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1.
2.
Lei Chen Hui-Qing Yang Cheng-Yu Jin Zhao-Xu Chen 《International journal of quantum chemistry》2020,120(22):e26366
We studied the ring opening of propylene oxide (PO) by salen-M coordinated OH− group [M = Al(III), Sc(III), Cr(III), Mn(III), Fe(III), Co(II), Co(III), Ni(II), Cu(II), Zn(II), Ru(III) and Rh(III)]. The results show that the ring-opening energy barriers for M(II) complexes are much lower than those with M(III) complexes in the gas phase, and the barriers correlate linearly with the negative charges on the OH− group and the Fukui function condensed on the OH− group. The nucleophilicity ordering in the gas phase can be rationalized by the ratio of formal positive charges/radius of M cations. Solvent effect greatly increases the barriers of M(II) complexes but slightly changes the results of M(III) ones, making the barriers similar. Analysis indicates that the reaction heats are linearly proportional to the reverse reaction barriers. The relationships established here can be used to estimate the ring-opening barriers and to screen epoxide ring-opening catalysts. 相似文献
3.
A model is developed for the formation and propagation of cracks in a material sample that is heated at its top surface, pyrolyses, and then thermally degrades to form char. In this work the sample is heated uniformly over its entire top surface by a hypothetical flame (a heat source). The pyrolysis mechanism is described by a one-step overall reaction that is dependent nonlinearly on the temperature (Arrhenius form). Stresses develop in response to the thermal degradation of the material by means of a shrinkage strain caused by local mass loss during pyrolysis. When the principal stress exceeds a prescribed threshold value, the material forms a local crack. Cracks are found to generally originate at the surface in response to heating, but occasionally they form in the bulk, away from ever-changing material boundaries. The resulting cracks evolve and form patterns whose characteristics are described. Quantities examined in detail are: the crack spacing in the pyrolysis zone; the crack length evolution; the formation and nature of crack loops which are defined as individual cracks that have joined to form loops that are disconnected from the remaining material; the formation of enhanced pyrolysis area; and the impact of all of the former quantities on mass flux. It is determined that the mass flux from the sample can be greatly enhanced over its nominal (non-cracking) counterpart. The mass efflux profile qualitatively resembles those observed in Cone Calorimeter tests. 相似文献
4.
Beyond Stereoselectivity,Switchable Catalysis: Some of the Last Frontier Challenges in Ring‐Opening Polymerization of Cyclic Esters
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Dr. Sophie M. Guillaume Dr. Evgueni Kirillov Dr. Yann Sarazin Prof. Dr. Jean‐François Carpentier 《Chemistry (Weinheim an der Bergstrasse, Germany)》2015,21(22):7988-8003
Metal‐based catalysts and initiators have played a pivotal role in the ring‐opening polymerization (ROP) of cyclic esters, thanks to their high activity and remarkable ability to control precisely the architectures of the resulting polyesters in terms of molar mass, dispersity, microstructure, or tacticity. Today, after two decades of extensive research, the field is slowly reaching maturity. However, several challenges remain, while original concepts have emerged around new types or new applications of catalysis. This Review is not intended to comprehensively cover all of these aspects. Rather, it provides a personal overview of the very recent progress achieved in some selected, important aspects of ROP catalysis—stereocontrol and switchable catalysis. Hence, the first part addresses the development of new metal‐based catalysts for the isoselective ROP of racemic lactide towards stereoblock copolymers, and the use of syndioselective ROP metal catalysts to control the monomer sequence in copolymers. A second part covers the development of ROP catalysts—primarily metal‐based catalysts, but also organocatalysts—that can be externally regulated by the use of chemical or photo stimuli to switch them between two states with different catalytic abilities. Current challenges and opportunities are highlighted. 相似文献
5.
HIRONOBU Ishihara 《Geometriae Dedicata》1997,67(3):309-336
Several classification results for ample vector bundles of rank 2 on Hirzebruch surfaces, and on Del Pezzo surfaces, are obtained. In particular, we classify rank 2 ample vector bundles with c2 less than seven on Hirzebruch surfaces, and with c2 less than four on Del Pezzo surfaces. 相似文献
6.
An Improved Gradient Projection-based Decomposition Technique for Support Vector Machines 总被引:2,自引:0,他引:2
Luca Zanni 《Computational Management Science》2006,3(2):131-145
In this paper we propose some improvements to a recent decomposition technique for the large quadratic program arising in
training support vector machines. As standard decomposition approaches, the technique we consider is based on the idea to
optimize, at each iteration, a subset of the variables through the solution of a quadratic programming subproblem. The innovative
features of this approach consist in using a very effective gradient projection method for the inner subproblems and a special
rule for selecting the variables to be optimized at each step. These features allow to obtain promising performance by decomposing
the problem into few large subproblems instead of many small subproblems as usually done by other decomposition schemes. We
improve this technique by introducing a new inner solver and a simple strategy for reducing the computational cost of each
iteration. We evaluate the effectiveness of these improvements by solving large-scale benchmark problems and by comparison
with a widely used decomposition package. 相似文献
7.
Formalization for problems of multicriteria decision making under uncertainty is constructed in terms of guaranteed and weak
estimates. A relevant definition of the vector maximinimax value is given. Parameterization and approximation of maximum,
minimax, and maximinimax values based on the inverse logical convolution are suggested. An application for multicommodity
networks is considered.
Received: December 13, 2000 / Accepted: August 21, 2001?Published online May 8, 2002 相似文献
8.
第五讲新型光纤水听器和矢量水听器 总被引:2,自引:0,他引:2
光纤水听器和矢量水听器作为当前水声研究领域最具有代表性的两大技术倍受业界关注。光纤水听器的重要贡献在于,从一个全新的角度出发,试图解决传统的水声传感和声纳数据传输一体化设计和实现的一系列问题,这有助于改善声纳系统的可靠性,并且有可能降低其制造、使用和维护的总成本。矢量水听器则由于其特有的指向性和矢量一相位处理方法,在低频和甚低频水声微弱目标探测方面具有潜在的优势.经过不懈的努力,光纤水听器和矢量水听器系统已经从实验室逐渐进入到工程应用阶段.这些对未来声纳系统的发展会产生相当重要的影响.文章尝试从声纳设计的角度对这两者的技术现状进行简要综述,包括它们各自的物理基础、工作原理、关键技术和应用领域. 相似文献
9.
本文介绍了近年来普通物理实验课程体系和教学内容改革的实践,并针对目前实验教学中仍存在的一些问题提出了开放式实验教学的改革思路。 相似文献
10.
Mathematical economics has a long history and covers many interdisciplinary areas between mathematics and economics. At its center lies the theory of market equilibrium. The purpose of this expository article is to introduce mathematicians to price decentralization in general equilibrium theory. In particular, it concentrates on the role of positivity in the theory of convex economic analysis and the role of normal cones in the theory of non-convex economies. 相似文献