Progressive studies on the novel samarium-catalyzed diastereoselective tandem semipinacol rearrangement/Tishchenko reduction of secondary alpha-hydroxy epoxides

A novel and highly diastereoselective samarium-catalyzed tandem rearrangement/reduction of secondary alpha-hydroxy epoxides, which involves a C1 to C3 carbon migration rearrangement and a very interesting hetero-Tishchenko reduction of the intermediate aldehyde and the reductant aldehyde, has been reported. This reaction could be developed to provide a facile and stereoselective construction of 2-quarternary 1,3-diol units with an hydroxymethyl moiety attached to the diastereogenic quaternary carbon center. Detailed investigations have been carried out concerning the screening of the aldehydes as a reductant, the optimization of reaction conditions, and the substrate scope of this tandem reaction. A catalytic cycle for this reaction, the electronic and steric effects of the reductant aldehydes, and the mechanism for the acyl migration of 1,3-diol monoesters are proposed.     

Temperature effects on the enantioselectivity of basic analytes in capillary EKC using sulfated beta-CDs as chiral selectors

The thermodynamic processes were investigated to reveal the temperature effects during chiral separation by capillary EKC with reversed polarity mode using sulfated beta-CD (S-beta-CD) as chiral selectors. The temperature effects on enantioselectivities of basic analytes (ephedrine, norephedrine, synephrine, and epinephrine) were investigated in detail over a temperature range of 20-60 degrees C. An increase of the capillary temperature produced the decrease of enantioselectivities for ephedrine and norephedrine, but increase of enantioselectivities for synephrine and epinephrine. The thermodynamic variations showed that the interactions between the basic analytes and chiral selectors were always enthalpy- driven. However, the difference in enthalpy and entropy showed that the enantioseparation was an enthalpy-driven process for ephedrine and norephedrine, but an entropydriven process for synephrine and epinephrine. Just because of the different driving forces, there exist two kinds of temperature effects on enantioselectivities mentioned above.     

Theoretical description of improving measurement accuracy for incoherence Mie Doppler wind lidar

For the nonlinearity of Fabry-Perot interferometer(FPI) transmission spectrum,the measurement uncertainty of incoherent Mie Doppler wind lidar based on it increases evidently with the increase of backscattering signal Doppler shift.A method of repeating the use of the approximate linear part of FPI transmission spectra for reducing the high uncertainty of a big Doppler shift is proposed.One of the ways of realizing this method is discussed in detail,in which the characteristics of FPI transmission spectrum changing with thickness and incident angle are utilized simultaneously.Under different atmosphere conditions,it has been proved theoretically that the range of measurement uncertainty drops to one-sixth while its minimum has no serious change.This method can be used not only to guide the new system design,but also as a new working way for the fabricated system.     

An efficient total synthesis of (+/-)-lycoramine

[reaction: see text] A short and unique approach to (+/-)-lycoramine as one of the galanthamine-type alkaloids has been efficiently developed. The alternative advantage lies in that three stereocenters, including a crucial quaternary carbon center, were constructed with high diasteroselectivity via a key one-step NBS-mediated semipinacol rearrangement of the allylic alcohol.     

Implementation and verification of different ECC mitigation designs for BRAMs in flash-based FPGAs

Embedded RAM blocks(BRAMs) in field programmable gate arrays(FPGAs) are susceptible to single event effects(SEEs) induced by environmental factors such as cosmic rays, heavy ions, alpha particles and so on. As technology scales, the issue will be more serious. In order to tackle this issue, two different error correcting codes(ECCs), the shortened Hamming codes and shortened BCH codes, are investigated in this paper. The concrete design methods of the codes are presented. Also, the codes are both implemented in flash-based FPGAs. Finally, the synthesis report and simulation results are presented in the paper. Moreover, heavy-ion experiments are performed,and the experimental results indicate that the error cross-section of the device using the shortened Hamming codes can be reduced by two orders of magnitude compared with the device without mitigation, and no errors are discovered in the experiments for the device using the shortened BCH codes.     

PETN炸药NQR信号处理方法

利用核四极共振(Nuclear Quadrupole Resonance, NQR)原理探测隐藏炸药,具有准确率高、误报率低、无放射性沾染和防护问题等优点. 但NQR信号十分微弱,湮没在噪声中,检测困难,这成为制约NQR技术发展的一项瓶颈. 为提升NQR信号信噪比,根据NQR信号的特点,提出了一种基于改进阈值函数小波变换的NQR信号去噪方法. 计算表明该方法可以有效消除外界噪声对信号的干扰,提高探测的准确性.      

Separation of Organomercury Species Using Nonaqueous Capillary Electrophoresis Coupled with Sample Stacking and Electrokinetic Injection Techniques

A nonaqueous capillary electrophoresis (NACE) method, 30 mM ammonium acetate in methanol as background electrolyte (BGE), was developed for separation of the organomercury species without complexing reagents. The effects of different solutes and solvents in BGE were studied. Three species of organomercury, methylmercury, ethylmercury and phenylmercury, were separated well and all the number of theoretical plates were over 10⁶. The present NACE method was also coupled with sample stacking and electrokinetic injection techniques to enhance the detection sensitivity. Under the optimum conditions, the limit of detection (S/N = 3) is 18 ng mL⁻¹ and the linear relation range from 40 to 750 ng mL⁻¹ were obtained for methylmercury.     

苯并螺环β-溴代酮Wagner-Meerwein重排反应研究及其在(±)-Colchicine形式合成中的应用

报道了在AgBF₄促进下苯并螺环β-溴代酮的Wagner-Meerwein重排反应, 从而发展了一条简捷新颖的构筑天然产物中广泛存在的n,7,6-三环骨架的方法. 作为该反应的应用, 合成了(±)-colchicine的7,7,6-三环母核, 完成了(±)-colchicine的形式合成.     

基于直角网格法的单个和阵列布置下柔性水翼绕流数值模拟

研究柔性水翼在不可压缩流体中的水动力特性,对于船舵和减摇鳍等海洋结构物的设计和性能优化具有重要意义.本文将自主开发的径向基函数虚拟网格法求解器扩展到模拟绕单个或多个柔性水翼的不可压缩流动问题.数值模型基于虚拟网格有限差分法考虑浸入边界对流场的影响,引入紧支径向基函数(compact supported radial basis function,CSRBF)以物面Lagrangian质点追踪复杂的柔性动边界.基于该方法,首先模拟了均匀流中主动拍动的柔性水翼,升阻力系数良好的网格收敛性结果验证了本文方法的精度和可靠性.并研究了柔性水翼在不同振荡频率下的水动力特性,阐述了柔性水翼的推力生成机制.然后模拟了绕阵列布置柔性水翼的流动现象,研究了不同间距和不同振荡频率下水翼表面的升阻力系数变化规律和尾涡特性,观察到紧密布置的柔性水翼在高频振荡下推力系数存在显著的放大效应,同时推力为零时的临界频率提前.     

Comparison of two capillary electrophoresis online stacking modes by analysis of polycyclic aromatic hydrocarbons in airborne particulates

Naphthalene, fluorene, pyrene, anthracene, phenanthrene, and chrysene were successfully separated by CD-modified MEKC (CD-MEKC) using 20 mM borate (pH 9.0) containing 90 mM SDS and 75 mM beta-CD. Two online stacking methods, i.e., sweeping and field-enhanced sample injection (FESI), were explored to enhance the detection sensitivity. The influences of some crucial parameters in sweeping and FESI procedures were investigated. For FESI method, a plug of water and low-conductivity sample matrix was used to increase the stacking efficiency. Compared with the sweeping method, FESI can increase the sensitivity in the range of 10-20-fold. The proposed method was used for the analysis of polycyclic aromatic hydrocarbons in airborne particulates.