熔盐电化学的新进展

本文主要介绍熔盐体系、熔盐电池、熔盐电沉积金属以及合金、电合成化合物材料等方面的新进展 ,预期熔盐电化学在能源、环境保护和资源利用等领域中的应用 .     

两相催化体系中辛烯的氢甲酰化反应研究

考察了反应温度、膦／铑化、表面活性剂种类及浓度、CO／H2压力比等因素对水溶性铑－膦配合物RhCI(CO)(TPPTS)2催化剂催化1－辛烯、2－辛烯氢甲酰化反应活性的影响,并选择出了优化的反应条件。研究结果表明,在该体系中表面活性剂的结果是影响RhCI(CO)(TPPTS)2催化2－辛烯转化率和选择性的重要原因,并对在两相体系2－辛烯氢甲酰化反应中表面活性剂十四烷基二甲基苄基氯化铵（BDAC）明显优于十六烷基三甲基溴化铵（CTAB）的原因进行了探讨。     

ZnCl2-氨基酸 (Leu/Try/Val/Thr)-H2O体系的等温溶度

The solubility properties of the zinc chloride amino acids(Leu/Try/ Val/Thr) water systems at 25 ℃ in the whole concentration range have been investigated by equilibrium method, the corresponding phase diagrams and refractive index curves were constructed. The results indicate the formation of the congruently soluble compound of Zn(Leu)Cl2（A） in Leu system and the incongruently soluble compounds of Zn(Try)Cl2•1/2H2O(B)、 Zn(Val)Cl2 •H2O(C)、 Zn(Val)2Cl2(D)、 Zn(Thr)Cl2•H2O(E) and Zn(Thr)2Cl2(F) in Try/Val/Thr systems, which have not been reported in literature. According to the phase equilibrium result, six solid complexes have been prepared in water, and their compositions have been determined by chemical analysis which are consistent with the results of phase diagrams.     

注射用生物可降解胰岛素纳米微球的制备

共聚物;药剂释放体系;注射用生物可降解胰岛素纳米微球的制备     

REVERSE ATOM TRANSFER RADICAL POLYMERIZATION OF STYRENE WITH COPPER-BASED CATALYST

 "Living"/controlled radical polymerization of styrene was carried out with diethyl 2,3-dicyano-2,3-diphenylsuccinate (DCDPS)/CuCl₂/bipyridine (bipy) initiation system at 120℃. The molecular weights of resultant PSt increased with the monomer conversion and the polydispersities were in the range of 1.37 ～ 1.52. A linear ln([M]o/[M])versus time plot was also obtained indicating the constant concentration of growing radicals during the polymerization with this initiation system. End group analysis by ¹H-NMR spectroscopic studies showed that the end groups of the polymer obtained is cω-functionalized by a chlorine group from the catalyst and a-functionalized by a (carbethoxy-cyano-phenyl)methyl group from the fragments of the initiator. Having C1 atom at the chain end, the PSt obtained can be used as a macroinitiator to promote a chain-extension reaction with fresh St and block copolymerization reaction with a second monomer, such as methyl methacrylate, in the presence of CuC1/bipy catalyst via a conventional ATRP process.     

非理想二元表面活性剂复配增效理论的进一步研究

在Rubingh与Rosen 提出非理想二元表面活性剂复配增效条件基础上,利用相分离模型和正规溶液理论,导出了体系降低表面张力的能力增效条件βs-βm<0,及最佳摩尔分数α1*、最低表面张力γ*cmc12和γ*cmc处对应的临界胶束浓度cmc*12.通过作三条γ～logc曲线或两条γ～logc曲线加上一个cmc值的方法,对C12NMe3Br～C12SO4Na、 C12NMe3Br～C8SO4N两种复配体系进行验证,计算结果与实验结果相符.     

CsF–Si(OEt)4 catalyzed addition of (hetero)aromatic amides to ethyl acrylate

The conjugate addition of some (hetero)aromatic amides to an α,β‐unsaturated ester (ethyl acrylate) proceeds efficiently in the presence of an equimolar amount of the CsF–Si(OEt)₄ system to afford the corresponding ethyl esters of N‐substituted β‐amino acids. Copyright © 2001 John Wiley & Sons, Ltd.     

玻碳电极表面复合配位银电结晶机理研究

以具有实际应用价值的复合配位体系无氰镀银电解液为研究对象, 运用循环伏安和电位阶跃等实验方法, 结合 Scharifker-Hill 经典理论模型分析, 成功获得了Ag在玻碳电极（GCE）表面电沉积的成核机理及成核动力学参数, 并分析了温度对成核方式及成核动力学参数的影响. 结果表明, 该体系下Ag在GCE表面的电沉积是由扩散控制的不可逆过程, 遵循三维瞬时成核生长机理. 随着阶跃电位从-750 mV 负移至-825 mV, 峰值还原电流Im逐渐增大, 达到峰值还原电流所需时间tm逐渐缩短; 扩散系数D变化不大, 基本稳定在（7.61±0.34）×10^-5 cm²·s^-1; 成核密度数N₀则从3.26 ×10⁵ cm^-2提高至10.2×10⁵ cm^-2. 银沉积初期的形貌观察, 验证了其三维瞬时成核生长机理. 提高温度可以显著改善电解液中具备活性的银配位离子的扩散能力, 缩短成核时间, 提升成核密度数N0.     

Quantum evolution speed and its limit in the driven double-well system

We investigate quantum evolution speed in the driven double-well system using the entangled trajectory molecular dynamics method. We emphasize not only the evolution speed of the quantum state but also its limit according to different definitions. The Wasserstein 1-distance is used to quantify the distance between distinguishable quantum states in the phase space, the quantum speed limit based on the geometry has been shown to be the strictest one. The single trajectory's contribution to the quantum speed limit is discussed, which is related to both the time evolution of the trajectory and its position in the total Wigner function. The resonance and chaos strongly enhance the evolution speed and its limit in the driven double-well system. The resonance effect makes a large proportion of representative points pass through the well as a whole, nevertheless, the chaos makes the Wigner function disperse in the phase space.     

One-pot synthesis of selenocarbamates from isocyanates and diselenides using the Zn/AlCl3 system

Several N-alkyl/aryl-Se-alkyl/(aryl)selenocarbamates were prepared from various isocyanates and diselenides by reductive cleavage of Se-Se bond with the Zn/AlCl3 system in dry acetonitrile at 80℃.