Eigenschaften von Chalkogen-Chalkogen-Bindungen. XII. Reversible Tellurierung von Tetraisopropyldiphosphan; Stabilisierung von Tellurobis(diisopropylphosphan) als Tetracarbonylchromkomplex

Properties of Chalcogene-Chalcogene Bonds. XII. Reversible Telluration of Tetraisopropyldiphosphane, Stabilisation of Tellurobis(diisopropylphosphane) as Tetracarbonylchromium Complex Tetraisopropyldiphosphane 1 reacts with elemental tellurium by tellurium atom insertion to give tellurobis(diisopropylphosphane) 2. 2 is also available from sodium telluride with chlorodiisopropyl phosphane. ^lH, ^l3C, ^3lP and ^l25Te n.m.r. spectra confirm that in solution 2 is in an equilibrium with the educt 1 and elemental tellurium. Reaction of this equilibrium mixture with tetracarbonyl(norbornadiene)chromium(0) provides tetracarbonyl[tellurobis(diisopropylphosphane)]-chromium(0) 3. 3 was isolated in pure state as stable compound; different from 2,3 does not suffer from loss of tellurium at room temperature.     

Migration characteristics of radionuclides 85+89Sr2+, 134Cs+, 125I-, 75SeO3 2- and 152+154Eu(III) in Chinese soils

The migration of radionuclides ⁸⁵⁺⁸⁹Sr²⁺, ¹³⁴Cs⁺, ¹²⁵I^- and ⁷⁵SeO₃ ^2- in calcareous soil from Yuzhong county of Gansu Province (China) at pH 7.8±0.2 and ^152+154Eu(III) in red earth from Yingtan county of Jiangxi Province (China) at pH 4.6±0.2, in presence of CaCl₂ was studied using column experiments. Results indicate that the negative anions, iodide and selenide are mobile nuclides while the migration of positive cations is related to the sorption capacity for the element. Iodide can be assumed to be non-reactive in calcareous soil. The breakthrough curves (BTCs) were fitted to the analytical solution or numerical solution of one-dimensional convection-dispersion transport models. Good agreements were obtained between the measured and predicted concentration profiles.     

有机硅氨基酸衍生物的研究

本文利用含氢有机硅化合物与含双键的氨基酸酯的加成反应,合成了5种新的有机硅氨基酸衍生物。介绍了一种合成N-烷基取代氨基酸酯的新方法。对新化合物进行了元素和光谱分析鉴定。     

水溶液中痕量游离氯的气动电流法测定

气动电流法是适用于水溶液中痕量溶质分析的一种新方法。在试样被酸化的同时,通过氮气使游离氯转入气相,并在覆膜电极检定器上还原为Cl~-加以测定。检定池的电解质为9NH_2SO_4。厚0.5-Mil的聚四氯乙烯膜由表面粗糙化和用聚合物质处理以后,覆膜电极检定器的电流响应一般增加100倍以上。使用处理过的膜其寿命可达六个月。游离氯的检定极限在2ml试样中估计为1.0μg     

微乳液介质—1—（2—吡啶偶氮）—2—萘酚光度法测定汽油中环烷酸铁的含量

本研究了微乳液为介质时，铁与１－（２－吡啶偶氮）－２－萘酚（ＰＡＮ）的显色反应。选择７３０ｎｍ处为测定波长，ε为１．４×１０＾４Ｌ．ｍｏｌ＾－＾１．ｃｍ＾－＾１，铁量在０－５０μｇ／２５ｍｌ范围内符合比耳定律，该法适用于汽油中环烷酸铁的测定。     

双冠醚研究(Ⅳ)——Schiff碱型和仲胺型双-(苯并15冠-5)对碱金属苦味酸盐的萃取行为

仲胺型双冠醚与四苯硼酸碱金属盐在丙酮溶液中。25℃下的电导说明它们与Na~+可能形成1∶1络合物(冠醚单元∶金属离子),而与K~+、Rb~+、Cs~+离子则形成2∶1络合物。用Schlff碱型和仲胺型双-(苯并15-冠-5)在水-氯仿体系中进行萃取,测量了分配比D和萃取平衡常数K,发现后者的K值均大于前者。双冠醚F_2对K~+的萃取能力最强,选择性最佳。     

Poly(methyl methacrylate)/silica/titania ternary nanocomposites with greatly improved thermal and ultraviolet-shielding properties

Poly(methyl methacrylate) (PMMA)/silica/titania ternary nanocomposites with covalent bonding interaction between polymer and inorganic phases have been prepared using a novel non-hydrolytic sol-gel method. Transmission electron microscope (TEM) image of silica/titania binary inorganic component indicates a core-shell-like structure. Scanning electron microscope (SEM) images suggest that the well dispersed silica/titania particles in the hybrid are on the nanometer-scale. The transparencies of nanocomposites are maintained in visible region while the absorption band in ultraviolet (UV) region is red shifted with increasing inorganic content. The thermogravimetric analysis (TGA) results show that the thermal stability of PMMA copolymer increases dramatically with the addition of silica/titania moieties both in nitrogen and in air.     

Effect of the Secondary Reduction on the Enantioselectivity and Function of Additives in the Chiral Oxazaborolidine‐Catalyzed Asymmetric Borane Reduction of Ketones

The secondary reduction in the direct and oxazaborolidine‐catalyzed asymmetric borane reduction of ketones was investigated by the use of GC/MS tracing titration and control experiments. The results indicate that the secondary reduction affects the enantioselectivity only in noncoordinated solvents at low temperature and not under the usual catalytic reduction conditions because the intermediate alkoxyborane is unstable and quickly converts to borane and dialkoxyborane. The function of an alcohol additive in the asymmetric borane reduction of ketones is to consume excess borane in the reduction system thus inhibiting noncatalytic reduction, which leads to increased enantioselectivity in the catalytic reduction.