Organization of the interior of molecular capsules by hydrogen bonding
Organization of the interior of molecular capsules by hydrogen bonding
复制标题
DOI：
10.1073/pnas.082659799
复制
发表时间：
2002-04-16
影响因子：
11.1
通讯作者：
Jerga, A
中科院分区：
文献类型：
--
作者：
Atwood, JL;Barbour, LJ;Jerga, A
将功能实体包围在保护边界内是生物系统的一个基本特征。在分子尺度上，已经合成和研究了十多年的独立胶囊，其内部体积足够大，可以容纳分子物种。这些胶囊通过共价合成或自组装制备，内部体积从200埃到1500埃不等(3)。尽管生物系统在保护边界内具有显著的有序性，但到目前为止，只有空间限制被用于在分子胶囊内对客人进行排序。在本文中，我们描述了通过氢键结合在一起的六聚体分子胶囊的合成和表征。这些胶囊具有由胶囊骨架内的氢键供体带来的客人的内部秩序，但不被胶囊框架使用。该六聚体胶囊的基本构件是与间苯二酚[4]芳烃和焦性没食子烯相关的四聚大环。前者含有四个通过-CHR单元桥联在一起的1，3-二酚苯环，而后者含有四个桥联在一起的1，2，3-三酚苯环。我们现在报道了相关的混合大环的合成，主要集中在由三个1，2，3-三羟基苯环和一个13-二苯基苯环桥联而成的大环。混合的大环从密切相关的化合物的混合物中自组装，形成内部有序的六面体胶囊。
The enclosure of functional entities within a protective boundary is an essential feature of biological systems. On a molecular scale, free-standing capsules with an internal volume sufficiently large to house molecular species have been synthesized and studied for more than a decade. These capsules have been prepared by either covalent synthesis or self-assembly, and the internal volumes have ranged from 200 to 1,500 Angstrom(3). Although biological systems possess a remarkable degree of order within the protective boundaries, to date only steric constraints have been used to order the guests within molecular capsules. In this article we describe the synthesis and characterization of hexameric molecular capsules held together by hydrogen bonding. These capsules possess internal order of the guests brought about by hydrogen bond donors within, but not used by, the framework of the capsule. The basic building blocks of the hexameric capsules are tetrameric macrocycles related to resorcin[4]arenes and pyrogallo](4]arenes. The former contain four 1,3-dihydroxybenzene rings bridged together by -CHR- units, whereas the latter contain four 1,2,3-trihydroxybenzene rings bridged together. We now report the synthesis of related mixed macrocycles, and the main focus is on the macrocycle composed of three 1,2,3-trihydroxybenzene rings and one 13-dilhydroxybenzene ring bridged together. The mixed macrocycles self-assemble from a mixture of closely related compounds to form the hexameric capsule with internally ordered guests.