Synthesis and properties of p-per fluoroalkylcalix [4]arenes

p-Perfluoroalkylealix[4]arenes were prepared readily from the reaction of calix-[4]arene with perfluoroalkyl iodides in the presence of sodium dithionite or sodium hydroxy-methanesulfinate under mild conditions,These fluorine-containing calixarenes showed bettersolubilities in common organic solvents as compared to their nonperfluoroalkylation analogand formed inclusion complexes with many neutral molecules as well as fluorocarbons.     

IrO2电极在含有机小分子水溶液中的电化学活性

通过循环伏安（CV）与电化学阻抗谱（EIS）测试研究了Ti基IrO2系活性涂层电极在含甲醇、甲酸及甲醛三种有机小分子的Na2SO4溶液中的电化学活性,其中以电极/溶液界面的双电层电容来表征电极的活性.结果表明,与同浓度H2SO4溶液相比,该电极在Na2SO4溶液中的电化学活性发生明显下降.有机小分子的加入降低了电极的活性表面积.发现有机物能在较宽的电位范围内发生氧化反应,但在该种电极上的电氧化速率较慢.然而,伴随着析氧反应的发生,有机物的氧化也随之加快.     

Numerical simulations of the process of multiple shock–flame interactions

Based on a weighted essentially nonoscillatory scheme, the multiple interactions of a flame interface with an incident shock wave and its reshock waves are numerically simulated by solving the compressible reactive Navier–Stokes equations with a single-step Arrhenius chemical reaction. The two-dimensional sinusoidally perturbed premixed flames with different initial perturbed amplitudes are used to investigate the effect of the initial perturbation on the flame evolutions. The results show that the development of the flame interface is directly affected by the initial perturbed amplitudes before the passages of reshock waves, and the perturbation development is mainly controlled by the Richtmyer–Meshkov instability(RMI). After the successive impacts of multiple reshock waves, the chemical reaction accelerates the consumption of reactants and leads to a gradual disappearance of the initial perturbed information. The perturbation developments in frozen flows with the same initial interface as those in reactive flows are also demonstrated.Comparisons of results between the reactive and frozen flows show that a chemical reaction changes the perturbation pattern of the flame interface by decreasing the density gradient,thereby weakening the baroclinic torque in the flame mixing region, and therefore plays a dominant role after the passage of reshock waves.     

二氧化碳气体制备层状聚苯乙烯发泡材料

将珠状和粒状聚苯乙烯(PS)样品模压后在高压CO₂条件下饱和, 采取快速升温法制备了结构新颖的层状发泡材料. 通过扫描电子显微镜(SEM)以及不同饱和条件下CO₂在PS中溶解度的分析, 初步研究了区域性弱链段缠结力对气体成核、泡孔形态、泡孔尺寸和分布的影响. 结果表明珠状PS在压制成型过程中其珠粒界面链段相互作用力较弱. 由于基体中界面区域链段的缠结能力不同, 在不同区域CO₂气体的成核和增长也不同, 通过控制发泡的过程参数, 可以得到独特的PS层状泡孔形态.     

以醋酸盐为矿化剂合成金属有机骨架MIL-101

以醋酸钠为矿化剂, 通过水热合成法直接获得了较纯净的Material Institut Lavoisier-101(MIL-101). 样品经粉末X射线衍射、比表面积及孔径分布和热重分析表征, 并与以氢氟酸为矿化剂合成的MIL-101进行了比较. 结果表明, 以醋酸钠为矿化剂合成的MIL-101的性能优于以氢氟酸作为矿化剂合成的MIL-101, 并且样品经后续纯化处理后能进一步提高比表面积和孔容; 用非定域密度泛函法(NLDFT)分析计算得到了MIL-101的孔结构信息. 合成的MIL-101骨架能稳定至300 ℃以上, 其热稳定性略低于以氢氟酸作为矿化剂合成的MIL-101.     

Regiospecific organocatalytic asymmetric aldol reaction of methyl ketones and alpha,beta-unsaturated trifluoromethyl ketones

[structure: see text]. The aldol reaction of methyl ketones and alpha,beta-unsaturated trifluoromethyl ketones occurred under mild conditions with the combination of proline-derived N-sulfonylamide and trifluoroacetic acid as the catalyst to give the corresponding unsaturated alpha-trifluoromethyl tertiary alcohols in high yields with good enatioselectivities.     

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 Fe₂O₄和Ni_xMn_1-xFe₂O₄立方相中的Zn²⁺、Ni²⁺、Mn²⁺以及Fe³⁺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Mn²⁺完全占据在8a亚晶格上,Fe³⁺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_0.09³⁺Mn_0.91²⁺)[Fe_1.91³⁺Mn_0.09²⁺]O₄,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_0.11³⁺ Mn_0.89²⁺)[Fe_1.89³⁺Mn_0.11²⁺]O₄,均与实验结果符合较好。在锌铁氧体中,室温下Zn²⁺完全占据在8a亚晶格上,Fe³⁺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,Zn²⁺和Fe³⁺发生部分置换,符合实验结果。在镍铁氧体中,半数的Fe³⁺在室温下占据在8a亚晶格上,Ni²⁺与剩下另一半的Fe³⁺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预测建立了立方相尖晶石结构的Zn_xMn_1-xFe₂O₄、Ni_xMn_1-xFe₂O₄复合体系中阳离子占位行为与热处理温度对占位的影响。     

LD侧面抽运Nd∶YAG多波长激光器

利用单根Nd∶YAG晶体棒,实现1 064 nm和1 319 nm双波长基频光振荡及其倍频光532 nm、660 nm激光的输出.采用LD侧面抽运单根Nd∶YAG晶体棒实现1 064 nm和1 319 nm基频光振荡,在此基础上使用非线性频率变换技术获得532 nm和660 nm倍频光的输出.结果表明:1 064 nm和1 319 nm基频激光同时输出时功率分别为30.5 W和8.78 W,单独输出时功率分别为35.6 W和11.2 W|在声光调Q频率分别为10.5 kHz和20.5 kHz时,获得了功率分别为5.34 W和1.353 W的532 nm激光和660 nm激光两路同时运转输出、功率分别为6.72 W和1.902 W各路单独输出,两种情况下倍频转换效率均为17.5%和15.4%,不稳定度小于2%.     

2-Chlorotetrafluoroethanesulfinamide induced asymmetric vinylogous Mannich reaction

The generality of (S)-2-chlorotetrafluoroethanesulfinamide (CTFSA) induced asymmetric vinylogous Mannich (AVM) addition reaction has been investigated. The reaction of aldimines derived from (S)-CTFSA with 2-(tert-butyldimethylsilyloxy) furan (TBSOF) took place regioselectively at the γ-site at room temperature in DMSO under air atmosphere to give the desired addition products in syn-configuration with high diastereoselectivities (up to 98:2 dr). However, anti-configuration product as major isomer was obtained in the presence of tetra-butyl ammonium fluoride (TBAF) at −78 °C. Facile removal of the auxiliary group without epimerization demonstrated their synthetic potential for piperidone derivatives.     

Highly enantioselective direct Michael addition of 1,3-dicarbonyl compounds to β-fluoroalkyl-α-nitroalkenes

Cinchona alkaloid catalysts were used in the Michael addition reaction of 1,3-dicarbonyl compounds to β-fluoroalkyl-α-nitroalkenes for the first time. The catalytic system performed well over a broad scope of substrates including β-keto esters and 1,3-diketones with high diastereoselectivities and excellent enantioselectivities (up to 99% ee) under mild conditions. A wide range of useful fluorinated chiral building blocks was synthesized.