新型冠醚及其超分子配合物研究的新进展

介绍了冠醚化学的产生、发展及应用,详细介绍了：几种新型臂式冠醚及其超分子金属配合物的合成;取代冠醚及其金属配合物的合成及应用;新型氮杂冠醚及其金属配合物的合成及应用。并对冠醚化学的发展进行了展望。     

新型冠醚化合物的合成应用新进展

简要介绍了冠醚化学的产生、发展及应用;重点介绍了:(1)新型冠醚化合物的合成及应用;(2)新型冠醚超分子聚合物的合成及自组装;(3)新型金属冠醚的合成及应用,并对冠醚化学的发展进行了展望。     

蓬勃发展的冠醚化学

简要介绍了冠醚的结构、性能,冠醚化学的产生、发展及应用。重点介绍了：①新型冠醚及其金属配合物的合成;②新型冠醚的选择性络合及其自组装;③新型冠醚的络合作用及催化作用。并展望了其广阔的应用前景。     

新型冠醚及其金属配合物的合成及应用

简要介绍了冠醚化学的产生、发展及应用。详细介绍了:(1)新型金属冠醚配合物的合成及应用;(2)新型冠醚及金属配合物的合成及在电磁学中的应用;(3)新型冠醚化合物的合成及在医药学中的应用。并对冠醚化学的发展进行了展望。     

植根深远的冠醚化学

简要介绍了冠醚化学的产生、发展及应用。详细介绍了:(1)新型冠醚化合物的合成及在光学材料中的应用;(2)新型冠醚化合物的合成及在分析分离科学中的应用;(3)新型冠醚化合物的合成及在催化科学中的应用。并对冠醚化学的发展进行了展望。     

冠醚化合物合成应用研究的新进展

简要介绍了冠醚化合物的结构特征及应用，重点综述了新型冠醚的合成及选择性组装键合作用、新型冠醚衍生物的合成及应用、特殊结构冠醚的合成及应用，并对冠醚化学的发展进行了展望。     

新型冠醚化合物的合成及选择性识别作用

介绍了新型冠醚化合物的合成、特殊结构冠醚的合成及选择性识别作用、冠醚对金属离子的选择性络合作用,并对冠醚化学的发展进行了展望。     

新型超分子化合物的合成自组装及应用研究的新进展

简要介绍了超分子化学的定义、概念、产生及应用,详细介绍了:①新型超分子化合物合成及自组装;②新型超分子化合物的合成及选择性识别作用;③超分子冠醚金属配合物的合成及应用。     

大环化学的发展现状与展望

简要介绍了大环化学的产生发展及应用。重点介绍了:新型柱芳烃的合成及应用;新型大环多胺及其衍生物的合成及应用;新型轮烷化合物的合成及应用。并对大环化学的发展进行了展望。     

手性合成手性识别手性拆分及在医药学中应用

简要介绍了手性物质的合成、手性识别、手性拆分及在医药学上的应用。详细综述了:(1)手性合成手性识别手性拆分及在医药学中的应用;(2)新型金属手性超分子配合物的合成及应用;(3)手性杯芳冠醚的合成分子识别及应用。并对手性化学的发展进行了展望。     

硫杂冠醚对Ag(I)和Tl(I)的萃取

基于冠醚的配位化学及软硬酸碱理论,设计并合成了五种硫杂冠醚,系统研究了其对Ag(I)和Tl(I)两种软酸离子的络合能力。模拟计算结果表明,五种冠醚与Ag(I)和Tl(I)络合后构型均发生了转变,且结构优化后的五种冠醚与Ag(I)络合过程的ΔG和ΔU均较负,表现出了一定的配位能力,而与Tl(I)络合过程的ΔG和ΔU均接近于0,配位能力相对较差。五种冠醚对Ag(I)和Tl(I)的萃取实验结果表明,五种冠醚对Ag(I)的络合常数分别为3.97, 6.58, 20.61, 9.76, 13.40,对Tl(I)的络合常数分别为4.24, 4.65, 5.80, 4.77, 4.33;在复杂体系中,冠醚2, 3, 4, 5对Ag(I)均具有较高的萃取率及选择性识别能力,而冠醚1对Ag(I)表现出较差的选择性识别能力。五种冠醚对Tl(I)几乎不具有选择性萃取能力。     

Effect of some potassium selective crown ethers on the permeability and structure of a phospholipid membrane

The effect of some new crown ethers on the cation efflux and phase transition parameters of dipalmitoyl phosphatidylcholine liposomes was studied. The effects were correlated with the lipophilicity of the crown ethers. The results indicate that the presence of two crown ring structures in one crown ether molecule is a prerequisite for the increase of ion permeability of liposomes. The effective crown ethers decrease the temperature, enthalpy and cooperativity of the gel-to-liquid crystalline phase transition. The crown ethers increase membrane permeability for potassium and, to a lesser extent, for rubidium and sodium. The ratio of permeability increase for potassium/rubidium significantly correlates with the lipophilicity of the crown ethers.     

RING-SIZE AND SUBSTTTUENT EFFECTS IN THE SOLVENT EXTRACTION OF ALKALI METAL NITRATES BY CROWN ETHERS IN 1,2-DICHLOROETHANE AND 1 -OCTANOL

ABSTRACT

The extraction of alkali metal nitrate salts by solutions of crown ethers in each of the two diluents 1,2-dichlorethane and 1-octanol has been surveyed. The crown ethers include 18-crown-6, 21-crown-7, and 24-crown-8 ethers bearing cyclohexano, benzo, t-alkylbenzo, and/or furano substitutents. The extraction efficiencies of the different crown ethers are examined in terms of ring-size, substituent, and solvent effects. Partition ratios for the crown ethers between water and either 1,2-dichloroethane or 1-octanol are discussed. The extraction selectivities, expressed as the separation factor for cesium over sodium, are examined in relation to crown ether structure.     

Studies of the Size-Selective Extraction of Alkali Metal Ions by the Synergistic Extraction System,Crown Ether-DI(2-Ethylhexyl) Phosphoric Acid-Benzene

Abstract

In order to take practical advantage of the size-selective cation-coordinating ability of the cyclic polyethers (crown ethers), experiments seeking a means of avoiding the problem of solubilizing a mineral-acid anion in a nonpolar organic diluent were performed. Mixtures of several known extractants and crown ethers were tried. Results presented indicate that organic soluble cation exchangers mixed in solution with crown ethers produce a synergistic extractant mixture that largely exhibits the size-selective properties expected of the crown ether. Data are presented for the extraction of macro concentrations of alkali metals by di(2-ethylhexyl) phosphoric acid—dicyclohexyl-18-crown-6 mixtures at a single pH, and at nonloading condition(σ metal cone < 0.04 M) as a function of pH, 2 to 6. In both cases potassium is synergized most strongly presumably because of its best fit to the crown ether cavity. Other data indicate, however, that the size-fit principle is not as consistent for all alkali metal ions and crown ethers as for potassium and dicyclohexyl-18-crown-6. Other effects such as competition for ion hydration and aqueous-phase distribution of the complex may have important effects that have not been elucidated.     

Crown ether complex cation ionic liquids: synthesis and catalytic applications for the synthesis of tetrahydro-4H-chromene and 1,4-dihydropyridine derivatives

A series of crown ether complex cation ionic liquids (CECILs) are synthesized by crown ethers chelated with sodium benzenesulfonates, and used as a green and environmental catalyst, for the synthesis of tetrahydro-4H-chromene and 1,4-dihydropyridine derivatives by three-component reactions of aromatic aldehydes and malononitrile with cyclic β-dicarbonyls or cyclic β-enaminoketones respectively, in H₂O/EtOH (1:1), at the reflux condition. CECILs, as a green and environmental catalyst, can be easily obtained and are stable. Furthermore, high conversions, short reaction times, and cleaner reaction profiles are some of the advantages of this method.     

Ligands for selective metal ion extraction: A molecular modeling approach

We present a density functional theory (DFT) based study on interaction of alkali metal cations (Li⁺ and Na⁺) with macrocyclic crown ethers of different ring sizes. The minimum energy structures, binding energies, and binding enthalpies of crown ether–cation complexes have been determined with a correlated hybrid density functional, namely Becke’s three-parameter functional, B3LYP using a split valence basis function, 6-311++G(d, p). Geometry optimizations for all the crown ether–cation complexes were carried out with several initial guess structures based on semi-empirical PM3 optimized results. For both metal ions, the calculated values of binding energy and binding enthalpy increase with the increase in size of the crown ether ring, i.e. with the increase in the number of donor oxygen atoms in crown ether. The calculated values of gas phase binding energy for lithium ions are always higher than those for sodium ions in the case of all macrocyclic crown ethers studied at present. The calculated values of binding enthalpy are in good agreement with the reported experimental data.     

杯芳烃及其衍生物的合成与工业应用

杯芳烃是继环糊精，冠醚之后又一类新兴的大环化合物，以其出色的超分子化学性能日益引起化学，化工界的关注。本文综合近年来的文献报道，介绍了杯芳烃及其衍生物的合成以及目前杯芳烃在诸多工业领域中的应用与发展前景。