Synthesis of Catenane-based Polymers and Materials Using Orthogonal Metal Templation

在化学系大分子、超分子和纳米化学项目的支持下，华盛顿大学圣彼得堡分校的乔纳森·巴恩斯博士说。路易斯(WUSTL)将研究和扩展有效的合成方法，以制备一系列基于顺丁烯二烯的聚合物和网络材料。链烷是一类机械互锁分子(MIMs)，由于其特殊的分子连接和结构而引起了人们的研究兴趣。例如，机械互锁分子(MIMs)具有定义明确的拓扑结构和独特的分子结构，可以在分子水平上提供传统聚合物无法获得的构象和平移自由度。该项目将导致开发新类别的聚[n]链烷和基于链烷的材料，从而为未来在拓扑控制聚合物和材料领域的研究和开发奠定基础。为了让年轻学生参与STEM(科学、技术、工程和数学)，巴恩斯将与圣路易斯国际象棋俱乐部(SLCC)合作，开发融合国际象棋和科学(如分析思维、规划、专注等)重叠原则的外展活动。WUSTL青年科学家计划(YSP)的学生将接受实习指导。该项目寻求通过实施金属模板化、聚合合成来弥合小分子和聚[n]链烷之间的合成差距，同时还通过开发可与传统单体配对的官能化顺丁烯单体和交联剂来解决潜在的可扩展性问题。这项研究旨在消除合成更高分子量低聚[n]链烷的一些限制。目前的方法在每次迭代后显示产量下降，和/或因为一锅法经常导致无效的交叉反应，从而产生不想要的动力学副产品。从拟议的研究中获得的合成和物理聚合物的基础知识有望帮助开发基于MIM的下一代材料和应用。这些聚合物和材料的表征将允许将关键指标列表，例如热转变温度(Tg+Tm)、缠结的分子量阈值(Mc，Me)和材料特性，包括剪切和杨氏模量，以及韧性、拉伸强度等。本文提出的研究的最终结果将是开发新类别的聚[n]环己烷和基于环戊烷的材料，这一成就将有助于为未来在拓扑控制聚合物和聚合材料领域的研究和开发奠定基础。该奖项反映了NSF的法定使命，并通过使用基金会的智力优势和更广泛的影响审查标准进行评估，被认为值得支持。

With the support of the Macromolecular, Supramolecular, and Nanochemistry Program in the Division of Chemistry, Jonathan Barnes of Washington University-St. Louis (WUSTL) will investigate and expand on efficient synthetic methods to prepare a series of catenane-based polymers and networked materials. Catenanes are mechanically interlocked molecules (MIMs) that have drawn research interest due to their unusual molecular linkages and structures. Mechanically interlocked molecules (MIMs), for example, possess well-defined topologies and unique molecular architectures and can offer conformational and translational degrees of freedom at the molecular level that are simply not accessible with traditional polymers. The project will result in the development of new classes of poly[n]catenanes and catenane-based materials, thus laying the foundation for future research and development in the area of topologically controlled polymers and materials. To engage young students in STEM (science, technology, engineering and mathematics), Barnes will build on a collaboration with the St. Louis Chess Club (SLCC) to develop outreach that would merge the overlapping principles of chess and science (e.g., analytical thinking, planning, focus, etc.). Students from the The Young Scientist Program (YSP) at WUSTL will be mentored with internships.The project seeks to bridge the synthetic gap between small-molecule and poly[n]catenanes by implementing metal-templated, convergent syntheses, while also addressing potential scalability issues through the development of functionalized catenane monomers and crosslinkers that can be paired with traditional monomers. The research aims to remove some of the limitations seen in synthesizing higher molecular weight oligo- and poly[n]catenanes. Current approaches show decreased yields after each iteration, and/or because one-pot approaches often lead to unproductive cross reactions that generate unwanted kinetic byproducts. The fundamental synthetic and physical polymer knowledge gained from the proposed research is expected to aid the development of next-generation MIM-based materials and applications. Characterization of these polymers and materials will allow key metrics to be tabulated, such as thermal transition temperatures (Tg + Tm), molecular weight thresholds for entanglement (Mc, Me), and material properties including shear and Young’s moduli, in addition to toughness, tensile strength, etc. The culmination of the research proposed herein would be the development of new classes of poly[n]catenanes and catenane-based materials, an achievement that would help build a foundation for future research and development in the area of topologically controlled polymers and polymeric materials.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.