Comprehensive Fluorescence-based Comparative Studies of the Inclusion Properties of Molecular Hosts

超分子化学涉及由两个或多个分子通过非共价分子间相互作用而结合在一起的结构。超分子体系最简单的例子是主客体包合物，其中客体分子被包含在更大的笼状宿主分子的空腔中。我们小组已经建立了两个异构体荧光客体的比较用法，1-苯胺基-8-萘磺酸盐(1，8-ANS)和2-苯胺基-6-萘磺酸盐(2，6-ANS)，它们只是形状不同。之前的工作涉及对两个最广泛使用的分子宿主家族环糊精和葫芦醛的性质的研究，这说明了使用这两个客体进行比较研究的价值。在这项提案中，这两个客体以及7-甲氧基香豆素(7MC)的结合将与另外两个大环主体家族，即杯芳烃和柱芳烃进行探索。这四个主体家族具有不同的空腔大小、形状和属性。在本提案的第一部分，将在水溶液中研究杯芳烃和柱芳烃中1，8-和2，6-AN的包合情况，以补充以前的工作，并对水中这四个宿主家族进行广泛的研究。提案的第二部分涉及对这四个主体家族在非水溶液中进行类似的广泛的比较结合研究，以确定溶剂在主客体包合中的作用。我们最近发表了一项关于柱芳烃在非水溶剂中包合两种ANS的研究，该研究表明结合强烈依赖于所使用的溶剂，并确立了我们进行这些非水研究的能力。这项提议的第三部分涉及使用7MC作为嘉宾，与ANS相比，7MC在形状和尺寸上都更紧凑。该客体在四个宿主家族中的结合将提供对它们的比较结合性质的进一步了解。本研究项目的主要目标是建立对这四个重要的主体家族在水和非水溶液中的空腔性质、客体偏好和包合驱动力的广泛了解，并建立一般和特定的结构结合关系。解决方案中的主客体包含法已经发现了广泛的研究和工业应用，例如在药物递送和消费品中。这四个大环家族的组合提供了一系列可供选择的宿主，了解它们的相对结合性质是至关重要的。以前还没有对这些主客体进行过如此大规模的全面研究；本文提出的创新和雄心勃勃的研究利用三个不同的客体、四个不同的宿主家族以及水溶液和非水溶剂，将提供对这一现象的深刻理解，这将对主客体包含的高效和变革性的学术和工业应用至关重要。

Supramolecular chemistry involves structures consisting of two or more molecules held together by non-covalent intermolecular interactions. The simplest example of a supramolecular system is a host-guest inclusion complex, in which a guest molecule becomes included within the cavity of a larger, cage-like host molecule. Our group has established the comparative use of two isomeric fluorescent guests, 1-anilino-8-naphthalene sulfonate (1,8-ANS) and 2-anilino-6-naphthalene sulfonate (2,6-ANS), which differ only in shape. Previous work involved studies of the properties of the two most widely used families of molecular hosts, cyclodextrins and cucurbiturils, which illustrated the value of using these two guests in comparative studies. In this proposal, the binding of these two guests as well as 7-methoxycoumarin (7MC) will be explored with two other families of macrocyclic hosts, namely calixarenes and pillarenes. These four families of hosts have varying cavity sizes, shapes, and properties. In the first part of this proposal, the inclusion of 1,8- and 2,6-ANS in calixarenes and pillarenes will be studied in aqueous solution, to complement previous work and give an extensive study of these four families of hosts in water. The second part of the proposal involves a similar extensive set of comparative binding studies of these four families of hosts in nonaqueous solution, to firmly establish the role of solvent in host-guest inclusion. We recently published a study of the inclusion of both ANS by a pillarene host in nonaqueous solvents, which showed strong dependence of the binding on the solvent used, and which established our ability to do these nonaqueous studies. The third part of this proposal involves the use 7MC as guest, which is more compact in shape and size compared to ANS. The binding of this guest in the four families of hosts will provide further understanding of their comparative binding properties. The major objective of this research project is to establish an extensive understanding of the cavity properties, guest preferences, and driving forces of inclusion amongst these four important families of hosts in both aqueous and nonaqueous solution, and to establish general and specific structure-binding relationships. Host-guest inclusion in solution has found extensive research and industrial applications, such as in drug delivery and consumer products. The suite of these four macrocyclic families provides an arsenal of hosts from which to choose, and it is essential to understand their comparative binding properties. There has been no previous such large scale comprehensive study with these hosts; the innovative and ambitious research proposed herein making use of three different guests, four different families of hosts, and both aqueous and nonaqueous solvents, will provide a deep understanding of this phenomenon, which will be essential for efficient and transformative academic and industrial applications of host-guest inclusion.