CHEMISTRY OF RECEPTOR MODELS AND FUNCTIONAL GROUP ARRAYS

分子力、溶剂化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 以细胞现象为特征的有序和化学反应控制。 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，并为我们的一般 水介质中分子作用力和聚集现象的知识 在极地较少的环境中。我们对物理方面特别感兴趣 生物活性脂类的选择性识别方面，小 碳水化合物和芳香氨基酸侧链。 这是一个研究有机分子化学的项目， 由于官能团相互作用而聚集或折叠，并研究 这类体系的结合特性和催化潜力。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。新知识和有用的新知识 数据在意料之中。新的观测值之间的概括和相关性 应该在这些研究过程中出现，并可供科学家工作 在医疗和生化领域。获取的定量信息 将对理论工作者进行检验和提炼有一定的参考价值 化学计算方法。新型催化体系的发展 或者，分离技术可能会通过公布结果而得到刺激 在此项目中预期。 我们的目标分为三个子项目： A.准备简单的受体模型和“分子扭转天平”以 提供有关弱分子间力的实验数据 生物过程。边-面芳香相互作用，阳离子-芳香族 将研究氢键的相互作用和上下文相关性。 B.研究脂环类和脂环类的水基模型受体 在之前的资助中开发的芳香族分子 句号。制备一种新的更简单的水溶性环纸，它将显示出高 1：1结合基序中的对映体选择性及测定其结合自由 能量和几个对映体客人。利用所获得的知识 探索氢键和亲油接触如何结合在一起创建 自组装三分子结构。我们将测量Delta-H如何， Delta-S和Delta-CP受底物形状、宿主形状、 亲油性表面接触面积，并考察极性基团的影响 与亲油性表面相邻。异戊二烯衍生的底物和 碳水化合物是目标。这些化合物的催化潜力 将对受体进行测试。 C.继续开发我们的羧酸 结构受限的手性脂环环境。这是第一次 手性包裹的酸及其羧酸盐的例子强烈地结合到 乌拉斯。这些独特的受体的对映选择性将被研究。 这些酸可用作对映选择性质子源和催化剂。

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.