Material Properties of Complex Macromolecules Containing Synthetic Polyamino Acids

含有合成聚氨基酸的复杂高分子的材料性能

• 批准号: 1809497
• 负责人: Yao Lin
• 金额: $ 36.71万
• 依托单位: University of Connecticut
• 依托单位国家: 美国
• 项目类别: Standard Grant
• 财政年份: 2018
• 资助国家: 美国
• 起止时间: 2018-06-01 至 2022-05-31
• 项目状态: 已结题
• 来源: https://www.nsf.gov/awardsearch/showAward?AWD_ID=1809497&HistoricalAwards=false
• 关键词: Material; Properties; Complex; Macromolecules; Containing

NON-TECHNICAL SUMMARY:The properties and performance of many biological materials rely on the structures and shapes of their constituent molecules, which could be in the form of helices or sheets. Some of the protein materials are even made from predominantly one type of such structure, showing that high material performance can be achieved by relatively simple structural motifs. This project aims to elucidate how a class of synthetic polymers, which possess both a relatively complex molecular architecture and well-defined secondary structural motifs, may allow for the development of new materials with predictable physical properties. The different ways of intermolecular and intramolecular interactions in these complex polymer molecules may turn out to be the primary factor that determines the macroscopic properties. Successful completion of this research may enable the generation of polymeric systems that will approach the level of sophistication and versatility found in some of nature's biomaterials and the properties of these materials may be tailored for a variety of applications. This research project entails the design and preparation of such complex molecules and their supramolecular assemblies, as well as the study of their properties. It also provides a model system of complex macromolecules, enabling comparison of the multiscale assembly and the material properties with predictions from computer simulations and modeling. Graduate and undergraduate students will be trained in this area and acquire skills in polymer synthesis, material characterization, and computer simulations. The program will integrate the research with the development of interdisciplinary courses on bioinspired polymeric materials, provide vibrant research experiences to undergraduates and high-school students, and promote polymer research and its impact on society through lectures and workshops for the public. Emphasis is given to involving underrepresented students at all levels.TECHNICAL SUMMARY:Using living polymerizations and other strategies, polymers with complex architectures and controlled molecular structures can be synthesized for new materials. One central question that arises is how to control the organization of these complex polymers at different scales to achieve targeted material properties. This research puts a particular emphasis on the secondary structures of complex synthetic polymers, and the connection between the different organizations of the structural motifs and the performance of resulting materials. The model system used in this research is the comb-like macromolecules containing polyamino acids (PAAs) as the side chains. Synthetic PAAs are polypeptide model systems that can form alpha-helix or beta-sheet structures, and that can be made on a large scale. Current studies mainly focus on the linear PAAs and their various copolymers. However, incorporating PAAs into complex macromolecular architectures (e.g., comb-like or brush-like) has profound effects on the association and physical properties of the polymers. The research aims to elucidate the relationship between the structural configuration and the material properties of the PAA-grafted comb macromolecules. The investigation begins with the use of water-soluble PAAs that form intermolecular beta-sheets, to guide the association of the comb macromolecules into fibril-based thin films. The mechanical properties of the polymer films will be compared with those made from proteins or linear PAAs. The study will then continue on the hydrophobic PAAs that form alpha-helices, and determine how different structural configurations of the helices may dictate the morphology and mechanical properties of the PAA-grafted comb macromolecules. At the end of the project, the stress-induced transformation of alpha-helix to beta-sheet in the PAA-grafted comb macromolecules will be examined.This award reflects NSF's statutory mission and has been deemed worthy of support through evaluation using the Foundation's intellectual merit and broader impacts review criteria.

非技术总结：许多生物材料的性质和性能取决于其组成分子的结构和形状，这些分子可能是螺旋或片层的形式。一些蛋白质材料甚至主要由一种类型的这种结构制成，表明高材料性能可以通过相对简单的结构基序实现。该项目旨在阐明一类具有相对复杂的分子结构和明确的二级结构基序的合成聚合物如何能够开发具有可预测物理性能的新材料。在这些复杂的聚合物分子中，分子间和分子内相互作用的不同方式可能是决定宏观性质的主要因素。这项研究的成功完成可能使聚合物系统的产生，将接近在一些自然界的生物材料中发现的复杂性和多功能性的水平，并且这些材料的特性可以针对各种应用进行定制。该研究项目涉及此类复杂分子及其超分子组装体的设计和制备，以及它们的性质研究。 它还提供了一个复杂大分子的模型系统，使多尺度组装和材料特性与计算机模拟和建模的预测进行比较。研究生和本科生将接受这方面的培训，并获得聚合物合成，材料表征和计算机模拟方面的技能。该计划将研究与生物启发聚合物材料的跨学科课程的开发相结合，为本科生和高中生提供充满活力的研究经验，并通过讲座和研讨会促进聚合物研究及其对社会的影响。技术概要：使用活性聚合和其他策略，可以合成具有复杂结构和可控分子结构的聚合物，用于新材料。出现的一个中心问题是如何控制这些复杂聚合物在不同尺度下的组织，以实现目标材料性能。本研究特别强调复杂合成聚合物的二级结构，以及结构基序的不同组织与所得材料的性能之间的联系。本研究所用的模型体系是以聚氨基酸（PAAs）为侧链的梳状大分子。合成PAA是可以形成α-螺旋或β-折叠结构的多肽模型系统，并且可以大规模制备。目前的研究主要集中在线性聚丙烯酸及其各种共聚物。然而，将PAA掺入复杂的大分子结构（例如，梳状或刷状）对聚合物的缔合和物理性能具有深远的影响。本研究旨在阐明PAA接枝梳形大分子的结构构型与材料性能之间的关系。该研究首先使用形成分子间β-片层的水溶性聚丙烯酸，引导梳状大分子结合成基于原纤维的薄膜。将聚合物膜的机械性能与由蛋白质或线性PAA制成的那些进行比较。然后，研究将继续对形成α-螺旋的疏水PAA，并确定螺旋的不同结构构型如何决定PAA接枝的梳状大分子的形态和机械性能。在项目结束时，PAA接枝梳状大分子中的α-螺旋向β-折叠的应力诱导转化将被检查。该奖项反映了NSF的法定使命，并通过使用基金会的知识价值和更广泛的影响审查标准进行评估，被认为值得支持。

项目成果

Modeling and Designing Particle-Regulated Amyloid-like Assembly of Synthetic Polypeptides in Aqueous Solution.

水溶液中合成多肽的颗粒调节类淀粉样蛋白组装的建模和设计。

• DOI: 10.1021/acs.biomac.1c01230
• 发表时间: 2022
• 期刊: Biomacromolecules
• 影响因子: 6.2
• 作者: Yang,Tianjian;Benson,Kyle;Fu,Hailin;Xue,Tianrui;Song,Ziyuan;Duan,Hanyi;Xia,Hongwei;Kalluri,Ankarao;He,Jie;Cheng,Jianjun;Kumar,ChallaV;Lin,Yao
• 通讯作者: Lin,Yao

Enzyme-mimetic self-catalyzed polymerization of polypeptide helices

• DOI: 10.1038/s41467-019-13502-w
• 发表时间: 2019-11-29
• 期刊: NATURE COMMUNICATIONS
• 影响因子: 16.6
• 作者: Song, Ziyuan;Fu, Hailin;Cheng, Jianjun
• 通讯作者: Cheng, Jianjun

Regulating the Supramolecular Polymerization of Fibrous Crystalline Structures in Aqueous Solution

水溶液中纤维晶体结构超分子聚合的调控

• DOI: 10.1002/marc.202000677
• 发表时间: 2021
• 期刊: Macromolecular Rapid Communications
• 影响因子: 4.6
• 作者: Xia, Hongwei;Fu, Hailin;Ren, Yuan;Bordett, Rosalie;Zhang, Yanfeng;Fu, Youjun;Lin, Yao
• 通讯作者: Lin, Yao

Generalized Model of Cooperative Covalent Polymerization: Connecting the Supramolecular Binding Interactions with the Catalytic Behavior

协同共价聚合的广义模型：将超分子结合相互作用与催化行为联系起来

• DOI: 10.1021/acs.macromol.1c02606
• 发表时间: 2022
• 期刊: Macromolecules
• 影响因子: 5.5
• 作者: Fu, Hailin;Baumgartner, Ryan;Song, Ziyuan;Chen, Chongyi;Cheng, Jianjun;Lin, Yao
• 通讯作者: Lin, Yao