LARGE-RING AND HELICAL COMPLEXING AGENTS FOR METAL IONS

拟议研究的目标是开发新型有机食品 可以与金属离子结合的分子，形成可溶于 有机溶剂和膜。在这些新分子中，吡啶和 其他杂环则朝向金属结合腔、裂隙或 通过环的融合，形成最高度预组织的配体 为人所知。提出了8种大环络合剂或螺旋络合剂。 学习。六个是环，其中由完整形成一个大环 环的融合。其中四个环已经被合成了。 对第一环的研究将扩大到包括具有 元素周期表中的所有金属。我们将特别强调 对重金属和稀土络合物的研究可能会导致 金属传感器、发光标记和核磁共振成像等应用 探员们。一种新的环合成方法将应用于“管状”的形成 盘状中间相(液晶)。两个新的“扩展”或 提出了“混合杂环”环及其与大分子的络合 将研究金属离子和过渡金属团簇。两条螺旋线 提出了不同大小的配体及其结合的研究。 将对碱金属进行检查。这些螺旋配体和小管 液晶是合成离子通道的潜在途径， 可用于模拟生物膜通道或生产渗透选择性 膜。双螺旋甚至三螺旋多核配合物 可能由这些新的配体形成。这些络合物的类似物可能 被开发成与螺旋生物分子特异性地相互作用，例如 蛋白质和核苷酸。所有的络合物都将被研究 从光谱学和结晶学角度改善基本面 了解金属与生物分子的相互作用。新的 络合剂将作为离子载体在离子选择性中进行测试 生物体液中金属分析用电极。多核技术 由膨胀环形成的过渡金属络合物可用作 金属酶模型及多官能团或多电子 催化剂。

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.