Controlled symmetry breaking in semicrystalline polymer crystalsomes

半结晶聚合物晶体体中的受控对称性破缺

• 批准号: 2104968
• 负责人: Christopher Li
• 金额: $ 63.67万
• 依托单位: Drexel University
• 依托单位国家: 美国
• 项目类别: Standard Grant
• 财政年份: 2021
• 资助国家: 美国
• 起止时间: 2021-06-01 至 2025-05-31
• 项目状态: 未结题
• 来源: https://www.nsf.gov/awardsearch/showAward?AWD_ID=2104968&HistoricalAwards=false
• 关键词: Controlled; symmetry; breaking; semicrystalline; polymer

NON-TECHNICAL SUMMARY:Semicrystalline polymers constitute the large majority of polymeric materials in use today. While the basic symmetries of polymer crystals are not different from their small molecular counterparts, the long-chain nature of polymers does significantly affect their crystallization behavior. Understanding the structure and morphology of semicrystalline polymers is crucial to improving their properties and broadening their applications. This project concerns the structural control of polymer crystals. The overarching goal of this research is to achieve unique spherical polymer crystals by controlling the crystallization conditions and/or the polymer molecular structure and to elucidate the morphology and the fundamental molecular-level processes involved in such curved-crystal growth. It is anticipated that these well-controlled spherical crystals may find applications in the fields of drug delivery and immunotherapy. The educational component of the proposal includes: 1) Mentoring graduate and undergraduate students. 2) Addressing the need for the education of modern polymer science by developing two class modules that will be used in graduate courses at Drexel University. 3) Involving high school students and teachers, particularly under-represented populations, in the proposed research activities.TECHNICAL SUMMARY: The long-chain nature of polymers brings the most interesting feature to their crystallization behavior: the intricate amorphous domains in a crystalline material. The hierarchical morphology of the intertwining crystalline and amorphous phases accounts for some unique properties of semicrystalline polymers. Based on the correlation between crystal morphology and translational symmetry, polymer crystals are divided into shape-symmetry commensurate crystals and shape-symmetry incommensurate crystals (SSICs). In the latter, crystal morphology dictates broken translational symmetry along at least one unit-cell axis. This project aims to systematically investigate a class of polymer spherical crystals in the context of SSICs. Two approaches, namely a top-down templating technique and a bottom-up molecular engineering method, will be employed to break the translational symmetry in polymer crystals. The recently discovered spherical crystalsomes will be used as the model system. Accordingly, the specific aims of the proposed work are: 1) Understanding curvature-dependent crystallization and melting in polymer crystalsomes. 2) Developing complex crystalsomes via morphological control. 3) Fabricating crystalsomes using spontaneous translational symmetry breaking. This project will advance the field of polymer crystallization and lead to a library of crystalsomes as tailor-designed polymeric nanoparticles. Potential applications for these include drug delivery and immunotherapy..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.

非技术摘要：半晶体聚合物构成了当今使用的大部分聚合物材料。 尽管聚合物晶体的基本对称性与它们的小分子对应物没有什么不同，但聚合物的长链性质确实会显着影响其结晶行为。了解半结构聚合物的结构和形态对于改善其性质并扩大其应用至关重要。该项目涉及聚合物晶体的结构控制。这项研究的总体目标是通过控制结晶条件和/或聚合物分子结构并阐明形态和基本分子水平的过程来实现独特的球形聚合物晶体。预计这些控制良好的球形晶体可能会在药物递送和免疫疗法领域找到应用。该提案的教育部分包括：1）指导毕业生和本科生。 2）通过开发将在德雷克塞尔大学的研究生课程中使用两个类模块来满足现代聚合物科学的教育。 3）在拟议的研究活动中涉及高中生和教师，特别是代表性不足的人群。技术摘要：聚合物的长链性质为他们的结晶行为带来了最有趣的特征：结晶材料中复杂的无定形领域。相互交织的晶体和无定形相的分层形态造成了半稳定聚合物的某些独特特性。基于晶体形态与平移对称性之间的相关性，将聚合物晶体分为形状对称性晶体和形状对称不对称的晶体（SSICS）。在后者中，晶体形态决定了沿着至少一个单位细胞轴的破碎的翻译对称性。该项目旨在在SSIC的背景下系统地研究一类聚合物球形晶体。将采用两种方法，即一种自上而下的模板技术和一种自下而上的分子工程方法，用于打破聚合物晶体中的翻译对称性。最近发现的球形晶体体将用作模型系统。因此，提出的工作的具体目的是：1）理解聚合物晶体体中曲率依赖性的结晶和熔化。 2）通过形态控制发展复杂的晶体体。 3）使用自发翻译对称性破坏制造晶体体。该项目将推进聚合物结晶的领域，并导致晶体库作为量身定制的聚合物纳米颗粒。 这些奖项反映了NSF的法定任务，并被认为是值得通过基金会的知识分子优点和更广泛的影响标准来评估的，反映了NSF的法定任务。

项目成果

Colloidosome-Templated Poly (L-lactic acid) Crystalsomes

• DOI: 10.1016/j.giant.2022.100124
• 发表时间: 2022-10
• 期刊: Giant
• 影响因子: 7
• 作者: Mark C. Staub;Shichen Yu;Christopher Y. Li

Poly (3‐hexylthiophene) (P3HT) Crystalsomes: Tiling 1D Polymer Crystals on a Spherical Surface

聚 (3-己基噻吩) (P3HT) 晶体：在球形表面上平铺一维聚合物晶体

• DOI: 10.1002/marc.202200529
• 发表时间: 2022
• 期刊: Macromolecular Rapid Communications
• 影响因子: 4.6
• 作者: Staub, Mark Clyde;Yu, Shichen;Li, Christopher Yuren
• 通讯作者: Li, Christopher Yuren