Novel asymmetric synthesis of oseltamivir phosphate (Tamiflu) from (−)-shikimic acid via cyclic sulfite intermediates

A novel asymmetric synthesis of oseltamivir phosphate 1 from the naturally abundant (?)-shikimic acid via 3,4-cyclic sulfite intermediate 3 (Scheme 1) is described. Target compound 1 was obtained in 39% overall yield from this nine-step synthesis, and the characteristic step of the synthesis is the regio- and stereospecific nucleophilic substitution with sodium azide at the allylic (C-3) position of 3,4-cyclic sulfite 3. Since the yield of the direct-aziridine-formation from the unprotected dihydroxyl azide 4 was not satisfactory, two improved preparations of the established compound 7 via protected 3,4-cyclic sulfites 10 and 13 (Scheme 2) have been developed. In these two improved preparations, compound 7 was obtained from 3,4-cyclic sulfite 3 in 7-steps in 64% or 62% overall yield, respectively.     

等离子体气动激励机理数值研究

基于介质阻挡与准直流电弧放电的物理过程, 分析了它们的气动激励机理, 建立了各自的气动激励模型, 并分别研究了它们对低速和超声速流动的激励效果. 结果显示: 介质挡板放电等离子体气动激励机理是改变了连续流体中的三种力, 即由牛顿内摩擦引起的剪切应力、由电动力学引起的体积力及由压力突变引起的冲击力, 其中基于电动力学的体积力效应占主导地位; 临近空间环境中体积力的作用效果更强, 诱导速度更大; 超声速来流下准直流电弧放电气动激励机理主要是等离子体的热阻塞效应, 本文所建立的爆炸丝传热模型可以用于仿真其控制激波的过程; 热电弧对于超声速来流而言就像一个具有一定斜坡角度的虚拟突起, 可用于高超声速飞行器前体激波的控制.     

Characterization of Bioimprinted Tannase and Its Kinetic and Thermodynamics Properties in Synthesis of Propyl Gallate by Transesterification in Anhydrous Medium

Tannase has been extensively applied to synthesize gallic acid esters. Bioimprinting technique can evidently enhance transesterification-catalyzing performance of tannase. In order to promote the practical utilization of the modified tannase, a few enzymatic characteristics of the enzyme and its kinetic and thermodynamics properties in synthesis of propyl gallate by transesterification in anhydrous medium have been studied. The investigations of pH and temperature found that the imprinted tannase holds an optimum activity at pH?5.0 and 40?°C. On the other hand, the bioimprinting technique has a profound enhancing effect on the adapted tannase in substrate affinity and thermostability. The kinetic and thermodynamic analyses showed that the modified tannase has a longer half-time of 1,710?h at 40?°C; the kinetic constants, the activation energy of reversible thermal inactivation, and the activation energy of irreversible thermal inactivation, respectively, are 0.054?mM, 17.35?kJ?mol^?1, and 85.54?kJ?mol^?1 with tannic acid as a substrate at 40?°C; the free energy of Gibbs (??G) and enthalpy (??H) were found to be 97.1 and 82.9?kJ?mol^-1 separately under the same conditions.     

Facile synthesis and responsive behavior of PDMS‐b‐PEG diblock copolymer brushes via photoinitiated “thiol‐ene” click reaction

We present herein a mild and rapid method to create diblock copolymer brushes on a silicon surface via photoinitiated “thiol‐ene” click reaction. The silicon surface was modified with 3‐mercaptopropyltrimethoxysilane (MPTMS) self‐assembled monolayer. Then, a mixture of divinyl‐terminated polydimethylsiloxane (PDMS) and photoinitiator was spin‐coated on the MPTMS surface and exposed to UV‐light. Thereafter, a mixture of thiol‐terminated polyethylene glycol (PEG) and photoinitiator were spin‐coated on the vinyl‐terminated PDMS‐treated surface, and the sequent photopolymerization was carried out under UV‐irradiation. The MPTMS, PDMS, and PEG layers were carefully identified by X‐ray photoelectron spectroscopy, atomic force microscopy, ellipsometry, and water contact angle measurements. The thickness of the polydimethylsiloxane‐block‐poly(ethylene glycol) (PDMS‐b‐PEG) diblock copolymer brush could be controlled by the irradiation time. The responsive behavior of diblock copolymer brushes treated in different solvents was also discussed. © 2012 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2012     

三唑和环戊烯苯并菲衍生物盘状液晶分子的电荷传输性质

电荷传输是有机电子材料的重要性质. 根据Marcus理论模型, 电荷传输为电子-电子相互作用和电子-声子相互作用过程, 电子-声子相互作用耦合强度越大, 重组能越大, 不利于电荷传输. 电子-电子相互作用耦合强度越大, 电荷传输矩阵元越大, 有利于电荷传输. 对含1, 2, 4-三唑、1, 2, 3-三唑和1, 2, 3-三氮-2, 3环戊烯边链的苯并菲衍生物分子的电荷传输性质进行理论研究. 结果表明, 含1, 2, 3-三唑的苯并菲衍生物分子的空穴传输速率和电子传输速率相当, 速率常数为2× 10¹²s^-1. 含1, 2, 4-三唑的苯并菲衍生物分子的空穴传输速率常数为5× 10¹²s^-1, 约为电子传输速率常数的10倍. 含1, 2, 3-三氮-2, 3环戊烯的苯并菲衍生物分子的电子传输速率常数为3× 10¹²s^-1, 约为空穴传输速率常数的10倍. 目标分子的空穴传输或电子传输速率主要受传输矩阵元的影响, 即电子-电子相互作用耦合强度的大小决定传输速率的变化.     

Quantum Discord for Two-Qubit System in a Symmetry-Broken Environment

In contrast with the entanglement, we study the quantum discord dynamics of the two-qubit system in a symmetry-broken environment consisting of a fermionic bath. The quantum discord decay induced by the bath is analysed. By considering the two qubits that are initially prepared in the different X-states, we find that the behaviors of quantum discord and entanglement are different, the robustness of quantum discord depends on the initial state prepared in.     

Controlled Dense Coding Through a Genuine Five-Atom Entangled State in Cavity QED

We present an experimentally feasible scheme for implementing controlled dense coding through a genuine five-atom entangled state in cavity QED. The scheme is insensitive to both the cavity decay and the thermal field. In the scheme that four-atom entangled states can be exactly distinguished with detecting the atomic state, and the controlled dense coding can be realized in a simple way.     

The electric and magnetic properties of epitaxially grown A0.5-xLaxSr0.5MnO3 （A=Pr, Nd） thin film

The epitaxial （single crystal-like） Pr0.4La0.1Sr0.5MnO3 （PLSMO） and Nd0.35La0.15Sr0.5MnO3 （NLSMO） thin films are prepared and characterized, and the electric and magnetic properties are examined. We find that both PLSMO and NLSMO have their own optimum deposition temperature （To） in their growing into epitaxial thin films. When the deposition temperature is higher than To, a c-axis oriented but polycrystalline thin film grows; when the deposition temperature is lower than To, the thin film tends to be a-axis oriented and also polycrystalline. The most important point is that for the epitaxial PLSMO and NLSMO thin films the electronic phase transitions are closely consistent with the magnetic phase transitions, i.e. an antiferromagnetic phase corresponds to an insulating state, a ferromagnetic phase corresponds to a metallic state and a paramagnetic phase corresponds to a semiconducting state, while for the polycrystalline thin films the electronic phase transitions are always not consistent with the magnetic transitions.     

多输入多输出量子密钥分发信道容量研究

量子安全通信是一个量子密钥分发过程,目前采用的通信技术严重制约了量子密钥分发的比特率.将多输入多输出（MIMO）技术应用于量子密钥分发系统,可提高量子密钥分发的比特率,促进量子安全通信向高速大容量发展.文中首先构造出MIMO量子密钥分发信道中多光子纠缠态Wigner算符矩阵.并在此基础上,推导出多光子双模压缩纠缠态Wigner算符矩阵和MIMO量子密钥分发信道容量.为开发稳健的MIMO量子安全通信空时处理算法和优化设计高性能MIMO量子密钥分发系统提供理论支撑和技术基础. 关键词： 多输入多输出 双模压缩态 多光子纠缠态 信道容量