Investigating the Structural Coupling of Main chain and Sidechain Packing in the Solution Structures of Amphiphilic Coil-Comb Block Copolymers with Crystallizable Sidechains

研究具有可结晶侧链的两亲性线圈-梳状嵌段共聚物溶液结构中主链和侧链堆积的结构耦合

• 批准号: 1609447
• 负责人: Donghui Zhang
• 金额: $ 33.88万
• 依托单位: Louisiana State University
• 依托单位国家: 美国
• 项目类别: Continuing Grant
• 财政年份: 2016
• 资助国家: 美国
• 起止时间: 2016-08-15 至 2022-07-31
• 项目状态: 已结题
• 来源: https://www.nsf.gov/awardsearch/showAward?AWD_ID=1609447&HistoricalAwards=false
• 关键词: Investigating; Structural; Coupling; Main; chain

Synthetic polymers (commonly known as plastics) have a wide range of important applications in our daily life. The properties of polymers are governed by their chemical structures and can be tailored through chemical synthesis. With the support from the Macromolecular, Supramolecular and Nanochemistry Program of the NSF Division of Chemistry, Professor Donghui Zhang of the Louisiana State University designs and synthesizes a type of polymer called polypeptoids. Polypeptoids are structurally very similar to polypeptides of proteins. Her research group seeks to understand how polypeptoids organize themselves to form very small objects of certain shapes and sizes in solution. This knowledge can inform further development of functional materials that are useful for biomedical applications (e.g., drug delivery carriers). This project provides an interdisciplinary training environment for graduate and undergraduate student researchers at all levels. Development of new course materials and outreach activities that are connected to the research topic serve to modernize the scientific curriculum, stimulate interest in chemistry, and enhance public awareness of scientific discoveries and impact. This project focuses on studying amphiphilic, coil-comb shaped block copolymers (BCP) of polypeptoids that have crystallizable sidechains. The goal is to understand the fundamental relationship between the molecular structures and the supramolecular assemblies of these copolymers in dilute solution. It is hypothesized that a highly polar backbone and hydrophobic crystallizing sidechains can lead to hierarchical ordering of the polypeptoid block copolymers at small length scales (in the sub-nanometer range) that are difficult to access by conventional means. BCPs based on polypeptoids are uniquely suited as models for this study due to the strong structural coupling of the main chain and sidechain crystalline packing, the strong tendency of the polar main chains and non-polar sidechains to undergo microphase segregation and the synthetic versatility in tuning the sidechain and main chain structures. Considering the wide range of polymers that have or can be readily modified with n-alkyl sidechains to undergo sidechain crystallization, this study is expected to have broad implications on the design of BCP nanostructures with hierarchical ordering and reversible thermo-responsive characteristics.

合成聚合物（俗称塑料）在我们的日常生活中有着广泛的重要应用。 聚合物的性能由其化学结构决定，并且可以通过化学合成来定制。 在美国国家科学基金会化学部高分子、超分子和纳米化学项目的支持下，路易斯安那州立大学的张东辉教授设计并合成了一种称为多肽的聚合物。 类多肽在结构上与蛋白质的多肽非常相似。 她的研究小组试图了解类多肽如何组织自身以在溶液中形成具有特定形状和尺寸的非常小的物体。 这些知识可以为进一步开发可用于生物医学应用的功能材料（例如药物输送载体）提供信息。 该项目为各级研究生和本科生研究人员提供了跨学科的培训环境。开发与研究主题相关的新课程材料和推广活动有助于实现科学课程现代化，激发对化学的兴趣，并提高公众对科学发现和影响的认识。 该项目重点研究具有可结晶侧链的两亲性、线圈梳状嵌段共聚物（BCP）。 目标是了解稀溶液中这些共聚物的分子结构和超分子组装体之间的基本关系。 据推测，高极性主链和疏水性结晶侧链可以导致多肽嵌段共聚物在小长度尺度（亚纳米范围内）的分层排序，而这是通过常规方法难以获得的。 基于多肽的 BCP 非常适合作为本研究的模型，因为主链和侧链晶体堆积的强结构耦合、极性主链和非极性侧链发生微相分离的强烈倾向以及调节中的合成多功能性侧链和主链结构。考虑到具有或可以容易地用正烷基侧链修饰以进行侧链结晶的多种聚合物，这项研究预计将对具有分级有序和可逆热响应特性的 BCP 纳米结构的设计产生广泛的影响。

项目成果

Solution Self-Assembly of Coil-Crystalline Diblock Copolypeptoids Bearing Alkyl Side Chains

带有烷基侧链的螺旋结晶二嵌段共聚肽的溶液自组装

• DOI: 10.3390/polym13183131
• 发表时间: 2021-09-01
• 期刊: Polymers
• 影响因子: 5
• 作者: Naisheng Jiang;Donghui Zhang
• 通讯作者: Donghui Zhang

Multiscale Crystalline Structure of Confined Polypeptoid Films: The Effect of Alkyl Side Chain Branching

限域多肽膜的多尺度晶体结构：烷基侧链支化的影响

• DOI: 10.1021/acsmacrolett.2c00271
• 发表时间: 2022-09
• 期刊: ACS Macro Letters
• 影响因子: 7.015
• 作者: Wang, Qi;Kang, Liying;Xu, Xiangyu;Zhang, Meng;Chao, Albert;Chen, Jianxia;Han, Zhijing;Yu, Huihui;Li, Ruipeng;Zhao, Yixin;et al
• 通讯作者: et al

Modulating the Molecular Geometry and Solution Self-Assembly of Amphiphilic Polypeptoid Block Copolymers by Side Chain Branching Pattern

通过侧链分支模式调节两亲性多肽嵌段共聚物的分子几何形状和溶液自组装

• DOI: 10.1021/jacs.1c01088
• 发表时间: 2021-04-21
• 期刊: Journal of the American Chemical Society
• 影响因子: 15
• 作者: Kang L;Chao A;Zhang M;Yu T;Wang J;Wang Q;Yu H;Jiang N;Zhang D
• 通讯作者: Zhang D