SGER: Template-Controlled Living Polymerization for Synthesis of Self-Assembling Polymers

沈有青，美国怀俄明大学，“SGER：模板控制的活性聚合合成自组装聚合物”。聚合物链与不受控制的氢键位点的结合，通过随机的分子内键和分子间键形成随机的簇和三维网络，从而导致自结合和交叉结合或两者兼而有之。相比之下，氢键位点分布明确的均匀聚合物链（分子间结构和长度相同）可以与其互补链自组装，即形成具有明确键序的高度排列的链双相体。这种聚合物的自组装，让人想起DNA的自组装，可以产生有价值的生物和非生物材料。挑战在于如何合成这种自组装聚合物。首席研究员提出了一种模板控制的活性聚合，用于合成自组装聚合物。探索性研究的目的是证明所提出的模板控制活性聚合是可行的，即聚合过程中单体可以保持在模板上，聚合可以沿着模板进行。本研究的具体目的如下：1)合成模板和单体。2)开发这些单体的活性聚合工艺。3)开发模板控制的活性聚合工艺。本研究将阐明模板控制活性聚合的两个主要问题。跨学科的研究，结合了高分子科学、超分子化学、生物化学、热力学和材料工程的元素，将增强我们对大分子必须均匀才能自组装的基本认识，而不是随机的自结合。这些认识将为今后聚合物自组装的研究奠定基础。除了建立知识库和播种未来的研究之外，拟议的项目还可以产生新的功能材料，例如具有特殊机械和热性能的新型丝状材料。

Youqing ShenUniversity of Wyoming "SGER: Template-Controlled Living Polymerization for Synthesis of Self-Assembling Polymers."Association of polymer chains with uncontrolled distribution of hydrogen bonding sites leads to random clusters and three-dimensional networks through a process of random intra- and intermolecular bonding which leads to self- and cross-association or both. By contrast, uniform polymer chains (same structure and length from molecule to molecule) with a well-defined distribution of hydrogen-bonding sites can self assemble with their complementary chains, that is, they can form highly aligned chain duplexes with well-defined bond sequences. Such polymer self-assembly, reminiscent of DNA self-assembly, can lead to valuable biotic and abiotic materials. The challenge is how to synthesize such self-assembling polymers.The principal investigator proposes a template-controlled living polymerization for the synthesis of self-assembling polymers. The goal of the exploratory research is to demonstrate that the proposed template-controlled living polymerization is viable, i.e. the monomers can be kept on the template during the polymerization and the polymerization can be kept along the template. Specific objectives of the proposed research are as follows:1) To synthesize template and monomers.2) To develop a living polymerization process for these monomers.3) To develop a template-controlled living polymerization process.This research will clarify the two main concerns to the template-controlled living polymerization. The interdisciplinary research, combining the elements of polymer science, supramolecular chemistry, biochemistry, thermodynamics and materials engineering, will enhance our fundamental understanding to which extent macromolecules must be uniform in order to self assemble, as opposed to randomly self associate. Such understanding will be the basis for future research on polymer self-assembly. In addition to building a knowledge base and seeding future research, the proposed project could result in novel functional materials, such as new silk-like materials having exceptional mechanical and thermal properties.