Intermolecular Stetter reaction of aromatic aldehydes with (E)-(2-nitrovinyl)cyclohexane induced by N-heterocyclic carbene and thiourea

Intermolecular Stetter reaction of aromatic aldehydes with (E)-(2-nitrovinyl)cyclohexane catalyzed by thiazolium A has been developed. The reaction rate and efficiency are profoundly impacted by the presence of thiourea B. The reaction affords moderate to good yields of the Stetter product. Some factors influencing yield were discussed.     

CL-20/TNT共晶炸药的分子动力学研究

运用分子动力学(MD)方法,选择凝聚态分子势能优化力场(COMPASS),对六硝基六氮杂异伍兹烷(ε-CL-20)、2,4,6-三硝基甲苯(TNT)晶体及其等摩尔比的CL-20/TNT混合炸药和共晶炸药进行不同温度下恒定粒子数等压等温(NPT)系综模拟研究.结果表明,CL-20/TNT共晶的内聚能密度(CED)和结合能随温度的升高逐渐减小;共晶的CED比混合炸药的大,结合能是混合炸药的2倍多,预示其稳定性明显增强.对相关函数和局部放大结构显示共晶中组分分子间作用主要来自TNT中H和CL-20中O以及CL-20中H和TNT中O之间形成的氢键.通过波动法求得的弹性力学性能结果表明,CL-20/TNT共晶的拉伸模量(E)、体积模量(K)和剪切模量(G)介于ε-CL-20和TNT晶体之间,且随温度的升高而下降,符合一般预期;但共晶炸药的柯西压(C12-C44,Cij弹性系数)、K/G和泊松比(ν)均比其组分炸药ε-CL-20和TNT高得多,预示该共晶具有异常高的延展性和弹性伸长,主要是二组分呈层状交替排列且之间存在较强相互作用所致.     

Synthesis,bioactivity and functional evaluation of linker-modified allatostatin analogs as potential insect growth regulators

Insect growth regulators play an important role in integrated pest management strategies.The FGLa–allatostatins(ASTs)are a family of neuropeptides that can inhibit juvenile hormone(JH)biosynthesis by the corpora allata(CA)of Diploptera punctata in vitro,are regarded as insect growth regulator candidates.In the search for new potential mimics and to explore the effect of linker length on inhibiting JH biosynthesis,a series of AST analogs were synthesized by modifying the linker of K24,which was found to have a significant effect on JH biosynthesis in vitro in our previous study.Functional evaluation demonstrated that all the target compounds can activate the Dippu-Ast R,albeit with different potencies.Analog L6 with the longest linker(n=5),exhibited not only a promising effect on inhibition of JH biosynthesis both in vitro and in vivo,but also good activity in inhibiting basal oocyte growth.Structure–activity relationships(SAR)studies showed that longer linkers provided greater contribution to activity.     

On the structure and volume growth of submanifolds in Riemannian manifolds

The aim of this note is two-fold. First, we investigate the relations between the volume growth of a submanifold and its second fundamental form. In the second part, we discuss the relations between the index of some Schrödinger operators and the structure of a submanifold, and prove some one-end theorems.     

Importance of the Correlation between Width and Length in the Shape Analysis of Nanorods: Use of a 2D Size Plot To Probe Such a Correlation

Analysis of nanoparticle size through a simple 2D plot is proposed in order to extract the correlation between length and width in a collection or a mixture of anisotropic particles. Compared to the usual statistics on the length associated with a second and independent statistical analysis of the width, this simple plot easily points out the various types of nanoparticles and their (an)isotropy. For each class of nano‐objects, the relationship between width and length (i.e., the strong or weak correlations between these two parameters) may suggest information concerning the nucleation/growth processes. It allows one to follow the effect on the shape and size distribution of physical or chemical processes such as simple ripening. Various electron microscopy pictures from the literature or from the authors′ own syntheses are used as examples to demonstrate the efficiency and simplicity of the proposed 2D plot combined with a multivariate analysis.     

Modified Lagrangian vortex method with improved boundary conditions for water waves past a thin bottom‐standing barrier

Herein, the modified Lagrangian vortex method (LVM), a hybrid analytical‐numerical algorithm per se, is devised to simulate the process of vortex formation and shedding from the sharp edge of a zero‐thickness vertical plate under linear water‐wave attack. Application of the Helmholtz decomposition facilitates a convenient switch between the inviscid‐ and viscous‐flow models, thereby enabling easy incorporation of vorticity effects into the potential‐flow calculations for the viscous‐dominated region. In evaluating the potential‐flow component, making good use of the quickly convergent technique with singular basis functions, correctly capturing the singular behavior in velocity fields near the tip of the plate, leads to a considerable reduction of computational burdens and to 12‐decimal‐place accuracy. The viscous correction is carried out via the meshless LVM with improved boundary conditions. Comparisons with previously published results show good agreement. Simulations of vortex generation and evolution illuminate the ability of the present method, and provide a supplement to pertinent experimental works. The hybrid scheme proposed herein allows flexibility for the former LVM and convenience in the code development. Such a compromise fits particularly well for the high‐resolution modeling of sharp‐edged vortex shedding without heavy numerical developments. Copyright © 2014 John Wiley & Sons, Ltd.     

Mechanism of Insertion Reactions between Silylenoid H2SiLiF and GeH3R (R =F,OH, NH2): a Theoretical Study

Theoretical investigations on the insertion reaction mechanisms of three- membered-ring silylenoid H2 Si Li F with GeH 3R(R = F, OH, NH2) have been systematically carried out by combined density functional theory(DFT) and ab initio quantum chemical calculations. The geometries of all stationary points for these reactions were optimized using the B3 LYP method and then the QCISD method was used to calculate the single-point energies. The calculated results indicate that, there are one precursor complex(Q), one transition state(TS), and one intermediate(IM) which connect the reactants and the products along the potential energy surface. The insertion reactions of three-membered-ring silylenoid with Ge H3 R proceed in a concerted manner, forming H2RSi-Ge H3 and Li F. The calculated potential energy barriers of the three reactions are 29.17, 30.90, and 54.07 k J/mol, and the reaction energies for the three reactions are –127.05, –116.91, and –103.31 k J/mol, respectively. The insertion reactions in solvents are similar to those in vacuum. Under the same situation, the insertion reactions should occur easily in the following order: GeH 3-F GeH 3-OH GeH 3-NH2. The elucidations of the mechanism of these insertion reactions provided a new mode of silicon-germanium bond formation.