Perfluoroalkylation of benzo crown ethers with sodium perfluoroalkanesulfinates in the presence of oxidant

Using Ce(SO4)2 or Mn(OAc)3 as oxidant, dibenzo crown ethers such as dibenzo-18-crown-6 (1) and dibenzo-24-crown-8 (5) and benzo-12-crown-4 (7) reacted smoothly with sodium perfluoroalkanesulfinates (2a-2e) to give the corresponding perfluoroalkylated products (3,4,6,7) in good yields with two isomers obtained in the case of dibenzo crown ethers. This provides a facile synthesis of perfluoroalkyl-containing crown ethers.     

The reaction of perhalofluoroalkanes with sodium hydrogen sulfite or sodium dithionite in the presence of triethylamine

Hydrodehalogenation or hydrosulfonate-dehalogenation products, hydrohalofluoro-carbons or 2-hydropolyhalofluoroalkanesulfonates, were formed respectively from the title reaction under mild condition in good yield.     

固体炸药的磁驱动准等熵压缩实验研究

较宽压力范围内未反应炸药的本构关系和状态方程对于深入和精确认识压缩波作用下炸药组分间相互作用的力学过程和起爆热点的形成机制具有重要意义。较之冲击压缩,磁驱动准等熵压缩加载(无冲击压缩)是获取较宽压力范围内未反应炸药的动态压缩力学特性更有效的手段。基于大电流产生的电磁力作用原理,在国内率先实现了炸药的磁驱动无冲击压缩实验技术。通过对负载电极、炸药样品参数的优化设计和安装工艺的控制,实现了5 GPa载荷内JO-9159炸药的磁驱动准等熵压缩加载。基于激光位移干涉测量技术和Lagrange数据处理方法,获得了JO-9159炸药的速度响应历史和准等熵压缩线。所得结果与文献数据进行了比较,结果表明,在实验压力范围内,JO-9159炸药的等熵压缩线与PBX9501炸药的等熵压缩线一致。     

Dressed Four-Wave Mixing Spectroscopy Modified by Polarization Interference and Atom-Wall Collision in Micrometric Thin Cells

Dressed four-wave mixing （DFWM） spectroscopy is investigated theoretically in some micrometric thin cells. It is found that DFWM spectra can be modified by polarization interference of atoms and transient effects induced by atom-wall collision. This modification can lead to width-narrowing of DFWM lines and facilitates to implement experiment of high resolution DFWM spectroscopy in a confined atomic system.     

基于静力悬浮原理的单晶硅球间微量密度差异精密测量方法研究

单晶硅球间微量密度差异测量是阿伏伽德罗常数量子基准定义的重要研究内容, 也是半导体产业中高纯度单晶硅制备工艺质量控制的主要方法. 为了改善现有非接触相移干涉法测量装置复杂和静力称重法测量不确定度低的特点, 根据单晶硅密度精密测量需要, 实现了一种基于静力悬浮原理的单晶硅球密度相对参比测量方法. 通过改变静压力和温度进行三溴丙烷和二溴乙烷混合液体密度的微量调节, 分别使两个待测单晶硅球在液体中悬浮, 根据悬浮状态时的液体温度和悬浮高度计算出待测单晶硅球密度差值. 通过双循环水浴和PID温度控制系统实现±100 μK的恒温液体测量环境. 通过图像识别和迭代拟合算法实现单晶硅球悬浮高度的测量. 使用PID静压力控制系统实现单晶硅球的稳定悬浮控制, 同时减少Joule-Thomson效应引起的液体温度改变. 利用静力悬浮模型中的温度变化和静压力变化线性关系准确测量出标准液体的压缩系数. 试验结果表明, 这种测量方法可以避免液体液面张力的影响, 测量相对标准不确定度达到2.1×10^-7, 能够实现单晶硅球密度差值的精密测量.     

Asymmetric aza-Henry reaction of fluoromethylated imines catalyzed by cinchona-derived bifunctional thiourea

The asymmetric aza-Henry reaction of fluoromethyl imines derived from 4-methoxyaniline with nitromethane was achieved under mild conditions using cinchona-derived bifunctional thiourea as catalyst. A series of chiral fluoromethylated β-nitroamines were synthesized and their transformation to optically pure 4-fluoromethyl-2-imidazolidones was illustrated.     

Asymmetric synthesis of either diastereomer of trifluoromethylated allylic amines by the selective reduction of trifluoromethyl alpha,beta-unsaturated N-tert-butanesulfinyl ketoimines

Regio- and diastereoselective reduction of chiral trifluoromethyl alpha,beta-unsaturated N-tert-butanesulfinyl ketoimines 1 was achieved by choosing appropriate reducing agent and either diastereomer of the corresponding trifluoromethylated allylic amines was obtained with good yield and excellent diastereoselectivity (up to >99:1 dr).     

Surfactant Mediated Microphase Separation in Miscible Block Copolymer of Poly(4-vinyl pyridine-b-hydroxybutylacrylate)

Chinese Journal of Polymer Science - Miscible disordered block copolymers (BCPs) are rarely studied due to the limits in self-assembly into ordered microstructures. Herein, we proposed a facile...     

AxMn1-xFe2O4铁氧体(A=Zn,Ni)中阳离子的占位有序化行为研究

基于尖晶石晶体结构信息,本文采用热力学三亚晶格模型,将材料热力学计算和第一性原理计算相结合,研究了Zn_xMn_(1-x) Fe_2O_4和Ni_xMn_(1-x)Fe_2O_4立方相中的Zn~(2+)、Ni~(2+)、Mn~(2+)以及Fe~(3+)在8a和16d亚晶格上的占位有序化行为。结果表明:在锰铁氧体中,室温下Mn~(2+)完全占据在8a亚晶格上,Fe~(3+)完全占据在16d亚晶格上,属于正尖晶石结构;随着热处理温度升高,在1 273 K达到热处理平衡时的占位构型为(Fe~(3+)0.09Mn~(2+)0.91)[Fe~(3+)1.91Mn~(2+)0.09]O_4,在热处理温度升至1 473 K时,达到热处理平衡时的占位构型为(Fe~(3+)0.11Mn~(2+)0.89)[Fe~(3+)1.89Mn~(2+)0.11]O_4,均与实验结果符合较好。在锌铁氧体中,室温下Zn~(2+)完全占据在8a亚晶格上,Fe~(3+)完全占据在16d亚晶格上,属于正尖晶石结构;在热处理温度较高时,Zn~(2+)和Fe~(3+)发生部分置换,符合实验结果。在镍铁氧体中,半数的Fe~(3+)在室温下占据在8a亚晶格上,Ni~(2+)与剩下另一半的Fe~(3+)共同占据在16d亚晶格上,仅在热处理温度较高的时候发生微弱变化,亦与已有的实验结果吻合。在此基础上,本文进一步通过热力学模型研究了立方相尖晶石结构的Zn_xMn_(1-x)Fe_2O_4、Ni_xMn_(1-x)Fe_2O_4复合体系中阳离子占位行为与热处理温度对占位的影响规律。