Application of macrocyclic compounds in chemical analysis
Application of macrocyclic compounds in chemical analysis
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DOI：
10.1021/ac50041a001
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发表时间：
1979-04
影响因子：
7.4
通讯作者：
I. Kolthoff
中科院分区：
文献类型：
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作者：
I. Kolthoff
大环化合物是不带电荷的，含有一个空腔，其中可以吸附阳离子。由此形成的复合物具有很大的分析意义，但与在各种非分析期刊上发表的数百篇论文相比，在分析期刊上发表的关于这些化合物的论文相对较少。在本综述和讨论中，我们通常将大环化合物称为配体，并将它们用符号L表示，而与阳离子Cn+的络合物用LCn+表示。早在1939年，有机化学家就已经制备了一些大环化合物，但直到60年代才认识到它们与阳离子的络合性质。天然大环化合物是一类抗生素，已成为生物化学、物理化学和电分析化学的研究热点。与钠相比，缬氨霉素和一些其他天然配体对K+（和Rb+）具有高度选择性。它们与亲脂型阴离子的钾盐的络合物穿透亲脂膜，从而在被膜分离的两种水溶液之间建立电势差。它们在单独的部分中讨论，并且它们在“电化学部分”中的膜中的应用。在“天然大环化合物”一节中也提到了一种叫做环糊精的化合物的性质，它可以包裹盐和非电解质的整个分子。1967年，Pedersen（1）发表了他的第一篇关于冠醚的论文，题目是“Cyclic Polyethers and Their Complexes with Metal Salts”。从那时起，这些配体和相关的合成大环化合物一直是物理，有机，无机和生物化学家感兴趣的中心，并在较小程度上，分析化学家。佩德森的出版后不久，Lehn等人。(2)在斯特拉斯堡开始了他们的大型系列论文的分析非常重要的大双环化合物称为穴状配体的莱恩。它们的性质和应用在本文的“双环，三环和四环穴醚”一节中介绍。
Macrocyclic compounds are uncharged and contain a cavity in which a cation can be encapsuled. The complexes thus formed are of great analytical interest, but relatively few papers dealing with these compounds have been published in analytical journals as compared to hundreds of publications in a variety of nonanalytical journals. In the present review and discussion, we will often refer to the macrocyclic compounds as ligands and denote them by the symbol L, while a complex with a cation Cn+ is denoted by LCn+.As early as 1939, a few macrocyclic compounds have been prepared by organic chemists, but their complexing properties with cations were not recognized until in the sixties. There are natural macrocyclic compounds which are antibiotics, which have remainedin the center of interest of biochemical, physical, and electroanalytical chemists. Valinomycin and some other natural ligands are highly selective toward K+(and Rb+) as compared to sodium. Their complexes with potassium salts with lipophilic type of anions penetrate through a lipophilic membrane, thus establishing a potential difference between two aqueous solutions separated by the membrane. They are discussed in a separate section and their application in membranes in the “Electrochemistry Section”. Also properties of compounds called cyclodextrins which can encave entire molecules of salts and nonelectrolytes, are mentioned in the section dealing with “Natural Macrocyclic Compounds”. It was in 1967 when Pedersen (1) published his first paper on crown ethers under the title “Cyclic Polyethers and Their Complexes with Metal Salts”. Since then, these ligands and related synthetic macrocyclic compounds have been in the center of interest for physical, organic, inorganic, and biochemists and, to a lesser extent, for analytical chemists. Soon after Pedersen’s publication, Lehn et al.(2) in Strasbourg started their large series on papers on the analytically very important macrobicyclic compounds called cryptands by Lehn. Their properties and applications are presented in the present paper in the section on “Bicyclic, Tricyclic, and Tetracyclic Cryptands”.