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131.
Tomislav P. Živković 《Theoretical chemistry accounts》1988,73(2-3):207-219
A new method for the calculation of bond orders in alternant hydrocarbons is presented. The method requires a summation over the contributions of various superposition diagrams. Quantitatively, the method is almost as reliable as PPP, and due to its simplicity it can be used for fast and relatively accurate calculation of bond orders. In addition some simple rules are derived, which in many cases can be used to predict the signs of bond orders between nonbonded atoms.Dedicated to Professor J. Koutecký on the occasion of his 65th birthdayResearch supported by the Robert A. Welch Foundation of Houston, Texas 相似文献
132.
Summary
UV Densitometric Method for the Determination of Estrogens and Androgens in Pharmaceutical Preparations
A convenient method for the determination of estradiol benzoate/testosterone propionate and of ethynylestradiol/methyltestosterone mixtures from ampoules and lingualets, is described. The procedure is simple since the method involves direct reading from the thin-layer plate, avoiding thus the elution of the spot.After TL Chromatographie separation of active substances, densitometric measurements were performed with a HPTL scanner at 254 nm, whereby good and precise results were obtained. The standard deviation was found to range from 0.022 to 0.183, whereas the relative standard deviation ranged from 0.93 to 2.7%.The results obtained show that the method is applicable to routine analysis. 相似文献
133.
Metal-catalyzed di-tert-butylsilylene transfer was developed as a mild, operationally simple, functional-group-tolerant method for silacyclopropane formation. Di-tert-butylsilylene was transferred from cyclohexene silacyclopropane 1 to an alkene through the use of a metal salt. Silacyclopropanation occurred at temperatures as low as -27 degrees C when AgOTf or AgOC(O)CF(3) were used as catalysts. Complex silacyclopropanes were formed stereospecifically and diastereoselectively from functionalized alkenes. Silacyclopropanes reacted with various carbonyl compounds, including aldehydes, ketones, formate esters, and formamides, in an overall process that efficiently converts alkenes into oxasilacyclopentanes with defined stereochemistry. 相似文献
134.
Djordje Vlaović Gordana Ćetković Ivan Juranić Jelica Balaž Stevan Lajšić Dejan Djoković 《Monatshefte für Chemie / Chemical Monthly》1990,121(11):931-939
Summary The syntheses andin vitro antibacterial and antifungal evaluation of certain (5-nitro-2-furyl)azomethines with different heterocyclic nuclei are described.
Die Anwendung von Lävulinsäure und 5-Nitro-2-furylmethylendiacetat in der Totalsynthese einiger neuer biologisch aktiver (5-Nitro-2-furyl)azomethine
Zusammenfassung Es wird die Synthese und diein-vitro-antibakterielle und antifungale Wirksamkeit für bestimmte (5-Nitro-2-furyl)azomethine mit verschiedenen heterocyclischen Kernen beschrieben.相似文献
135.
P. Fantucci S. Polezzo V. Bonačić-Koutecký J. Koutecký 《Zeitschrift für Physik D Atoms, Molecules and Clusters》1989,13(4):355-361
The core-valence correlation potential has been derived for Na and K employing atomic calculations which make use of the density functional formula worked out by Lee, Yang and Parr based on Colle-Salvetti approach. The numerical potential is fitted with a small number of Gaussians leading to a very simple expression for an one-electron corevalence correlation operator? cv . The core-valence correlation corrections can be computed by applying? cv on a quite general class of wavefunctions. Applications of the? cv operator within the framework of valence-electron-only calculations using effective Hamiltonians are presented for Na and K atoms, for Na2, K2, NaK and their cations. Almost all the corrections calculated for the physical properties due to the core-valence correlation lead to results which are in good agreement with those obtained from much more sophisticated treatments and experimental data. 相似文献
136.
Dž. Belkić 《Zeitschrift für Physik A Hadrons and Nuclei》1984,317(2):131-138
We examine a general Dalitz integral containing the usual Feynman-type two-denominator term together with the Fourier transform \(\tilde \phi _{nlm} (q)\) of the hydrogenlike wave-function. A single closed formula is obtained for an arbitrary set {nlm} of quantum numbers, which is expressed in terms of the multivariable Lauricella hypergeometric functionF D . The result is useful in a variety of calculations within the second Born approximation. 相似文献
137.
Silica gel impregnated with poly(ethylene glycol) of different molecular mass (400, 1000, 1540, 4000, and 5500) was investigated for salting-out thin-layer chromatography of 15 mixed aminocarboxylato Co(III) complexes using eight ammonium sulphate solutions as mobile phases. Regularities established earlier for non-impregnated adsorbents are also valid in this work. Poly(ethylene glycol) of high molecular mass increases the hydrophobicity of the adsorbent. Positive linear dependence of RM values and of salting-out efficiency on average poly(ethylene glycol) molecular mass was usually observed. In contrast with non-impregnated silica gel, separation was achieved between complexes with the smallest hydrocarbon groups. 相似文献
138.
Alan P. Marchand Anna Hazlewood Zilin Huang Satish Kumar Vadlakonda John-David R. Rocha Trevor D. Power Kata Mlinarić-Majerski Lada Klaić Goran Kragol Jeffrey C. Bryan 《Structural chemistry》2003,14(3):279-288
Bis-cage-annulated 18-crown-6 and 20-crown-6 macrocyclic ethers (i.e., 1 and 2, respectively) have been synthesized, and their alkali metal picrate extraction profiles have been determined. Host system 1 proved to be a significantly more avid alkali metal cation complexant than 2 and somewhat more avid than 18-crown-6. Both 1 and 18-crown-6 display modest selectivity toward K+ and Rb+. A stable host–guest complex was prepared by slow evaporation of a CH2Cl2–hexane solution of an equimolar mixture of 2 and potassium picrate. The X-ray crystal structure of this complex reveals that picrate anion functions as a bidentate ligand therein. The gas-phase interaction energy between the 2 K+ complex and picrate anion was calculated to be ca. –64.9 kcal mol–1, thereby indicating that participation of picrate anion as an additional bidentate ligand results in significant stabilization of complex 10. 相似文献
139.
The absorption spectra of Co(II) chloride complexes, containing variable concentrations of chloride ligand, in a molten mixture of 80 mol% acetamide–20 mol% calcium nitrate tetrahydrate, were studied at 313, 333, 353, and 363 K, in the wavelength range 400-800 nm. The melt contains three possible ligands (CH3CONH2, H2O, and NO3
-) for competition with added chloride ligand. Addition of chloride caused a shift of the absorption maximum of octahedral cobalt(II) nitrate towards lower energies and pronounced changes in the shape of the initial spectrum of cobalt(II) nitrate. The effect of temperature changes on the molar absorption coefficient of the Co(II) species was dependent on the chloride concentration and was attributed to the structural changes occurring in the cobalt(II) species. The STAR and STAR FA programs were applied to identify the complex ionic species and to calculate the stability constants of Co(II) complexes formed in this solvent. The results indicate the highest probability of formation of the following complex species: Co(NO3)4
2-, Co(NO3)2Cl2
2-, and CoCl4
2-. Stability constants of each complex were presented for the equilibria occurring at 313, 333, 353, and 363 K. Distribution of the Co(II) species was also calculated over the ranges of chloride concentration and temperature investigated. 相似文献
140.
Quantitative investigation of the reaction of the ferri-heme model compound Fe(III)(TPPS)(H(2)O)(2) (1) to give Fe(II)(TPPS)(NO) (2) (TPPS = tetra(4-sulfonato-phenyl)porphinato) in buffered aqueous solution demonstrates a slow pH-independent reductive nitrosylation pathway in the pH range 4-6. The rate of this reaction is subject to modest general base catalysis. In the course of this study, a surprising catalytic pathway whereby nitrite ion (NO(2)(-)) strongly catalyzes the reduction of 1 to 2 under reductive nitrosylation conditions was demonstrated. 相似文献