Self-Assembling Polymers: Synthesis and Characterization

自组装聚合物：合成和表征生物合成纳米级大分子能够氢(H)键介导的自组装成具有定制特性和功能的明确的3d结构，是聚合物科学和工程中的一个巨大挑战。这种通过特定的分子间相互作用进行的大分子超分子组装需要统一的链长和受控的h键位点序列。目前乙烯基单体的活性聚合可以产生链长可控的聚合物，但不能控制链的组成和顺序。因此，本研究的目标是合成具有长度和序列特异性的自组装聚合物，并表征其自组装特性。一种新型的模板-活自由基聚合（TLRP）方法将被用于合成此类聚合物，该方法利用活自由基聚合来控制链长，并利用模板来指导单体的分布和序列。模板及其子链具有互补的氢键位点，因此有望自组装成3d结构，如高度排列的双链，让人想起DNA杂交。所提出的研究的具体目标是：(1)设计和合成自组装单体和模板；(2)优化这些单体的活性自由基聚合条件，以获得均匀链和低多分散性为目标；(3)确定模板化-活性自由基聚合工艺条件；(4)分离模板及其子链，并表征其自组装特性。在准备本提案时，已演示了关键概念，以确认所提议研究的可行性。对样品单体进行了活性自由基聚合。此外，还证明了具有互补聚合物链的单体具有较好的自组装性，这是该TLRP的前提条件。智力优势：合成能够自组装成可控超分子结构的纳米级大分子是一个巨大的挑战。本项目将对乙烯基单体进行模板活自由基聚合，以合成这种自组装的乙烯基聚合物。本研究将对聚合物的模板聚合和自组装有一个基本的了解，并为我们使用肽核酸或寡核苷酸作为模板的长期目标提供指导。广泛影响：该项目包括强大的社会和教育组成部分。本研究将为合成新型功能高分子材料开辟一条新途径。这些材料有许多潜在的应用，如反义药物和生物传感器，以及具有特殊机械和热性能的新型丝状材料。结合这项研究，这个项目的教育目标是教育和培养新一代的技术工人队伍，吸引学生进入科学和工程领域。因此，教育活动将涉及各个层次的学生（大学和大学预科）。PI将包括更多的各级学生，特别是少数民族和女性学生，通过以下方式参与研究：(1)通过大学的多元文化事务暑期研究学徒计划接触到大学生，特别是代表性不足的美国印第安人；(2)通过暑期奖学金计划和大学的研究经验计划为本科生提供研究机会。PI还将把这项研究的结果，特别是生物启发材料的合成纳入他的化学工程课程。特别是，PI将为他的CHE 5190/4190和CHE 5170/4170创建一个聚合物实验室，提供给全校研究生和本科生，让学生在聚合物合成、表征和应用方面获得实践经验。因此，该项目将使PI能够接触和教育各个层次的学生，让他们参与研究，并使本科教育与研究和研究生培训计划保持一致。这将提供经验，帮助学生在知识领域之间建立联系和转移概念，并将激励和激发从事科学和工程的学生。

Self-Assembling Polymers: Synthesis and CharacterizationProject SummaryShen / Wyoming / 0650608Bioinspired synthetic nano-scale macromolecules capable of hydrogen (H)-bonding-mediated self-assembly into well-defined 3D-structures with tailored properties and functions is a grand challenge in polymer science and engineering. Such supra-molecular assembly of macromolecules via specific intermolecular interactions requires a uniform chain length and a controlled sequence of H-bonding sites. Current livingpolymerization of vinyl monomers can produce polymers of controlled chain lengths, but cannot control the chain composition and sequence. The goal of this research, therefore, is to synthesize length- and sequence- specific self-assembling polymers and characterize their self-assembly properties. A novel templated-living radical polymerization (TLRP) using living radical polymerization to control the chain lengths and using a template to direct the monomer distribution and sequence will be used to synthesize such polymers. The template and its daughter chain have complementary H-bonding sites and thus are expected to self-assemble into 3D-structures such as highly aligned duplexes, reminiscent of DNA hybridization. Specific aims of the proposed research are to (1) design and synthesize self-assembling monomers and templates; (2) optimize living radical polymerization conditions for these monomers aimed at uniform chains and low polydispersity; (3) define conditions for the templated-living radical polymerization process; and (4) separate the template and its daughter chain and characterize their self-assembling properties. In preparation of this proposal, critical concepts have been demonstrated to confirm the feasibility of the proposed research. Living radical polymerization of sample monomers has been conducted. The preferable self-assembly of the monomers with the complementary polymer chains to the monomers, which is the prerequisite for the proposed TLRP, has also been demonstrated.Intellectual Merit: Synthesis of nan0-scale macromolecules capable of self-assembly into controlled supramolecular structures is a great challenge. This project will produce a templated-living radical polymerization for vinyl monomers to synthesize such self-assembling vinyl polymers. This study will lead to a fundamental understanding of the templated-polymerization and self-assembly of polymers, and provide guidance for our long-term goal of using peptide nucleic acid or oligonucleotides as templates.Broad Impact: The project includes strong societal and educational components. The proposed research will develop a new approach to synthesize new functional polymer materials. These materials have many such potential applications as antisense medicines and biosensors, and new silk-like materials having exceptional mechanical and thermal properties. In conjunction with this research, the education goal of this project is to educate and train a new generation of skilled worker force and attract students to science and engineering. Thus, the education activities will involve students at all levels (college and precollege). The PI will include more students at all levels and particularly minority and women students involved in the research via (1) reaching out toprecollege students, particularly underrepresented American Indians through the university's Multicultural Affairs Summer Research Apprentice Program, and (2) providing research opportunities to undergraduates via the summer scholarship program and the University's Research Experience Program. The PI will also integrate the results from this research, particularly the synthesis of bioinspired materials into his chemical engineering curricula. Particularly, the PI will create a Polymer Lab for his CHE 5190/4190 and CHE 5170/4170 offered to campus-wide graduate and undergraduate students to give the students hands-on experience in polymer synthesis, characterization and applications. Thus, this project will allow the PI to reach out and educate students at all levels, have them involved in the research, and align undergraduate education with research and graduate training programs. This will provide experiences that would help students to make connections and transfer concepts across spheres of knowledge and would stimulate and excite students engaged in science and engineering.