高立体选择性地合成薄荷基溴和新薄荷基溴

薄荷基溴和新薄荷基溴是一类非常有用的不对称合成中间体。以L-薄荷醇为原料,通过与不同的溴化剂反应高立体选择性地得到薄荷基溴和和新薄荷基溴。当L-薄荷醇与盐酸和无水溴化锌反应时高立体选择性地得到薄荷基溴,当L-薄荷醇与三溴化磷反应时高立体选择性地得到新薄荷基溴.     

Synthesis and structural characterisation of five copper(I) and silver(I) complexes with 2-aminopyridine (2-APy), [Cu(μ-Cl)(2-Apy)(PPh3)]2, [Ag(μ-X)(2-Apy)(PPh3)]2 (X = Cl,Br), [Ag(μ-ONO2)(2-Apy)(EPh3)]2 (E = P,As)

Five new copper(I)/silver(I) complexes containing 2-aminopyridine, [Cu(μ-Cl)(2-Apy)(PPh₃)]₂(1), [Ag(μ-Cl)(2-Apy)(PPh₃)]₂(2), [Ag(μ-Br)(2-Apy)PPh₃)]₂(3), [Ag(μ-ONO₂)(2-Apy)(PPh₃)]₂(4), [Ag(μ-ONO₂)(2-Apy)(AsPh₃)]₂(5) have been synthesised for the first time. Complexes 1–5 are obtained by the reactions of MX (MX = CuCl for 1; M = Ag for 2–5; X = Cl, Br for 2–3; X = NO₃ for 4–5) with the monodentate ligands EPh₃ (E = P for 1–4; E = As for 5) and 2-Apy in the molar ratio of 1:1:2 in the mixed solvent of CH₂Cl₂ and MeOH. Complexes 1–5 are characterised by IR and X-ray diffraction. In 1–5, chloride, bromide and nitrate ions bridge two metal atoms to form dinuclear complexes containing the parallelogram cores M₂X₂ (M = Cu, Ag).     

Assignment on the X,A, B,C, and D states of the C6H5Br+ cation based on high‐level calculations

Geometries, frequencies, and energies of the 1²B₁, 1²A₂, 1²B₂, 2²B₁, 2²B₂, and 1²A₁, of the C₆H₅Br⁺ ion were calculated by using CASSCF and CASPT2 methods in conjunction with an ANO‐RCC basis. The CASPT2//CASSCF adiabatic excitation energies and CASPT2 relative energies for the six states are in good agreement with experiment. The X, A, B, C, and D electronic states of the C₆H₅Br⁺ ion were assigned to be X²B₁, A²A₂, B²B₂, C²B₁, and D²B₂ based on the CASSCF and CASPT2 calculations. The assignment on the D state of the C₆H₅Br⁺ ion is different from the previously published works. © 2009 Wiley Periodicals, Inc. Int J Quantum Chem, 2010     

Rhodium-catalyzed Asymmetric Ring-opening Reactions of N-Boc-azabenzonorbornadiene with N-Substituted Piperazine Nucleophiles

Asymmetric ring‐opening reactions of N‐Boc‐azabenzonorbornadiene with N‐substituted piperazine nucleophiles in the presence of 5 mol% of [Rh(COD)Cl]₂ and 10 mol% of chiral ligand, (R,S)‐PPF‐P‐t‐Bu₂, gave the corresponding 1,2‐diamine product in moderate to excellent yields (up to 95%) with reasonable enantiomeric excesses (up to 70% ee). The results showed that the nature of ligands had significant influence on the yields and the enantiomeric excesses.     

Calculations of the free energy of interaction of the c-Fos-c-Jun coiled coil: effects of the solvation model and the inclusion of polarization effects

The leucine zipper region of activator protein-1 (AP-1) comprises the c-Jun and c-Fos proteins and constitutes a well-known coiled coil protein-protein interaction motif. We have used molecular dynamics (MD) simulations in conjunction with the molecular mechanics/Poisson-Boltzmann generalized-Born surface area [MM/PB(GB)SA] methods to predict the free energy of interaction of these proteins. In particular, the influence of the choice of solvation model, protein force field, and water potential on the stability and dynamic properties of the c-Fos-c-Jun complex were investigated. Use of the AMBER polarizable force field ff02 in combination with the polarizable POL3 water potential was found to result in increased stability of the c-Fos-c-Jun complex. MM/PB(GB)SA calculations revealed that MD simulations using the POL3 water potential give the lowest predicted free energies of interaction compared to other nonpolarizable water potentials. In addition, the calculated absolute free energy of binding was predicted to be closest to the experimental value using the MM/GBSA method with independent MD simulation trajectories using the POL3 water potential and the polarizable ff02 force field, while all other binding affinities were overestimated.     

From Monomers to π Stacks, from Nonconductive to Conductive: Syntheses, Characterization, and Crystal Structures of Benzidine Radical Cations

Salts that contain radical cations of benzidine (BZ), 3,3',5,5'-tetramethylbenzidine (TMB), 2,2',6,6'-tetraisopropylbenzidine (TPB), and 4,4'-terphenyldiamine (DATP) have been isolated with weakly coordinating anions [Al(OR(F) )(4) ](-) (OR(F) =OC(CF(3) )(3) ) or SbF(6) (-) . They were prepared by reaction of the respective silver(I) salts with stoichiometric amounts of benzidine or its alkyl-substituted derivatives in CH(2) Cl(2) . The salts were characterized by UV absorption and EPR spectroscopy as well as by their single-crystal X-ray structures. Variable-temperature UV/Vis absorption spectra of BZ(.) (+) [Al(OR(F) )(4) ](-) and TMB(.) (+) [Al(OR(F) )(4) ](-) in acetonitrile indicate an equilibrium between monomeric free radical cations and a radical-cation dimer. In contrast, the absorption spectrum of TPB(.) (+) SbF(6) (-) in acetonitrile indicates that the oxidation of TPB only resulted in a monomeric radical cation. Single-crystal X-ray diffraction studies show that in the solid state BZ and its methylation derivative (TMB) form radical-cation π dimers upon oxidation, whereas that modified with isopropyl groups (TPB) becomes a monomeric free radical cation. By increasing the chain length, π stacks of π dimers are obtained for the radical cation of DATP. The single-crystal conductivity measurements show that monomerized or π-dimerized radicals (BZ(.) (+) , TMB(.) (+) , and TPB(.) (+) ) are nonconductive, whereas the π-stacked radical (DATP(.) (+) ) is conductive. A conduction mechanism between chains through π stacks is proposed.     

A label-free fluorescent molecular beacon based on DNA-templated silver nanoclusters for detection of adenosine and adenosine deaminase

A simple and reliable fluorescent molecular beacon is developed utilizing DNA-templated silver nanoclusters as a signal indicator and adenosine triphosphate (ATP) and adenosine deaminase as mechanical activators.     

Role of surface metal nanoparticles on the absorption in solar cells

The effect of absorption enhancement with metallic nanoparticles on solar cell surfaces is often confused with various optical processes. In this work, the effective absorption rates in the active materials of solar cells are explicitly calculated including all possible factors. The results show that, although the total absorption is highly enhanced in general, the effective absorption in the active region is not much enhanced and even strongly reduced in the blue-violet regime. As the solar spectrum is considered, the integrated absorbed power in the solar cell materials is shown to be similar for structures with or without metallic nanoparticles.     

基于库仑定律的二极管空间电荷限制效应研究

真空二极管是电子束源装置中的一个关键部件, 其阴极发射的电子束进入二极管阴阳极间隙区会产生很强的空间电荷限制效应. 本文针对平板真空二极管中的空间电荷限制效应物理模型, 从库仑定律的积分形式出发, 选取了不同参数的阴极半径与阴阳极间隙距离之比, 计算得到了真空二极管阴阳极间隙区的电场分布情况, 从而避免了采用Poisson方程求解时需要处理复杂的非线性偏微分方程这一问题. 结果表明, 基于库仑定律的计算结果与从Child-Langmuir定律分析得到的结果仅相差一个与二 极管极板边界条件有关的修正量. 当二极管阴极半径与阴阳极间隙距离之比 R/D>10时,一维空间电荷限制定律将是一个较好的近似结果,当 R/D较小时, 用该定律计算误差较大,在实际物理问题中需要谨慎使用.     

力学共振吸收谱探测耦合振动模式

提出探测复杂力学振动系统耦合振动模式的方法:通过测量力学振动系统中某一易于探测的振动模式对外力的响应行为,在该振动模式应变落后于应力的相位差-频率谱(表观机械能耗散-频率谱)中,除了能观察到与被测量振动模式本征频率所对应的相位变化外,与被测量振动模式耦合的其他振动模式也表现为共振吸收峰;从共振吸收峰的性质,如峰位、峰宽、峰高等可以得到相应耦合振动模式的本征频率、损耗以及耦合强度等信息.以倒扭摆力学系统为例,通过测量扭摆的扭转振动模式应变落后于应力的相位差-频率谱研究了扭摆系统中摆杆的进动振动模式.