Solvent extraction and bulk liquid membrane transport of Co(II) and Ni(II) ammine cations by proton-ionizable crown ethers

Separation efficiencies and selectivities in solvent extraction of Co(II) and Ni(H) ammine cations from aqueous solutions into chloroform and toluene and in transport through bulk toluene membranes by proton-ionizable crown ethers have been determined. Six proton-ionizable crown ethers with differing lipophilicities, polyether cavity sizes and ionizable groups (carboxylic and sulfonic acid functions) were examined. Higher selectivity and efficiency for Co(II) ammine cation extraction was observed for the more lipophilic, proton-ionizable crown ethers. Highly lipophilic crown carboxylic acids provided effective and selective transport of Co(II) ammine cations through bulk toluene membranes.Presented in part at the 6th International Symposium on High Purity Materials in Science and Technology: Preparation, Characterization and Application of Well-Defined Materials, Dresden, GDR, May 1985, Poster D91, Poster Abstracts, pp. 144, 145.All extraction and transport experiments were conducted at this location.     

1－N－（苯并咪唑－1－乙酰基）－4－苯基－3－氨基硫脲金属配合物的合成及结构表征

合成了新配体１－Ｎ－（苯并咪唑－１－乙酰基）－４－苯基－３－氨基硫脲（ＢＰＭＳ），将其与Ｍｎ（Ⅱ）、Ｃｏ（Ⅱ）、Ｎｉ（Ⅱ）、Ｃｕ（Ⅱ）、Ｃｄ（Ⅱ）、Ｚｎ（Ⅱ）、ＵＯ２（Ⅱ）等金属的醋酸盐反应，合成了７个新配合物。所有化合物均经元素分析、ＩＲ、１ＨＮＭＲ和热重分析等表征。红外光谱表明，配体以四齿方式通过烯醇式羰基氧原子、烯醇式硫羰基硫原子以及Ｃ＝Ｎ１和Ｃ＝Ｎ２的氮原子与金属配位     

NETWORK CROWN ETHER POLYMERS WITH CENTRIC FUNCTIONAL GROUP (Ⅳ) SYNTHESIS OF NETWORK CROWN ETHER POLYMER WITH PENDANT DIETHYLAMINO THIAALKYL GROUP AND ITS PLATINUM COMPLEX*

The title polymer was prepared from 5-diethylamino-3-thia-pentyl glycidyl ether anddiethylene glycol bisglycidyl ether via ring-opening copolymerization. It was found that thisreaction could be catalyzed by sodium, but not Lewis acid. The obtained polymer can coordinatewith platinum compound, and the platinum complex is a new kind of catalyst for thehydrosilylation of olefins with triethoxysilane.     

使用手性冠醚及手性柱的HPCE和HPLC法拆分伯胺类药物对映体的对比研究

报道了在缓冲液中添加 1 8-冠 - 6 -四甲酸 (1 8C6 H4 )的高效毛细管电泳法(HPCE)对 8个含氨基的药物进行拆分 ,低 p H值 (2 .0 6 )和较高浓度的 Tris缓冲液(2 0 mmol· L- 1)可加快手性分离。用手性柱 Crownpak CR(+)的高效液相色谱(HPLC)法对与前相同的 8个含氨基药物进行拆分 ,甲醇浓度增大 ,分离度 RS值有所减小。实验结果还表明 ,使用 HPCE法拆分的各物质 RS值大于使用 HPLC法拆分相应物质的 RS值。     

An Explanation on the Electron Ionization Mass Spectra of Crown Ethers by MNDO Computational Method

ＡｎＥｘｐｌａｎａｔｉｏｎｏｎｔｈｅＥｌｅｃｔｒｏｎＩｏｎｉｚａｔｉｏｎＭａｓｓＳｐｅｃｔｒａｏｆＣｒｏｗｎＥｔｈｅｒｓｂｙＭＮＤＯＣｏｍｐｕｔａｔｉｏｎａｌＭｅｔｈｏｄＹＵＡＮＨｕ－ｓｈａｎ，ＴＡＮＧＭｉｎｇ－ｓｈｅｎｇａｎｄＷＵＹａｎｇ－ｊｉｅ（...     

苯并硫杂冠醚的质谱研究

报道了两个苯并硫杂冠醚的电子电离质谱，利用高分辩质谱（ＨＲＭＳ）和碰撞活化－质量分析动能谱（ＣＡＤ－ＭＩＫＥ谱）研究了它们的离子碎裂途径。苯并硫杂冠醚含两个硫原子的碎片离子进一步断裂时以丢失Ｃ２Ｈ４Ｓ为特征。     

Bi(III) halides as efficient catalysts for the O-acylative cleavage of tetrahydrofurans: an expeditious entry to tetralins

The mild (DCM/20 °C), quantitative, regioselective, O-acylative cleavage of tetrahydrofurans using organic acid halides with catalytic Bi(III) halides is reported. X-ray crystallography is used to rationalise the failure of the reaction in the case of certain crowded acid chlorides, and a useful aspect of chemoselectivity is revealed. The synthetic potential of this reaction is illustrated with a highly efficient O-acylative cleavage/intramolecular alkylation approach to tetralins.     

Prediction of Complexation Properties of Crown Ethers Using Computational Neural Networks

A computational neural network method was used for the prediction of stability constants of simple crown ether complexes. The essence of the method lies in the ability of a computer neural network to recognize the structure-property relationships in these host-guest systems. Testing of the computational method has demonstrated that stability constants of alkali metal cation (Na+, K+, Cs+)-crown ether complexes in methanol at 25 °C can be predicted with an average error of ±0.3 log K units based on the chemical structure of the crown ethers alone. The computer model was then used for the preliminary analysis of trends in the stabilities of the above complexes.     

Enantiomeric resolution of underivatized small peptides by HPLC with a chiral crown ether stationary phase

Factors influencing the stereoisomeric resolution of underivatized dipeptides and a representative tripeptide on Crownpak (CR) columns have been investigated. The elution order and relative retention suggest that a combination of chiral, steric, and hydrophobic interactions effects the extent of chiral recognition and the retention achieved during separations. Some dipeptides whose amine terminus is located three atoms from the asymmetric center (such as dipeptides of D ,L -glycine) were resolved, but the elution order was the opposite of that expected for the type of Crownpak column used (CR(+)). Peptides containing hydrophobic substituents were strongly retained, but their retention times could be significantly reduced, and detectability improved, by use of gradient elution. Analysis of a commercial sample of D ,L -leucine-D ,L -alanine revealed the stereoisomers to be present in an unexpected quantitative ratio and demonstrated the utility of these separations for quality assurance and quantitative analyses.     

杂元素冠醚研究（Ⅺ）：邻苯二硒型硒杂冠醚的合成

在碱性条件下，聚邻二硒代苯被硼氢化钾还原成双硒离子后与二卤代和缩后关环得到７个邻苯二硒型硒杂冠醚化合物，其结构经元素分析、ＭＳ、ＩＲ和ＨＮＭＲ证实。