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991.
J.B Goodenough J.-S Zhou F Rivadulla E Winkler 《Journal of solid state chemistry》2003,175(1):116-123
Bond-length fluctuations in transition-metal oxoperovskites may give rise to two-phase fluctuations in what appears to be a single phase to a diffraction experiment. Orbital disorder at Jahn-Teller ions results in bond-length fluctuations that give 3D-ferromagnetic, vibronic Mn(III)-O-Mn(III) superexchange interactions and allow disproportionation into Mn(IV) and Mn(II) in LaMnO3; where orbitally ordered and disordered phases coexist, an external magnetic field stabilizes the orbitally disordered, ferromagnetic phase relative to the orbitally ordered, antiferromagnetic phase. Spin-lattice interactions in the paramagnetic phase of charge-transfer compounds give bond-length fluctuations arising from the semicovalent component of the superexchange interactions. At the crossover from localized to itinerant electronic behavior, the coexistence of two-phase fluctuations has been demonstrated in both the single-valent RNiO3 family (R=rare-earth, A=alkaline-earth) and the mixed-valent R0.5A0.5MnO3 perovskites. “Bad-metal” behavior is found to be associated with bond-length fluctuations. 相似文献
992.
Yuri N. Belokon’Devayani Bhave Daniela D'AddarioElizabetta Groaz Viktor MaleevMichael North Armine Pertrosyan 《Tetrahedron letters》2003,44(10):2045-2048
Copper(salen) complex 1 has been found to catalyse the asymmetric alkylation of enolates derived from a variety of amino acids. There is a clear relationship between the size of the side chain in the substrate and the enantioselectivity of the process, so that the enantioselectivity decreases in the order alanine>aminobutyric acid>allylglycine>leucine>phenylalanine>valine. A transition state model which accounts for the influence of the size of the side chain on the enantioselectivity of the reactions is presented. 相似文献
993.
A. M. Demchenko V. A. Yanchenko V. V. Kisly M. S. Lozinskii 《Chemistry of Heterocyclic Compounds》2005,41(5):668-672
We have developed a method for synthesis of aryl isothiocyanates by means of thiocarbamoylation of aromatic amines by tetramethylthiuram disulfide followed by degradation of the intermediate N(1)-aryl-N,N-dimethylthiourea by concentrated HCl. We have shown that thiocarbamoylation of 4-amino-5-ethyl-4H-1,2,4-triazole-3-thiol occurs at the 2 position of the triazole ring, while thiocarbamoylation of 4-amino-3-methyl-6-phenyl-4,5-dihydro-1,2,4-triazin-5-one leads to the dihetaryl-substituted thiourea. We consider the possibility of using N(1)-aryl-N,N-dimethylthioureas as analogs of isothiocyanates in reactions with N-nucleophiles.__________Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 5, pp. 775–780, May, 2005. 相似文献
994.
The present paper describes constructional details and evaluations of an at-column injector for capillary GC. Injections were made via a sample loop on a 0.32 mm i.d. capillary column. Two rotary valves were employed to allow a wash of the sample loop and a backflush of the transfer line. Repeatability, calculated from absolute area counts for n-alkanes was between 0.3–1% RSD, for injected sample volumes between 5 and 100 μl. Promising results were also obtained with syringe-based injections on narrow bore (100 μ i.d.) columns. Repeatability on the basis of normalized area counts was in the order of 0.1–0.2% RSD, while solvent tailing was practically absent. 相似文献
995.
Chemical modification of commercial high performance thin-layer chromatography plates with various mixtures of cyano-propyltrichlorosilane and octadecyltrichlorosilane is described. Surface coverage by different treatments is demonstrated as well as the variations in chromatographic performance. With regard to the development in aqueous media the utility of CN/ ODS plates compared to ODS plates is also shown. 相似文献
996.
K. Ranfft und R. Gerstl 《Fresenius' Journal of Analytical Chemistry》1972,276(1):51-54
Zusammenfassung Es wird eine Methode zur gas-chromatographischen Bestimmung von Glykokollbetain in Mischfuttermitteln beschrieben. Die Extraktion erfolgt mit Alkohol, anschließend wird die Lösung über einen Kationenaustauscher gereinigt. Das Betain wird mit N-O-Bis-(trimethylsilyl)-trifluoracetamid und Acetonitril verestert und gas-chromatographisch bestimmt. Für die beschriebene Methode errechnete sich bei einem Mittelwert von 2309 ppm und 7 Parallelen ein Variationskoeffizient von 1,79%.
Gas-chromatographic determination of glycocoll betaine in feeding-stuffs
The betaine is extracted with ethanol, purified by cation-exchange chromatography, esterified with N-O-bis-trimethylsilyl-trifluoracetamide and determined by gas chromatography. The coefficient of variation for the described method for 7 parallels and an average of 2309 ppm was 1.79%.相似文献
997.
As an alternative to acid pretreated UCON and FFAP capillaries for the analysis of wide-boiling free fatty acid mixtures, OV-1 : FFAP phase mixtures were used on high-temperature silylated inert glass capillary columns. The HETP-carrier gas velocity curves, peak asymmetry factors, coating efficiency, gas phase and stationary phase contributions to the mass transfer resistance were determined for various OV-1 : FFAP ratios. Mixed-phase capillaries showed optimum performance at a 2 : 1 OV-1 : FFAP ratio. The thermal and long-term stability of OV-1-stabilized FFAP columns surpassed those of the UCON and pure FFAP reference column used. 相似文献
998.
具有优良NLO性质的芪唑盐(记为S)已被用于制备LB薄膜,但其成膜性不好,稳定性差;S和花生酸镉(记为A)的混合系虽可改善成膜性,但在此混合膜系中,S相的稳定性仍然不佳。应用SAXS和微机模型拟合(MCMI)研究了上述两类LB薄膜的凝聚态结构,结果指出:在LB薄膜的二维类晶系结构中,S分子中呈哑铃形的芪唑基倾向于作倾斜状的密堆砌,S分子中的丙条脂肪链则倾向于采取全反式燕尾式构象,而且脂肪链只占S分子长的2/3,这就导致了S分子在二维类晶系结构中凝聚力的下降,以及造成LB薄膜层状超分子结构的破坏和崩塌。 相似文献
999.
Summary The international motions of a single cyclohexane molecule are studied by molecular dynamics calculations. Classical trajectories are calculated by integrating Newton's equation of motion. The potential functions used are essentially the same as in Allinger's MM2 program which is widely applied for calculations on conformational energies of organic molecules.Geometries and relative energies are reported for all stable low energy conformers and some transition states of cyclohexane. Vibrational frequencies of classical oscillations of individual bonds — computed for ethane as reference system — are close to the experimental values.Two trajectories of the molecular dynamics of cyclohexane were simulated. In the first we were able to follow the process of ring inversion: chair twisted forms inverted chair. The reaction path is analysed in detail and compared with static approaches. The second trajectory shows the correlated reorientation of the possible twisted forms alone. This process is known as pseudorotation.Dedicated to Prof. Dr. Karl Schlögl 相似文献
1000.
Summary A semi-continuous, counter-current chromatographic refiner (SCCR) was packed with an anion resin in the bisulphite form and used to separate mixtures of sugars from different feedstocks. Products with purities of more than 99% were achieved and solid concentrations of the fructose products of 12% w/v were possible. The deterioration of the anion resin was controlled by simple precautions and thus its useful life was substantially prolonged. 相似文献