Molecular dynamics of the intramolecular 1, 3-dipolar ene reaction of a nitrile oxide and an alkene: non-statistical behavior of a reaction involving a diradical intermediate*

ABSTRACT

Potential energy surfaces and molecular dynamics of the intramolecular 1, 3-dipolar cycloaddition and ene reaction of a nitrile oxide with an alkene were performed in the gas phase and in dichloromethane with density functional theory. One hundred trajectories were propagated in the gas phase and in dichloromethane, respectively. Twenty percent of the trajectories in the gas phase involve bicyclic intermediate and the mean time gap is 472fs. A dynamically stepwise reaction is observed. In dichloromethane, more reactive trajectories were obtained and the time gap is larger than that in the gas phase.     

Formation of the intermediate semiconductor larger for the Ohmic contact to silicon carbide using Germanium implantation

By formation of an intermediate semiconductor layer (ISL) with a narrow band gap at the metallic contact/SiC interface, this paper realises a new method to fabricate the low-resistance Ohmic contacts for SiC. An array of transfer length method (TLM) test patterns is formed on N-wells created by P⁺ ion implantation into Si-faced p-type 4H-SiC epilayer. The ISL of nickel-metal Ohmic contacts to n-type 4H-SiC could be formed by using Germanium ion implantation into SiC. The specific contact resistance ρ_c as low as 4.23× 10^-5~Ωega \cdotcm² is achieved after annealing in N₂ at 800~°C for 3~min, which is much lower than that (>900~°C) in the typical SiC metallisation process. The sheet resistance R_sh of the implanted layers is 1.5~kΩega /\Box. The technique for converting photoresist into nanocrystalline graphite is used to protect the SiC surface in the annealing after Ge⁺ ion implantations.     

基于聚类分割和形态学的可见光与SAR图像配准

针对可见光与SAR图像灰度差异大,共有特征提取难的问题,提出了一种基于k-均值聚类分割和形态学处理的轮廓特征配准方法。利用k-均值聚类算法对两类图像进行分割,得到图像分割区域;通过形态学处理,有效减少SAR图像斑点噪声影响,准确提取两类图像的封闭轮廓;采用轮廓不变矩理论,引入矩变量距离均值、方差约束机制和一致性检查的匹配策略,获取最佳匹配对,实现了两类图像的配准。通过实验,三组图像的配准精度分别达到0.3450、0.2163和0.1810,结果表明该法可行且能达到亚像素的配准精度。     

数值积分公式中间点的渐近性质及其应用

主要研究了三类数值积分公式的中间点的渐近性质,得到了更一般性的结果.基于中间点的渐近性质,获得了数值积分的校正公式及其条件误差估计.数值例子显示了校正公式的精度明显高于对应的计算公式.     

新一代太阳电池概述

文章对新一代太阳电池的基本概念、研究现状和研究目标进行了详细的介绍.从“充分吸收光能,减少能量转换损失”的角度,分析了新一代太阳电池的结构设计特征.以纳米技术与叠层电池结构为基础,就高能光子的利用,介绍了宽带隙吸收层窗口电池、量子点热载流子电池和多重激子激发（MEG）的量子点电池;为解决低能光子损失,介绍了窄带隙光伏材料和中间带光伏器件包括量子点中间带和高失配构建的中间带电池;探讨了利用光-光转换的模式,对上转换和下转换的电池体系以及可能的极限效率进行了阐述.     

Recyclable MoO3 nanobelts for photocatalytic degradation of Rhodamine B by near infrared irradiation

Molybdenum trioxide (MoO₃) represented an excellent photocatalytic performance with many applications, including degradation of organic contaminants and splitting of water. This paper presented a new route to synthesize MoO₃ nanobelts with high aspect ratios and crystallinity by a hydrothermal technique. This work showed that the as-synthesized nanobelts exhibited strong photocatalytic activity to degrade an organic dye of Rhodamine B (RhB) in aqueous solution under the exposure of the light source in the near infrared wavelength range, significantly improving the photocatalytic activity of the nanobelts. The results also showed that for a small concentration of RhB at 7.5 mg/L a complete photodegradation (for a given MoO₃ nanobelts quantity of 0.1 g) can be reached after exposing for 60 min. For all concentrations of the RhB solution, the photodegradation exhibited an exponential dependence on the exposure time followed by a sudden shutdown, but no complete photodegradation can be reached. Also, the residual quantity of RhB in solution after the photocatalytic reaction was determined by the initial RhB concentration. The photocatalytic degradation can be interpreted by the pseudo–first-order equation for the absorption of liquid/solid based on solid capacity; thus, photocatalytic degradation can be attributed to the interaction between the photoexcited electrons in the substrate and the antibonding orbital of the RhB in solution. The sudden shutdown was due to the inability of the photoexcited electrons in the substrate hopping to the antibonding orbital of RhB in the presence of the RhB intermediate products from the degraded RhB. In addition, this work showed that the photocatalytic reaction can be recovered after a thermal treatment of postreacted MoO₃ nanobelts, enhancing the utilization efficiency of the catalysis.     

IN SITU IR SPECTROSCOPIC STUDIES OF HCOOH DECOMPOSITION OVER V-TI-O CATALYST

Decomposition of formic acid over V-Ti-O catalysts was studied by in situ IR spectroscopy. Four surface compounds, among which are H-bonded acid, one mono- and two bidentate formates (BF1 and BF2), were identified in the temperature range of 100-190°C. The activation energy and rate of the BF2 decomposition were found equal to those for the CO formation. This equality points to the involvement of BF2 in the HCOOH decomposition into carbon monoxide.     

A theoretical study of topomerization of imine systems: Inversion,rotation or mixed mechanisms?

The different mechanisms, rotation, inversion, or intermediate mechanism, by which occur the topomerization of imine systems R₂ CN X have been studied by applying ab initio, B3LYP, and MP2 methods. The effect of a wide variety of substituents R and X on the isomerization pathway have been examined by computing fully optimized structures of the ground and transition states (136 isomers belonging to different imine families were studied and more than 300 transition structures were determined at various levels of theory). Energy barriers have been also obtained and it was found that the groups R and X have a strong influence on the type of mechanism involved and the activation energies. Thus, and depending on the type of substituents, transition state structures related to the following kinds of processes were found: pure inversion, intermediate mechanisms, rotation, and enhanced rotation (hyper‐rotation). In turn, the corresponding activation energies range between very low (<10 kcal/mol) and extremely high (> 70 kcal/mol) values. A simple index that allows us to quantify the percentage of inversion or rotation mechanism is proposed. © 2009 Wiley Periodicals, Inc. J Comput Chem, 2010     

Design,synthesis, biological activity evaluation and mechanism of action of myricetin derivatives containing thioether quinazolinone

Plant bacteria and viruses have a huge negative impact on food crops in the world. Therefore, it is important to create new and efficient green pesticides. In this paper, a series of myricetin derivatives containing quinazolinone sulfide were introduced. Good antibacterial and antiviral activities of the drug molecules 2-((3-((5,7-dimethoxy-4-oxo-2-(3,4,5-trimethoxyphenyl)-4H-chromen-3-yl)oxy)propyl)thio)-6-fluoro-3-phenylquinazolin-4(3H)-one (T5) and 2-((4-((5,7-dimethoxy-4-oxo-2-(3,4,5-trimethoxyphenyl)-4H-chromen-3-yl)oxy)butyl)thio)-6-methyl-3-phenylquinazolin-4(3H)-one (T15) respectively were found by biological activity screening. The value of dissociation constant (K_d) of compound T15 to TMV CP was 0.024 ± 0.006 μM, determined by Microscale thermophoresis (MST), which was far less than the value of 8.491 ± 2.027 μM of commercial drug ningnanmycin (NNM). The interaction between compound T15 and TMV CP was further verified by molecular docking. Compound T15 formed strong hydrogen bonds with residues SER:49 and SER:15 (1.92 Å, 2.20 Å, respectively), which were superior to the traditional hydrogen bonds formed by NNM with residue SER:215 (3.64 Å). In addition, the effects of compound T15 on the contents of chlorophyll and peroxidase (POD) in tobacco were studied, and the results indicated that compound T15 could enhance the disease resistance of tobacco plants to a certain extent.     

Rh/Al2O3上CO和NO的吸附性能及相互作用

利用ＴＰ－ＩＲ动态方法研究了ＣＯ和ＮＯ在Ｒｈ／Ａｌ２Ｏ３上吸附性能和相互作用的动态行为，结果表明，Ｒｈ／Ａｌ２Ｏ３的孪生中心对ＣＯ的吸附强于对ＮＯ的吸会，线式和桥式中心则对ＮＯ的吸附强于对ＣＯ的吸附，ＣＯ和ＮＯ共吸附－ＴＰ（ＣＯ和ＮＯ中）－ＩＲ动态过程结果揭示出２２２４ｃｍ＾－１谱带的出现和强度的增加与孪生ＣＯ谱带以及吸附的ＮＯ谱带的强度减弱同时发生，表明是由吸附的ＮＯ和孪生ＣＯ形成Ｒｈ－ＮＣＯ。