Potential energy surface for the CCl4 + H --> CCl3 + ClH reaction: kinetics and dynamics study

An analytical potential energy surface for the gas-phase CCl4 + H --> CCl3 + ClH reaction was constructed with suitable functional forms to represent vibrational modes. This surface is completely symmetric with respect to the permutation of the four chlorine atoms and is calibrated with respect to experimental thermal rate constants available over the temperature range 297-904 K. On this surface, the thermal rate constants were calculated using variational transition-state theory with semiclassical transmission coefficients over a wider temperature range 300-2500 K, therefore obtaining kinetics information at higher temperatures than are experimentally available. This surface was also used to analyze dynamical features, such as tunneling and reaction-path curvature. In the first case, the influence of the tunneling factor is very small since a heavy chlorine atom has to pass through the barrier. In the second, it was found that vibrational excitation of the Cl-H stretching mode can be expected in the exit channel.     

Efficient synthesis of 3H-imidazo[4,5-b]pyridines from malononitrile and 5-amino-4-(cyanoformimidoyl)imidazoles

1-Aryl-5-amino-4-(cyanoformimidoyl)imidazoles 2 were reacted with malononitrile under mild experimental conditions and led to 3-aryl-5,7-diamino-6-cyano-3H-imidazo[4,5-b]pyridines 5, when the reaction was carried out in the presence of DBU, or to 3-aryl-5-amino-6,7-dicyano-3H-imidazo[4,5-b]pyridines 3, in its absence. Both reactions evolved from the adduct formed by nucleophilic attack of the malononitrile anion to the carbon of the cyanoformimidoyl substituent. A 5-amino-1-aryl-4-(1-amino-2,2-dicyanovinyl)imidazole 4 was isolated when this reaction was carried out in the presence of DBU. The structure of compound 4 was confirmed by spectroscopic methods and by reaction with triethyl orthoformate and with acetic anhydride, leading respectively to 9-aryl-6-(cyanomethylidene)purines 11 and 12. Imidazole 2b was also reacted with ethyl acetoacetate, a carbon acid with a pK(a) comparable to that of malononitrile. Similar reaction conditions were used and the product isolated was a 6-carbamoyl-1,2-dihydropurine 10, showing that a different mechanism was operating in this case.     

Development of Postgraduate Education in Chemical Engineering

1 Development of Postgraduate Education There were only 200 postgraduates were honored master degree from the year 1935 to 1949 in old China. While, after the establishment of new China, the postgraduate education has developed in a certain degree, there were 23,000 postgraduates were enrolled from 1950 to 1965, and there were no postgraduates during the period of 1966 to 1977 due to the "culture revolution".     

CHARACTERIZATION OF SOL-GEL-DERIVED ZrO2 FILM BY PHOTOTHERMAL RADIOMETRY

In modern industry,thin film on the substratc has much important role to decide the properties of product, especially for electrical, optical and wear-resistant etc, production. There are some technical methods to prepare thin film,including plasma spray,physical vapor deposition (PVD),chemical vapor deposition (CVD) and sol-gel,etc. Among of them,sol-gel method has been developed a popular tech nique for preparing thin films.     

一类非线性系统的快速鲁棒故障诊断

.结合在线估计器和滑模观测器方法,基于所给出的一种新的自适应学习算法,提出了一种针对非线性不确定系统的鲁棒故障诊断方法.滑模观测器可以消除建模不确定性的影响以得到准确的状态估计,而在线估计器可以实时估计故障的大小.在此,基于李亚普诺夫函数,在理论上证明了所给出的状态和参数估计误差都是一致有界的;针对三容水箱DTS200所做的仿真实验,其结果验证了该方法的可行性.研究结果表明,由于滑模项的引入,使得该方法的故障检测时间大大缩短,其性能比Polycarpou所提出的在线估计器方法的性能要好.     

一种改进的M元扩频通信算法

针对采用码相位循环移位获得的M元扩频需要额外同步信息的问题,提出一种改进型扩频通信算法.该算法采用m序列及其倒序序列构成系统扩频码集;在同相支路上利用扩频码的码极性调制进行传输,同时在正交支路利用扩频码码相位调制,实现M元扩频.该算法利用2种扩频方式的自身特点可快速准确地获取载波相位信息,具有不需要额外提供同步资源的优势.仿真结果表明,该算法可有效提高系统资源的利用率.     

Cytotoxic and NF-κB inhibitory sesquiterpene lactones from Piptocoma rufescens

Six new (1-6) and eight known germacranolide-type sesquiterpene lactones, along with several known phenylpropanol coumarates and methylated flavonoids, were isolated from the leaves of Piptocoma rufescens, collected in the Dominican Republic. The new compounds were identified by analysis of their spectroscopic data, with the molecular structure of 3 being established by single-crystal X-ray diffraction. The absolute configurations of the sesquiterpene lactones isolated were determined from their CD and NOESY NMR spectra, together with the analysis of Mosher ester reactions. Bioassay screening results showed the majority of the sesquiterpene lactones isolated (1-13) to be highly cytotoxic toward the HT-29 human colon cancer cell line, with the most potent compound being 15-deoxygoyazensolide (10, IC(50), 0.26 μM). In addition, several of the sesquiterpene lactones exhibited NF-κB (p65) inhibitory activity.     

Oscillatory persistent currents in self-assembled quantum rings

We report the direct measurement of the persistent current carried by a single electron by means of magnetization experiments on self-assembled InAs/GaAs quantum rings. We measured the first Aharonov-Bohm oscillation at a field of 14 T, in perfect agreement with our model based on the structural properties determined by cross-sectional scanning tunneling microscopy measurements. The observed oscillation magnitude of the magnetic moment per electron is remarkably large for the topology of our nanostructures, which are singly connected and exhibit a pronounced shape asymmetry.     

Spin-orbit-coupled Bose-Einstein condensates

Spin-orbit (SO) coupling--the interaction between a quantum particle's spin and its momentum--is ubiquitous in physical systems. In condensed matter systems, SO coupling is crucial for the spin-Hall effect and topological insulators; it contributes to the electronic properties of materials such as GaAs, and is important for spintronic devices. Quantum many-body systems of ultracold atoms can be precisely controlled experimentally, and would therefore seem to provide an ideal platform on which to study SO coupling. Although an atom's intrinsic SO coupling affects its electronic structure, it does not lead to coupling between the spin and the centre-of-mass motion of the atom. Here, we engineer SO coupling (with equal Rashba and Dresselhaus strengths) in a neutral atomic Bose-Einstein condensate by dressing two atomic spin states with a pair of lasers. Such coupling has not been realized previously for ultracold atomic gases, or indeed any bosonic system. Furthermore, in the presence of the laser coupling, the interactions between the two dressed atomic spin states are modified, driving a quantum phase transition from a spatially spin-mixed state (lasers off) to a phase-separated state (above a critical laser intensity). We develop a many-body theory that provides quantitative agreement with the observed location of the transition. The engineered SO coupling--equally applicable for bosons and fermions--sets the stage for the realization of topological insulators in fermionic neutral atom systems.