The mechanism of ethylene polymerization by nickel salicylaldiminato catalysts - Agostic interactions and their kinetic isotope effects

The ethylene polymerization reaction of a neutral nickel catalyst was studied by DFT calculations at the Becke3LYP/6-31G(d) level of theory. As in related cases a β-agostic bond stabilizes the nickel alkyl ground states. Transition states for the insertion of the olefin show a distinct α-agostic interaction, which has not been observed for late metal polymerization catalysts before. An ethylene-alkyl complex was identified as the resting state of the reaction. The overall barrier height of the reaction amounts to 17.54 kcal/mol, which slightly increases to 17.60 kcal/mol for the polymerization of deuterated ethylene. Therefore, a small positive kinetic isotope effect (k_H/k_D = 1.09) can be calculated, which is caused by the α-agostic interaction in the transition state. A comparison to other late metal based polymerization systems reveals that the ethylene coordination step of highly active catalysts is significantly lower in energy compared to catalysts which are only moderately active.     

Sensitivity analysis of thermal performances of flat plate solar air heaters

Sensitivity analysis is a mathematical tool, first developed for optimization methods, which aim is to characterize a system response through the variations of its output parameters following modifications imposed on the input parameters of the system. Such an analysis may quickly become laborious when the thermal model under consideration is complex or the number of input parameters is high. In this paper, we develop a mathematical model to analyse the heat exchanges in four different types of solar air collectors. When building this thermal model we show that for each collector, at quasi-steady state, the energy balance equations of the components of the collector cascade into a single first-order non-linear differential equation that is able to predict the thermal behaviour of the collector. Our heat transfer model clearly demonstrates the existence of an important dimensionless parameter, referred to as the thermal performance factor of the collector, that compares the useful thermal energy which can be extracted from the heater to the overall thermal losses of that collector for a given set of input parameters. A sensitivity analysis of our thermal model has been performed for the most significant input parameters such as the incident solar irradiation, the inlet fluid temperature, the air mass flow rate, the depth of the fluid channel, the number and nature of the transparent covers in order to measure the impact of each of these parameters on our model. An important result which can be drawn from this study is that the heat transfer model developed is robust enough to be used for thermal design studies of most known flat plate solar air heaters, but also of flat plate solar water collectors and linear solar concentrators.     

Existence of the uniformly minimum risk equivariant estimators of parameters in a class of normal linear models

In this paper, we study the existence of the uniformly minimum risk equivariant (UMRE) estimators of parameters in a class of normal linear models, which include the normal variance components model, the growth curve model, the extended growth curve model, and the seemingly unrelated regression equations model, and so on. The necessary and sufficient conditions are given for the existence of UMRE estimators of the estimable linear functions of regression coefficients, the covariance matrixV and (trV)^α, where α > 0 is known, in the models under an affine group of transformations for quadratic losses and matrix losses, respectively. Under the (extended) growth curve model and the seemingly unrelated regression equations model, the conclusions given in literature for estimating regression coefficients can be derived by applying the general results in this paper, and the sufficient conditions for non-existence of UMRE estimators ofV and tr(V) are expanded to be necessary and sufficient conditions. In addition, the necessary and sufficient conditions that there exist UMRE estimators of parameters in the variance components model are obtained for the first time.     

On the Local Uniqueness of Solutions of Variational Inequalities Under H-Differentiability

In this paper, we give some sufficient conditions for the local uniqueness of solutions to nonsmooth variational inequalities where the underlying functions are H-differentiable and the underlying set is a closed convex set/polyhedral set/box/polyhedral cone. We show how the solution of a linearized variational inequality is related to the solution of the variational inequality. These results extend/unify various similar results proved for C ¹ and locally Lipschitzian variational inequality problems. When specialized to the nonlinear complementarity problem, our results extend/unify those of C ² and C ¹ nonlinear complementarity problems.     

Pulse radiolysis study of the initial steps of the polymerization of cyclohexyl acrylate and cyclohexyl methacrylate

Pulse radiolysis with kinetic spectroscopic detection was applied to study the kinetics of the first steps of radiation induced polymerization of cyclohexyl acrylate and cyclohexyl methacrylate in cyclohexane solvent. The reactions were initiated by cyclohexyl radicals produced in the radiolysis of the solvent. The transient absorption spectra of the -carboxyalkyl type radicals produced in addition reaction show maxima around 300 nm. This shifts to longer wavelength with time after the pulse. This phenomenon was explained by the oligomerization reaction. From the kinetic curves average rate coefficients of termination for the oligomer radicals (2k_t) were determined as a function of time elapsed after the electron pulse. The values obtained were compared with those calculated for other (acrylate and methacrylate type) monomers.     

静脉滴注的临床决策

提出了静脉滴注的动力学一般模型，讨论了模型的性质，在给药剂量确定的条件下，探讨了调整滴注速率使治疗效果达到最佳的临床决策方法。     

The number of powers of 2 in a representation of large even integers II

It is proved that for any integerk≥ 54 000, there isN _k >0 depending onk only such that every even integer ≥N _k is a sum of two odd prime numbers andk powers of 2. Project partially supported by RGC Research Grant (No.HKU 7122/97P) and Post-Doctoral Fellowship of the University of Hong Kong.     

Thermal gradient induced sidebranching in directional solidification

The polycrystalline perovskitelike manganese oxides La_1-xA_xMnO (A = Na, and K, ) have been fabricated by sol-gel technique. For all the compositions explored in this work, the average manganese oxidation state is practically constant, at for A = Na, and for A = K, respectively. A close relationship is confirmed to hold between the Curie temperature (T_c) and the bond distance of Mn-O. Results of magnetic measurements show that these materials can be utilized as suitable candidates for magnetic refrigerants with wide applied temperature span, for their significant entropy change and the easily tuned Curie temperature. Received: 12 September 1997 / Revised: 18 December 1997 / Accepted: 21 January 1998     

用等厚干涉测定液体折射率

介绍一种采用等厚干涉原理测定液体折射率的简单可靠的方法。     

氢化丁苯共聚物结构的核磁共振波谱表征Ⅱ.微观结构的定量计算

在氢化丁苯共聚物¹³C-NMR谱脂肪碳部分谱带归属的基础上,根据各谱带的主要来源,推导出六个二单元浓度的计算公式。计算出二单元、一单元的相对含量,各结构单元的数均序列长度、嵌段含量和其它结构参数。加氢前后的¹H-和¹³C-NMR谱的组成计算结果基本一致。初步探讨了作为粘度指数改进剂的氢化丁苯共聚物微观结构与性能的关系,为合成提供了依据。