Enantioselective Synthesis of a Chiral Coordination Polymer with Circularly Polarized Visible Laser

Circular dichroism is known to be the feature of a chiral agent which has inspired scientist to study the interesting phenomena of circularly polarized light (CPL) modulated molecular chirality. Although several organic molecules or assemblies have been found to be CPL‐responsive, the influence of CPL on the assembly of chiral coordination compounds remains unknown. Herein, a chiral coordination polymer, which is constructed from achiral agents, was used to study the CPL‐induced enantioselective synthesis. By irradiation with either left‐handed or right‐handed CPL during the reaction and crystallization, enantiomeric excesses of the crystalline product were obtained. Left‐handed CPL resulted in crystals with a left‐handed helical structure, and right‐handed CPL led to crystals with a right‐handed helical structure. It is exciting that the absolute asymmetric synthesis of a chiral coordination polymer could be enantioselective when using CPL, and provides a strategy for the control of the chirality of chiral coordination polymers.     

Simulation of three‐dimensional flows over moving objects by an improved immersed boundary–lattice Boltzmann method

An improved immersed boundary–lattice Boltzmann method (IB–LBM) developed recently [28] was applied in this work to simulate three‐dimensional (3D) flows over moving objects. By enforcing the non‐slip boundary condition, the method could avoid any flow penetration to the wall. In the developed IB–LBM solver, the flow field is obtained on the non‐uniform mesh by the efficient LBM that is based on the second‐order one‐dimensional interpolation. As a consequence, its coefficients could be computed simply. By simulating flows over a stationary sphere and torus [28] accurately and efficiently, the proposed IB–LBM showed its ability to handle 3D flow problems with curved boundaries. In this paper, we further applied this method to simulate 3D flows around moving boundaries. As a first example, the flow over a rotating sphere was simulated. The obtained results agreed very well with the previous data in the literature. Then, simulation of flow over a rotating torus was conducted. The capability of the improved IB–LBM for solving 3D flows over moving objects with complex geometries was demonstrated via the simulations of fish swimming and dragonfly flight. The numerical results displayed quantitative and qualitative agreement with the date in the literature. Copyright © 2011 John Wiley & Sons, Ltd.     

层叠Blumlein线多开关导通时间分散性

高介电常数陶瓷储能脉冲形成线需要用到多开关触发的层叠Blumlein线结构。从形成线波过程理论出发，分析了多开关导通时间分散性对层叠Blumlein线及其输出波形的影响。主要包括两方面影响:其一是造成输出方波脉冲的前沿和后沿均出现阶梯形畸变；其二是使得各延迟导通的平行平板Blumlein线承受过电压，容易引起陶瓷储能介质的电击穿。在不单独考虑开关电感的理想情况下，利用PSpice电路程序模拟了开关导通时间分散性对四级层叠Blumlein线的影响，模拟结果与波过程理论分析一致。为减弱这些影响，提出了可行的解决方案。     

Interference of Transformer oil Matrices to the Internal Standards on PCB Quantification

Abstract

Polychlorinated biphenyls (PCBs) are toxic, perssstent, global environmental contaminants which were formulated as complex mixtures of congeners. Many methods have been developed in the past to analyze PCB in transformer oil samples for regulatory purposes. The most important consideration in the cleanup procedure is the ability to remove the oil from the sample matrix, since trace amount of oil will interfere with the subsequent GC-MS analysis. Electron capture detection (ECD) has been the most common method for gas chromatographic analysis of PCBs because of its high sensitivity toward halogenated compounds. ECD can also respond to some non-PCB compound resulting in biased concentrations of PCB. In this work, a two-stage cleanup method, using DMSO liquid/liquid extraction and HPLC column chromatography. has been applied to two types of transformer oil. Five internal standards have been selected to show their performance in the presence of different oil matrices. The comparison of the PCB quantification at different conditions for GC-MS and GC-ECD will be demonstrated.     

Synthesis and characterization of fluorine-containing cholesteric liquid crystalline polysiloxanes bearing trifluoromethyl-substituted mesogens

A series of side-chain liquid crystal (LC) polysiloxanes were synthesised with Poly(methylhydrogeno)siloxane, 4?-(undec-10-enoyloxy) biphenyl – 4 – yl 4- (trifluoromethyl) benzoate (M_th) and a chiral nematic (N*) LC monomer 1-allyl 10-(cholesteryl)-decanedioate (M_ch). The chemical structures and LC properties of the monomers and polymers were characterised by FTIR, ¹H-NMR, differential scanning calorimetry, thermogravimetric analysis, POM and X-ray diffractometer. M_ch is monotropic N* LC. The homopolymer derived from monomer M_ch is enantiotropic N* LC. Monomer M_th is a smectic A liquid crystal. The copolymers derived from M_ch and M_th are N* LCs. The temperatures at which 5% weight loss occurred are greater than 300°C for all the fluoro-containing polymers, and the residue weights of the samples at 600°C increased slightly as the content of trifluoromethyl mesogens increased in the polymers. The glass transition temperatures of the polymers increased as trifluoromethyl mesogens increased, too. The N*–I phase transition temperatures show a negative deviate from ideal or linear behaviour. The values of the enthalpy changes for the cholesteryl containing polymers are rather low and this is attributed to the biaxiality of cholesteryl moiety which tends to reduce the change in the orientational order at the N*–I transition. Compared to the monomers, the polymers show wider mesophase region.     

Pinacol Coupling of Aromatic Aldehydes and Ketones in Ethyl Acetate Mediated by TiCl4‐Mg

Titanium tetrachloride in ethyl acetate can be reduced by Mg powder to the corresponding low‐valent titanium complexes, which can reduce some aromatic aldehydes and ketones to the corresponding pinacols in 38–85% yields within 15–60 min at rt with stirring.     

General Synthetic Route to Monosubstituted Cycloheptadienes from Organometallic Compounds

An examination of the literature reveals that only a limited number of monosubstituted cycloheptadiene compounds have been reported. An obvious synthetic route to 5-substituted -1, 3-cycloheptadiene derivatives would be the reaction of nucleophiles with the cycloheptadienyl cation, but this pathway is generally unsuccessful due to the limited stability of the cation. On the other hand, the iron tricarbonyl complex of this cation shows remarkable stability¹ and an ability to react with nucleophiles². If the -Fe(CO)₃ group could be removed easily, a facile route to this family of organic compounds would be available. This work reports our investigation of the range of nucleophiles that can be utilized and the oxidizing agents that can remove efficiently the -Fe(CO)₃ group.