CAREER: Cooperative Supramolecular Polymerization from Polypeptide-containing Macromolecules

技术综述：超分子化学在将具有配位、非共价相互作用的小分子组装成超分子结构方面取得了重大进展。然而，合成大分子作为超分子聚合的单体单元的成功应用一直受到限制。从蛋白质的超分子聚合物中推断，大分子单体可以构建巨大的聚合物超结构，并且它们有望具有显著的材料性能和优异的稳定性。这一职业研究的目标是开发经过可控超分子聚合的合成大分子，以形成具有可预测的形态和物理性能的纳米材料。该方法首先研究含有接枝多肽的合成大分子，并利用接枝多肽二级结构之间可预测的相互作用来驱动组装。本研究的目的是：(1)从选择的多肽接枝梳状大分子中合成超分子聚合物并表征其结构；(2)表征超分子聚合物的力学性能并阐明其性质的分子基础；(3)从大分子单元出发，进行动力学和热力学研究以建立超分子聚合中的协同组装机理；(4)推导出用于协同组装和聚合的合成大分子单元设计的一般原则。这项拟议的研究最终可能导致产生接近自然界中发现的复杂程度的聚合物系统？S自组织超分子聚合物。非技术摘要：由生物大分子组装的纳米结构的非凡物理性质长期以来一直激励科学家创造出具有类似精度和效率的合成系统。生物启发合成材料的实用设计已经出现在聚合物科学、化学和生物学的界面上，并可能在可持续塑料、生物医学材料和可再生能源中得到应用。这项拟议的研究将为受控组装创造新的高分子构建块，为组装机制提供见解，并开发具有优异机械强度和自我修复性能的纳米结构材料。在这样的界面上，聚合物研究的增长提供了教育学生和激励他们追求科学和工程职业的机会。该职业奖将允许PI在康涅狄格大学开发一个关于生物灵感聚合物材料的综合研究和教育项目。该项目将满足学生在这一新兴领域对跨学科教育和高质量研究经验的主要需求。拟议的外展计划旨在：(1)将拟议的研究与开发跨学科的聚合物课程相结合；(2)为本科生和高中生提供充满活力的聚合物研究体验；(3)通过为公众提供讲座，促进聚合物研究及其对社会的影响。重点是让代表不足的学生参加所有级别的活动。

TECHNICAL SUMMARY:Supramolecular chemistry has made great progress in assembling small molecules capable of coordinated, non-covalent interactions into supramolecular structures. However, success in the use of large synthetic macromolecules as the monomer units for supramolecular polymerization has been limited. As inferred from supramolecular polymers from proteins, giant polymeric superstructures can be constructed from macromolecular monomers, and they are expected to have remarkable material performance and superior stability. The objective of this CAREER research is to develop synthetic macromolecules that undergo controlled supramolecular polymerization to form nanomaterials with predictable morphology and physical properties. The approach begins with investigations of synthetic macromolecules bearing grafted polypeptides, and takes advantage of the predictable interactions among grafted polypeptide secondary structures to drive the assembly. The research seeks to: (1) synthesize supramolecular polymers from selected polypeptide-grafted comb macromolecules and characterize their structures, (2) characterize the mechanical properties of supramolecular polymers and elucidate the molecular basis of the properties, (3) conduct kinetic and thermodynamic studies to establish the cooperative assembly mechanisms in the supramolecular polymerization from macromolecular units, and (4) deduce the general principles involved in the design of synthetic macromolecular units for cooperative assembly and polymerizations. The proposed research could ultimately lead to the generation of polymeric systems that will approach the level of sophistication and complexity found in nature?s self-organized supramolecular polymers.NON-TECHNICAL SUMMARY:The remarkable physical properties of nanostructures assembled from biological macromolecules have long inspired scientists to create synthetic systems that work with similar precision and efficiency. Practical design of biologically inspired synthetic materials has emerged at the interface of polymer science, chemistry and biology, and may find applications in sustainable plastics, biomedical materials and renewable energy. The proposed research will create new macromolecular building blocks for controlled assembly, provide insights into the assembly mechanisms, and develop nanostructured materials with superior mechanical strength and self-healing properties. The growth of polymer research at such an interface provides opportunities to educate students and inspire them to pursue careers in science and engineering. The CAREER award will allow the PI to develop an integrated research and education program on Bioinspired Polymeric Materials at University of Connecticut. The program will address students' major needs for interdisciplinary education and high quality research experiences in this emerging field. The proposed outreach program seeks to: (1) integrate the proposed research with the development of interdisciplinary polymer courses; (2) provide vibrant polymer research experiences to undergraduates and high-school students and (3) promote polymer research and its impact on society through providing lectures for the general public. Emphasis will be given to involve underrepresented students at all levels.