Preparation of α-oxygenated ketones by the dioxygenation of alkenyl boronic acids

Two in two: Dioxygenation of alkenyl boronic acids has been achieved with N-hydroxyphthalimide. The two-step process involves etherification of an alkenyl boronic acid with N-hydroxyphthalimide followed by a [3,3] rearrangement. The dioxygenated product can then be hydrolyzed to form either the corresponding α-hydroxy ketone or the α-benzoyloxy ketone.     

The role of nitrogen bridges perturbing the photophysical properties in the porphyrin framework

We have investigated the photophysical properties of vacataporphyrins possessing systematically controlled butadiene linkers on their π-electron pathways.     

Computer-aided drug design: lead discovery and optimization

Over the past decade, there have been remarkable advances in the area of computer-aided drug design (CADD), which has been applied at almost all stages in the drug discovery pipeline. The generation of initial lead compounds and the subsequent optimization aimed at improving potency and pharmacological properties are the core activities among all. The development in these aspects over the past years will be the focus of this review.     

Finite element simulations of window Josephson junctions

This paper deals with the numerical simulation of the steady state two dimensional window Josephson junctions by finite element method. The model is represented by a sine-Gordon type composite PDE problem. Convergence and error analysis of the finite element approximation for this semilinear problem are presented. An efficient and reliable Newton-preconditioned conjugate gradient algorithm is proposed to solve the resulting nonlinear discrete system. Regular solution branches are computed using a simple continuation scheme. Numerical results associated with interesting physical phenomena are reported. Interface relaxation methods, which by taking advantage of special properties of the composite PDE, can further reduce the overall computational cost are proposed. The implementation and the associated numerical experiments of a particular interface relaxation scheme are also presented and discussed.     

The generalized block-localized wavefunction method: a case study on the conformational preference and C-O rotational barrier of formic acid

A Lewis structure corresponding to the most stable electron-localized state is often used as a reference for the measure of electron delocalization effect in the valence bond (VB) theory. As the simplest variant of ab initio VB theory, the generalized block-localized wavefunction (BLW) method defines the wavefunction for an electron-localized state with block-localized orbitals without the orthogonalization constraint on different blocks. The validity of the method can be critically examined with experimental evidences. Here the BLW method has been applied to the investigation of the roles of both the π conjugation and σ hyperconjugation effects in the conformational preference of formic acid for the trans (Z) conformer over the cis (E) conformer. On one hand, our computations showed that the deactivation of the π conjugation or σ hyperconjugation has little impact on the Z-E energy gap, thus neither is decisive and instead the local dipole-dipole electrostatic interaction between the carbonyl and hydroxyl groups is the key factor determining the Z-E energy gap. On the other hand, the present study supported the conventional view that π conjugation is largely responsible for the C-O rotation barrier in formic acid, though the existence of hyperconjugative interactions in the perpendicular structure lowers the barrier considerably.     

Selective recognition of cyanide anion via formation of multipoint NH and phenyl CH hydrogen bonding with acyclic ruthenium bipyridine imidazole receptors in water

Five imidazole-based anion receptors A-E are designed for cyanide anion recognition via hydrogen bonding interaction in water. Only receptors A [Ru(bpy)(2)(mpipH)](ClO(4))(2) (bpy is bipyridine and mpipH is 2-(4-methylphenyl)-imidazo[4,5-f]-1,10-phenanthroline) and E [Ru(2)(bpy)(4)(mbpibH(2))](ClO(4))(4) (mbpibH(2) is 1,3-bis([1,10]-phenanthroline-[5,6-d]imidazol-2-yl)benzene) selectively recognize CN(-) from OAc(-), F(-), Cl(-), Br(-), I(-), NO(3)(-), HSO(4)(-), ClO(4)(-), H(2)PO(4)(-), HCO(3)(-), N(3)(-), and SCN(-) anions in water (without organic solvent) at physiological conditions via formation of multiple hydrogen bonding interaction with binding constants of K(A(H2O)) = 345 ± 21 and K(E(H2O)) = 878 ± 41, respectively. The detection limits of A and E toward CN(-) in water are 100 and 5 μM, respectively. Receptor E has an appropriate pK(a2)* value (8.75) of N-H proton and a C-shape cavity structure with three-point hydrogen bonding, consisting of two NH and one cooperative phenyl CH hydrogen bonds. Appropriate acidity of N-H proton and multipoint hydrogen bonding are both important in enhancing the selectivity and sensitivity toward CN(-) in water. The phenyl CH···CN(-) hydrogen bonding interaction is observed by the HMBC NMR technique for the first time, which provides an efficient approach to directly probe the binding site of the receptor toward CN(-). Moreover, CN(-) induced emission lifetime change of the receptor has been exploited in water for the first time. The energy-optimized structure of E-CN adduct is also proposed on the basis of theoretical calculations.     

Vibrational behavior of a soundbox in an atmosphere with a variable speed of sound

This paper describes a semi-quantitative method, suitable for a student laboratory exercise that shows that the acoustic properties of the soundbox of a musical instrument depend on the sound speed of the atmosphere surrounding and filling the instrument. A gas tent was constructed and used to enclose instruments in helium, carbon dioxide and mixtures thereof, allowing the sound speed to be varied from 250 to 1000 m/s. Soundboard admittance data were taken using a guitar and a violin as examples. The data, expressed as contour plots, show clearly the qualitative relationship between air and wood modes, and the guitar data are compared with a simple mechanical model. Experimental details of the construction and operation of gas tent are given, with attention paid to safety issues.     

一种密钥协商协议的自动化设计方法

通过引入优胜劣汰的自然规律,提出了一种改进的基于演化计算的安全协议自动化设计方法.该方法采用SVO逻辑作为描述协议的基本工具,给出了能全面衡量安全协议个体性能的评估函数,并据此理论设计出一种满足安全目标的密钥协商协议,保证了最终生成协议为最优解.实验结果显示:由于在协议生成过程中,同时进行了该协议的安全验证,能很好地保证所涉及协议的正确性和安全性.表明该方法具有较强的可行性和适用性.     

锂离子在混凝土碱集料反应过程中的作用

在采用X射线衍射分析、化学组成分析和偏光显微镜分析对硅质碳酸盐集料的矿物学特征充分研究的基础上,研究了锂离子迁移渗透在混凝土碱集料反应过程中的行为特征.混凝土棱柱法(CSA A23.2-14A或ASTM C 1293)所测的膨胀结果表明:掺加[Li]/[Na+K]摩尔比1.11的LiNO3-能有效抑制混凝土碱集料反应膨胀;锂玻璃不仅不能抑制碱集料反应膨胀甚至会在一定程度上促进膨胀;与单一掺加混合材(粉煤灰或矿渣)相比,LiNO3与混合材的复合在一定程度上增强了相应的膨胀抑制效果;在混凝土碱集料反应过程中,存在Li+与Na+,K+之间的竞争.相对而言,Li+具有一定的优势.这与锂盐能表现出一定的混凝土碱集料反应膨胀抑制效果相一致.此外,强度对比研究结果表明,掺加锂盐一定程度上降低了混凝土的强度.     

基于载波抑制调制的毫米波ROF下行链路传输系统

为提高Radio-over-Fiber(ROF)系统传输带宽,降低系统成本,扩展传输距离,提出一种毫米波ROF下行链路传输系统。与传统ROF系统相比较,该系统利用MZM光调制器实现光载波抑制调制,产生高频毫米波信号,易于系统集成。文中详细分析了抑制载波调制的原理,搭建了系统实验。在中心站,光载波抑制调制结构产生并上变频加载33GHz的光学毫米波;在基站,下行数据流由高速光探测器接收,经过电混频器恢复基带数据信号。实验结果表明,该系统下行链路的2.5 Gb/s数据信号能够成功传输20 km单模光纤,与传统方法相比,传输容量和距离都得到了明显改善。