Hybrid Bonding Polymers

新技术的发展依赖于新材料的发现和设计。在过去的一个世纪里，聚合物在消费品、制造系统、运输、建筑和医疗产品等领域的生产中发挥了至关重要的作用。这些轻质的软材料是由被称为单体的化学物质生产的，这些化学物质反应形成极大的分子（大分子），这些分子对可持续性提出了挑战，例如众所周知的塑料污染问题。在过去的几十年里，创造被称为“超分子聚合物”的新材料的机会已经出现，这种材料中的单体不反应形成大分子，而是被设计成强烈的相互作用，并模仿传统聚合物的特性。这些结构往往不像传统聚合物那样机械坚固，但可以促进回收和生物降解，也可以产生用于能源，电子和医学等先进应用的材料。该项目研究了开发被称为“混合键合聚合物”的新材料的策略，这种新材料将传统聚合物和超分子聚合物结合在一起，创造出具有合适机械性能和新技术潜力的可持续系统。该项目将培养本科生、研究生和博士后（包括那些来自代表性不足群体的学生）进行高度跨学科的研究，以应对合成有机化学、聚合物化学和材料科学等领域未来的技术挑战。受资助的研究人员将被鼓励参加芝加哥地区K-12学生的科学推广项目。将共价键和非共价键合理地结合在一起的大分子和超分子聚合物的集成作为软材料的关键创新具有巨大的潜力。在这些“杂化键合聚合物”中，形成超分子结构域的小分子可以与具有相同分子功能化的共价聚合物共结晶。这可以产生功能结构，其中具有机械优势的聚合物骨干共价连接到晶体晶格的位置。杂化键还可以产生比全共价聚合物更可持续的结构，在全共价聚合物中，高附加值的小分子可以很容易地回收。这项工作将发展和研究这些独特的结构，它们的自组装机制，以及实验材料的性质。具体来说，要研究的系统将包括可结晶的发色团，如电子供体和受体，以及针对光催化、铁电性和超分子手性等特性的光敏剂。预计其潜在的应用可能包括用于光催化太阳能燃料生产的光收集材料、节能数据存储和传感等。除了潜在的技术影响之外，这里提出的研究将为化学、材料科学和工程专业的本科生、研究生和博士后提供有价值的跨学科培训。这批学生将包括代表性不足的群体的成员，他们将得到PI和实验室其他成员的充分支持。此外，在这个项目上工作的学生和博士后将被鼓励参加通过大学提供的K-12科学推广计划。该奖项反映了美国国家科学基金会的法定使命，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。

Part 1: NON-TECHNICAL SUMMARYThe development of new technologies relies on the discovery and design of new materials. Polymers have been of critical importance over the past century for the production of consumer goods, manufacturing systems, transportation, construction, and medical products, among others. These lightweight soft materials are produced with chemicals known as monomers that react to form extremely large molecules (macromolecules) that have posed challenges in sustainability such as the widely known problem of plastic pollution. Over the past few decades, the opportunity has emerged to create new materials known as “supramolecular polymers” in which monomers do not react to form macromolecules but instead are designed to strongly interact and emulate properties of traditional polymers. These structures tend not to be as mechanically robust as traditional polymers but could facilitate recycling and biodegradation, and also generate materials for advanced applications in energy, electronics, and medicine. This project investigates strategies to develop new materials termed “hybrid bonding polymers” which integrate traditional and supramolecular polymers to create sustainable systems that have suitable mechanical properties and potential for new technologies. The project will train undergraduate, graduate, and postdoctoral students--including those from underrepresented groups--in highly interdisciplinary research needed for future technical challenges at the interface of synthetic organic chemistry, polymer chemistry, and materials science. Researchers supported by the grant will be encouraged to participate in science outreach programs for K-12 students in the Chicago area.PART 2: TECHNICAL SUMMARY The integration of macromolecules and supramolecular polymers in which covalent and noncovalent bonds are rationally integrated has great potential as a key innovation in soft materials. In these “hybrid bonding polymers”, small molecules forming supramolecular domains could be co-crystallized with covalent polymers functionalized with the same molecules. This can generate functional structures in which polymer backbones with mechanical benefits are covalently connected to sites of crystalline lattices. Hybrid bonding could also generate more sustainable structures than fully covalent polymers in which high value-added small molecules can be easily recycled. The proposed work will develop and investigate these unique structures, their self-assembly mechanisms, and also the properties of experimental materials. Specifically, systems to be investigated will include crystallizable chromophores such as electron donors and acceptors as well as photosensitizers targeting properties such as photocatalysis, ferroelectricity, and supramolecular chirality. It is envisioned that potential applications could include light harvesting materials for photocatalytic solar fuel production, energy-efficient data storage, and sensing, among others. Beyond the potential technological impact, the studies proposed here will provide valuable cross disciplinary training to undergraduate, graduate, and postdoctoral students from both chemistry and materials science and engineering programs. The cohort of students will include members of underrepresented groups who will receive ample support from the PI and other members of the laboratory. Additionally, students and postdoctoral fellows working on this project will be encouraged to participate in K-12 science outreach programs that are available through the University. .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.