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71.
采用理论计算方法解释了氨逐级解离能降低的现象。计算结果表明,随着N与H原子结合数目的减少,键解离能降低、键长增长;随着N与H原子结合数目的增多,N的2s电子跃迁到N的2p轨道上的几率增大,减小了屏蔽作用;更多电子从H的1s轨道迁移到N的2p轨道,增大了N和H之间的静电作用;单电子或孤对电子与N-H键夹角的增大减小了排斥作用。这3个因素造成NH3的逐级键解离能有降低的趋势。 相似文献
72.
Automated flow-based anion-exchange method for high-throughput isolation and real-time monitoring of RuBisCO in plant extracts 总被引:1,自引:0,他引:1
In this work, a miniaturized, completely enclosed multisyringe-flow system is proposed for high-throughput purification of RuBisCO from Triticum aestivum extracts. The automated method capitalizes on the uptake of the target protein at 4 °C onto Q-Sepharose Fast Flow strong anion-exchanger packed in a cylindrical microcolumn (105 × 4 mm) followed by a stepwise ionic-strength gradient elution (0-0.8 mol/L NaCl) to eliminate concomitant extract components and retrieve highly purified RuBisCO. The manifold is furnished downstream with a flow-through diode-array UV/vis spectrophotometer for real-time monitoring of the column effluent at the protein-specific wavelength of 280 nm to detect the elution of RuBisCO. Quantitation of RuBisCO and total soluble proteins in the eluate fractions were undertaken using polyacrylamide gel electrophoresis (PAGE) and the spectrophotometric Bradford assay, respectively. A comprehensive investigation of the effect of distinct concentration gradients on the isolation of RuBisCO and experimental conditions (namely, type of resin, column dimensions and mobile-phase flow rate) upon column capacity and analyte breakthrough was effected. The assembled set-up was aimed to critically ascertain the efficiency of preliminary batchwise pre-treatments of crude plant extracts (viz., polyethylenglycol (PEG) precipitation, ammonium sulphate precipitation and sucrose gradient centrifugation) in terms of RuBisCO purification and absolute recovery prior to automated anion-exchange column separation. Under the optimum physical and chemical conditions, the flow-through column system is able to admit crude plant extracts and gives rise to RuBisCO purification yields better than 75%, which might be increased up to 96 ± 9% with a prior PEG fractionation followed by sucrose gradient step. 相似文献
73.
74.
Sandra S. Pröckl 《Tetrahedron》2005,61(41):9855-9859
In situ generation of highly active palladium species by intermediate dissolution of Pd from solid supported catalysts has been demonstrated to be a very successful approach for the activation of aryl chlorides in Heck reactions. The new ‘heterogeneous’ Pd catalysts act as reservoir for molecular Pd species with unsaturated coordination sphere in solution. Crucial Pd leaching and re-deposition onto the support can be controlled by optimization of reaction conditions and by the properties of the catalysts. Pd is re-deposited onto the support at the end of the reaction. The catalysts, palladium supported on activated carbon, on various metal oxides or fluorides and Pd complexes in zeolites, are easy to prepare, though the preparation conditions are crucial. The catalysts convert all aryl bromides completely within minutes (TON 100,000). Aryl chlorides (even deactivated ones) are converted with high yields, within 2-6 h. The catalysts belong to the most active ones in Heck reactions at all (including best homogeneous systems) and fulfill all relevant requirements for practical applications in laboratory and industry. 相似文献
75.
A strong solutions approximation approach for mild solutions of stochastic functional differential equations with Markovian switching driven by Lévy martingales in Hilbert spaces is considered. The Razumikhin–Lyapunov type function methods and comparison principles are studied in pursuit of sufficient conditions for the moment exponential stability and almost sure exponential stability of equations in which we are interested. The results of [A.V. Svishchuk, Yu.I. Kazmerchuk, Stability of stochastic delay equations of Itô form with jumps and Markovian switchings, and their applications in finance, Theor. Probab. Math. Statist. 64 (2002) 167–178] are generalized and improved as a special case of our theory. 相似文献
76.
77.
We consider one-way classification model in experimental design when the errors have generalized secant hyperbolic distribution. We obtain efficient and robust estimators for block effects by using the modified maximum likelihood estimation (MML) methodology. A test statistic analogous to the normal-theory F statistic is defined to test block effects. We also define a test statistic for testing linear contrasts. It is shown that test statistics based on MML estimators are efficient and robust. The methodology readily extends to unbalanced designs. 相似文献
78.
Miroslav Hušek 《Topology and its Applications》2008,155(14):1493-1501
Three approaches to a direct construction of Urysohn universal space are compared, namely those of Urysohn, Hausdorff and Katětov. More details are devoted to the unpublished Hausdorff's approach that is shown to work in a more general situation, too. 相似文献
79.
Victor Pambuccian 《Journal of Geometry》2008,88(1-2):134-139
We prove that, in plane absolute geometry, the Erdős-Mordell inequality is equivalent to the statement that the sum of the
angles of a triangle is less than or equal to two right angles.
相似文献
80.
By introducing a time relaxation term for the time derivative of higher frequency components, we proposed a stabilized semi-implicit Galerkin scheme for evolutionary Navier-Stokes equations in this paper. Analysis shows that such a scheme has weaker stability conditions than that of a classical semi-implicit Galerkin scheme and, when a suitable relaxation parameter σ is chosen, it generates an approximate solution with the same accuracy as the classical one. That means the proposed scheme might use a larger time step to generate a bounded approximate solution. Thus it is more suitable for long time simulations. 相似文献