LARGE RING AND HELICAL COMPLEXING AGENTS FOR METAL IONS

这项研究的目的是开发新型的有机 可以结合金属离子的分子，形成可溶于 有机溶剂和膜。 在这些新分子中，吡啶和 其它杂环朝向金属结合空腔、裂缝或 通过环的融合形成通道，形成最高度预组织的配体 知道的 提出了八种大环或螺旋络合剂， study. 其中六个是由完整的 环的融合 其中四个已经合成。 对第一个托兰的研究将扩展到包括与 元素周期表中的金属 将特别强调 重金属和镧系元素的络合物可能导致 应用，如金属传感器、发光标记和NMR成像 剂. 一种新的torand合成法将用于形成“管状” 分散的中间相（液晶）。 两个新的“扩大”或 提出了“混合杂环”配体，并讨论了它们与大分子配位的络合作用。 将检查金属离子和过渡金属簇。 两个螺旋 提出了不同大小的配体用于研究，并且它们与 将检查碱金属。 这些螺旋配体和管状配体 液晶是合成离子通道的潜在途径， 可以用来模拟生物膜通道， 膜。 双螺旋甚至三螺旋多核配合物 可以由这些新的配体形成。 这些复合物的类似物可能 被开发为与螺旋生物分子特异性地相互作用，例如 蛋白质和核苷酸。 所有的复合物都将被研究 光谱学和晶体学来改善基本的 了解金属与生物分子的相互作用。 新 络合剂将作为离子选择性离子载体进行测试。 用于分析生物液体中金属的电极。 多核 由膨胀的碳纳米管形成的过渡金属络合物可用作 金属酶模型和作为多功能或多电子 催化剂的

The objective of the proposed research is to develop new types of organic molecules that can bind metal ions, forming complexes that are soluble in organic solvents and membranes. In these new molecules, pyridine and other heterocycles are oriented toward the metal-binding cavity, cleft or channel by fusion of rings, forming the most highly preorganized ligands known. Eight large-ring or helical complexing agents are proposed for study. Six are torands in which a large ring is formed by complete fusion of rings. Four of these torands have already been synthesized. Studies of the first torand will be extended to include complexes with metals throughout the periodic table. Particular emphasis will be placed on complexes of heavy metals and lanthanides do may result in applications, such as metal sensors, luminescent markers and NMR imaging agents. A new torand synthesis will be applied to formation of "tubular" discotic mesophases (liquid crystals). Two new "expanded" or "mixed-heterocycle" torands are proposed and their complexation of large metal ions and transition metal clusters will be examined. Two helical ligands of different sizes are proposed for study and their binding of alkali metals will be examined. These helical ligands and the tubular liquid crystals are potential approaches to synthetic ion channels that could be used to model biomembrane channels or to produce permselective membranes. Double-helical or even triple-helical polynuclear complexes may be formed by these novel ligands. Analogues of these complexes might be developed to interact specifically with helical biomolecules, such as proteins and nucleotides. All complexes will be studied spectroscopically and crystallographically to improve fundamental understanding of the interactions of metals with biomolecules. The new complexing agents will be tested as ionophores in ion-selective electrodes for analysis of metals in biological fluids. The polynuclear transition metal complexes formed by expanded torands may be useful as metalloenzyme models and as polyfunctional or multiple-electron catalysts.