Structural Recognition in Complexation of Organic Compounds (Chemistry)

这项研究得到了有机化学和高分子化学项目的支持。这项研究涉及构建模拟自然界选择性络合和执行高度选择性反应的能力的分子。与酶相比，模型分子相对较小，但基于对相关因素的理解，构建模型分子是为了模拟它们的选择行为。克拉姆博士一直是这项工作的先驱，他最终获得了诺贝尔奖。其目标是了解有机化合物之间络合作用中的结构识别。生物系统中的分子交通控制主要依赖于络合作用中的结构识别，并启发了对简单非生物系统的络合作用的研究。具有聚合结合位点(主体)的有机化合物被设计和制备来与具有互补和发散结合位点(客体)的其他有机化合物络合。这一假说正在被检验，“更强和更具体的复合化适用于其内在结构在复合化(前组织)之前强制组织进行约束的主客合作伙伴。”主体和络合物的结构来源于晶体结构、核磁谱和质谱图以及元素分析。络合自由能与主客体结构有关。宿主中的预组织是通过组装刚性分子模块来形成分子尺寸的强制凹面，具有茶托、碗、杯或花瓶状形状(空洞)。结合基团或增溶基团组成或从其表面突出。分子细胞是通过在其边缘多个键合形成两个或多个空穴而形成的，其强制内部禁锢有机或无机客体，其性质随封装而改变。

This research is supported by the Organic and Macromolecular Chemistry Program. The research involves building molecules that mimic nature's ability to selectively complex and carry out highly selective reactions. The model molecules are relatively small compared to enzymes but are built to simulate their selective behavior, based upon an understanding of the responsible factors. Dr. Cram has been a pioneer in this work, it having culminated in his being awarded a Nobel Prize. The goal is to understand structural recognition in complexation between organic compounds. Molecular traffic control in biological systems depends centrally on structural recognition in complexation, and inspires study of complexation with simple non-biological systems. Organic compounds with convergent binding sites (hosts) are designed and prepared to complex other organic compounds with complementary, divergent binding sites (guests). The hypothesis is being tested "that stronger and more specific complexation applies to host-guest partners whose intrinsic structures enforce an organization for binding prior to complexation (preorganization)." Structures of hosts and complexes derive from crystal structures, nuclear magnetic and mass spectra, and elemental analyses. Free energies of complexation are correlated with host and guest structures. Preorganization in hosts is obtained through assembly of rigid molecular modules to form enforced concave surfaces of molecular dimensions with saucer, bowl, cup, or vase-like shapes (cavitands). Binding or solubilizing groups compose or protrude from their surfaces. Molecular cells are constructed by multiply bonding at their rims two or more cavitands to give carcerands, whose enforced interiors imprison organic or inorganic guests, whose properties change with encapsulation.