Supramolecular approach for synthesis and functionalization of cyclic macromolecules
Supramolecular approach for synthesis and functionalization of cyclic macromolecules
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DOI：
10.1016/j.reactfunctpolym.2007.07.010
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发表时间：
2007-11-01
影响因子：
5.1
通讯作者：
Oike, Hideaki
中科院分区：
文献类型：
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作者：
Oike, Hideaki
这份报告重点介绍了我们最近在基于超分子化学的环状聚合物的合成以及由螺旋肽和卟啉组成的环状大分子对螺旋的立体化学识别方面的研究结果。第一部分将集中于高效合成环状聚合物的静电自组装和共价固定策略。已经证明，单体聚合物组件仅由具有携带二羧酸盐反离子的环铵盐端基团的线性聚合物前驱体形成。通过随后的铵盐基的共价转化，实现了环状聚合物的有效合成。这一过程已经扩展到环状大单体的合成，从而产生了具有共价键和机械键的独特的聚合物网络。第二部分将集中于环宿主对螺旋的立体化学识别。合成了具有金属卟啉单元的α-氨基异丁酸(AIB)环状主体，用于客体结合和手性传感。通过使用这些空腔，通过螺旋多肽客体的络合实现了具有重要生物学意义的“多肽束”，其中三个螺旋链，其中两个来自宿主，一个来自客体，在一个受限的空腔中以立体化学的方式协调，导致在金属卟啉单元的吸收带中产生强烈的手性输出。通过手性构象匹配，还实现了基于主客体分子螺旋感觉的选择性多肽结合事件。(C)2007爱思唯尔有限公司。保留所有权利。
This report highlights our recent findings concerning the synthesis of cyclic polymers based on supramolecular chemistry as well as the stereochemical recognition of helices by a cyclic macromolecule consisting of helical peptides and porphyrins. The first part will focus on an electrostatic self-assembly and covalent fixation strategy for the efficient synthesis of cyclic polymers. It has been shown that a unimeric polymer assembly is formed exclusively from the linear polymer precursor having cyclic ammonium salt end groups carrying dicarboxylate counter ions. An effective synthesis of cyclic polymers has been achieved by the subsequent covalent transformation of the ammonium salt groups. The process has been extended to the synthesis of cyclic macromonomers, which produced a unique polymer network having both covalent and mechanical linkages. The second part will focus on the stereochemical recognition of helices by a cyclic host. alpha-Aminoisobutyric acid (Aib) peptide-based cyclic hosts having metalloporphyrin units have been synthesized for guest binding and chiroptical sensing. By using these cavities, biologically important "peptide bundling" has been realized through complexation of helical peptide guests, where the three helical chains, two of which are from the host and one from the guest, are harmonized stereochemically in a confined cavity, leading to intense chiroptical outputs in the absorption bands of the metalloporphyrin units. The selective peptide bundling events based on helical senses of the host/guest molecules has also been achieved with a chiral conformational matching. (c) 2007 Elsevier Ltd. All rights reserved.