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CHEMISTRY OF RECEPTOR MODELS AND FUNCTIONAL GROUP ARRAYS

受体模型和功能基团阵列的化学原理

基本信息

批准号：
2608834
负责人：
CRAIG S WILCOX
金额：
$ 21.41万
依托单位：
UNIVERSITY OF PITTSBURGH AT PITTSBURGH
依托单位国家：
美国
项目类别：
财政年份：
1987
资助国家：
美国
起止时间：
1987-06-01 至 1999-11-30
项目状态：
已结题

来源：
https://reporter.nih.gov/project-details/2608834
关键词：
carboxylate catalyst chemical binding chemical group chemical models chemical structure function chemical synthesis hydrogen bond hydropathy intermolecular interaction isoprenoid molecular shape receptor receptor binding stereochemistry thermodynamics water solution

项目摘要

Molecular forces, solvation, and controlled molecular interactions that result from these forces are the source of the astounding microscopic order and chemical reaction control that characterize cellular phenomena. The long range goal of this work is to answer significant questions about intermolecular and intramolecular force and to contribute to our general knowledge of molecular forces and aggregation phenomena in aqueous media and in less polar environments. We are particularly interested in physical aspects of the selective recognition of bioactive lipids, small carbohydrates, and aromatic aminoacid side chains. This is a project to study the chemistry of organic molecules that aggregate or fold due to functional group interactions and to study the binding properties and catalytic potential of such systems. The model systems in these projects are chosen based on their relevance to molecular interactions observed in biological systems. New knowledge and useful new data are expected. New generalizations and correlations among observations should arise during these studies and be available to scientists working in the medical and biochemical fields. Quantitative information obtained in this project will be useful to theoreticians for testing and refining chemical computational methods. The development of new catalytic systems or separation technologies may be stimulated by publication of the results expected in this project. Our goals are divided into three subprojects: A. Prepare simple model receptors and a "molecular torsion balance" to provide experimental data on weak intermolecular forces important to biological processes. Edge-face aromatic interactions, cation-aromatic interactions, and context dependence of hydrogen bonding will be studied. B. Investigate the aqueous-based model receptors for alicyclic and aromatic molecules that have been developed in the previous funding period. Prepare a new simpler water soluble cyclophane that will show high enantioselectivity in a 1:1 binding motif and measure its binding free energy with several enantiomeric guests. Use the knowledge gained to explore how hydrogen bonds and lipophilic contacts can combine to create self assembling termolecular structures. We will measure how delta-H, delta-S, and delta-Cp are affected by shape of substrate, shape of host, lipophilic surface contact area, and examine the effects of polar groups adjacent to the lipophilic surface. Isoprene derived subsubstrates and carbohydrates are to be targeted. The catalytic potential of these receptors will be tested. C. Continue the development of our carboxylic acids encased in a structurally restricted chiral alicyclic environment. These are the first examples of chirally encased acids and their carboxylates bind strongly to ureas. The enantioselectivity of these unique receptors will be studied. The acids may function as enantioselective proton sources and catalysts.

分子力，溶剂化作用和受控的分子相互作用，这些力量的结果是令人震惊的微观的来源，有序和化学反应控制表征细胞现象。这项工作的长期目标是回答以下重要问题分子间和分子内力，并有助于我们的一般水介质中分子力和聚集现象的知识以及在不那么极端的环境中。我们对物理特别感兴趣生物活性脂质的选择性识别方面，小碳水化合物和芳香族氨基酸侧链。这是一个研究有机分子化学的项目，聚集或折叠，由于官能团的相互作用，并研究这些系统的结合性能和催化潜力。模型这些项目中的系统是根据它们与分子的相关性来选择的。在生物系统中观察到的相互作用。新知识和有用的新闻数据预计。新的概括和观测之间的相关性应该在这些研究中出现，并提供给科学家，在医学和生物化学领域。获得的定量信息在这个项目将是有用的理论家进行测试和完善化学计算方法新催化体系的开发或分离技术可能会刺激出版的结果，预计在这个项目中。我们的目标分为三个子项目： A.准备简单的模型受体和“分子扭转天平”，提供了重要的弱分子间力的实验数据，生物过程。边-面芳族相互作用，阳离子-芳族将研究氢键的相互作用和背景依赖性。 B。研究脂环族和脂环族的水基模型受体，在之前的资助中开发的芳香分子，期制备一种新的更简单的水溶性环番， 1：1结合基序中的对映选择性，并测量其游离结合能量与几个对映体客人。利用获得的知识，探索氢键和亲脂接触如何联合收割机自组装三分子结构我们将测量Δ H， δ-S和δ-Cp受基底形状、主体形状亲脂性表面接触面积，并检查极性基团的影响与亲脂性表面相邻。异戊二烯衍生的亚基质和碳水化合物是目标。这些催化剂的潜力将测试受体。 C.继续开发我们的羧酸，结构受限的手性脂环环境。这些是第一手性包封的酸及其羧酸盐的实例强烈结合到尿素。将研究这些独特受体的对映选择性。酸可用作对映选择性质子源和催化剂。