, the rate constant increases with the polarity decrease passing from water and methanol to the dichloromethane—methanol
solvent mixture. Further, in non-aqueous solutions at this acid concentration the rate constant was higher than the rate constant
in the presence of Cl− only. The oxidation rate measured in the [FeCl]2+ complex in dichloromethane—methanol was slow in acidic medium and increased by decreasing the acid concentration. Approaching
the physiological pH conditions the rate constant attained the value of an order of magnitude of 103 dm3 mol−1 s−1, while very little alteration of stoichiometry of the oxidation reaction was observed. The rate constant measured in the
presence of Cl− strongly depends on electrolyte concentration at concentrations less than 0.5 mmol dm−3 HCl, both in MeOH and the solvent mixture. Based on these results, a possible mechanism of the influence of solvent, acidity,
and ligand type on the rate constant is discussed. We assume that the oxidation proceeds by an inner-sphere mechanism considering
that the breakdown of the successor inner-sphere complex forming reactive alkoxyl radicals is probably the rate-limiting step.
Presented at the 20th International Conference on the Coordination and Bioinorganic Chemistry organized by the Slovak Chemical
Society, Slovak University of Technology, Comenius University, and the Slovak Academy of Sciences, Smolenice Castle, 5–10
June 2005. 相似文献