LEAPS-MPS: Photodynamic Hybrid Polymer Network Sponges and their Structure-Property Relationships

该奖项全部或部分由《2021年美国救援计划法案》（公法117-2）资助。非技术总结：本研究的目标是对一系列选择性、光激活的智能材料海绵有一个基本的了解，这些海绵可用于环境修复无处不在的有毒污染物，例如全氟烷基（PFAS）“永远的化学品”。该项目还将融合一个多元化的研究团队来开展这项工作，并影响，培训和指导广泛的中间，高中生和本科生招募和培训他们未来在美国的成功科学劳动力。具体来说，PI的小组将合成硅基光-响应海绵，可以捕获特定的物质，并经历独特的可逆收缩现象，然后根据需要用特定的光波长和能量将它们排出。这种光驱动的过程在硅网络等固体材料中非常复杂，这项研究将有助于了解这些响应海绵在具有不同的构建块时的行为，这些构建块可以改变形状或使用光分解。调查还将确定材料的结构如何影响它们的行为和选择性吸收和释放特定物质的能力。最后，他们的能力和效率在修复PFAS型化合物，这是很难选择性地从水源中分离，将详细说明。种族和民族多样化的高中和本科生将有机会为该项目的发展做出贡献，并与BGSU的科学家一起获得实验室培训，以帮助学生群体向科学为基础的职业多样化。一系列研讨会的重点是智能光响应材料，环境修复和健康优先事项，以及有机会花时间在实验室里跟踪学生科学家将在少数民族高度集中的地方进行（沃伦，密歇根州/托莱多，俄亥俄州）。这些机会将有助于吸引和留住大批科学家。 技术总结：PI及其团队将开发可重复使用且坚固的高孔隙率“智能”海绵，这些海绵在光照射后可经历大体积变化，最终用于持久性污染物（例如PFAS）的环境修复。Q-倍半硅氧烷网络的凝胶和固体将与具有烯丙基或乙烯基官能化的设计的光可切换和动态基团交联。这些新型光响应材料的结构与性能关系将被确定 为了改善光响应行为，确定高性能材料的组成及其物质吸收/释放能力（即石油化学品）。尽管有机硅材料在各种家用和工业产品中普遍使用，但由于功能化和倍半硅氧烷固有刚性的复杂性，倍半硅氧烷作为动态材料的用途仍然比传统聚合物探索得少。这些材料通过克服合成、结构和致动限制而提供优于典型光动力海绵（即水凝胶、有机凝胶）的优点。这些包括由于硅氧烷核而增加的环境稳定性和更好的机械性能，对与许多目标物质一起工作的可调性的优异控制，以及容易的结构组装。该研究还将扩大探索改进方法，以捕获全氟烷基物质（PFAS）等致癌持久性“永久性化学品”，以改善人类和环境健康。对于教育计划，大学生将与区域公司一起参与科学工作，建立职业发展关系，并体验现实世界的科学挑战，作为公共影响推广的一部分。导师将给予一组不同的初中和高中学生，因为他们参加聚合物研讨会和实验室研究经验，以提供科学的重要性，以及如何拟议的研究可能会影响社会在个人和更广泛的范围内的见解。这些举措旨在通过动手互动，联系以及与来自不同背景的科学家群体合作，增加青年在STEM领域的参与。该奖项反映了NSF的法定使命，并被认为是值得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的支持。

This award is funded in whole or in part under the American Rescue Plan Act of 2021 (Public Law 117-2).NON-TECHNICAL SUMMARY:The goal of this research is to develop a fundamental understanding of a series of selective, light activated smart material sponges useful for environmental remediation of omnipresent toxic pollutants such as perfluoroalkyl (PFAS) “forever chemicals.” This project will also meld together a diverse team of researchers to carry out this work and to influence, train, and mentor a broad representation of middle, high school and undergraduate students to recruit and train them for future success in the U.S. science workforce.Specifically the PI's group will synthesize silicon-based light-responsive sponges that can capture specific substances and undergo unique reversible shrinking phenomena to then expel them on demand with certain light wavelengths and energies. This light-driven process is quite complex in solid materials such as silicon networks and this research will aid in gaining an understanding of how these responsive sponges behave when having different building blocks that either change shape or break apart using light. The investigation will also determine how the structures of the material influence their behavior and ability to selectively soak up and release explicit substances on demand. Lastly, their abilities and efficiencies in remediation of PFAS type compounds, which are difficult to selectively isolate from water sources, will be detailed. Racially and ethnically diverse high school and undergraduate students will have the opportunity to contribute to the development of this project and gain laboratory training with scientists at BGSU to aid in the diversification of the student body toward science-based careers. A series of workshops focused on smart light responsive materials, environmental remediation and health priorities as well as the opportunity to spend time shadowing student scientists in the laboratory will be conducted in local areas with high concentrations of under-represented minorities (Warren, MI / Toledo, OH). These opportunities will assist in both attracting and retaining an expansive array of scientists. TECHNICAL SUMMARY:The PI and his group will develop reusable and robust high porosity "smart" sponges that can experience large volume changes after light irradiation to ultimately be used for environmental remediation of persistent pollutants (e.g. PFAS). Gels and solids of Q-silsesquioxane networks will be cross-linked with designed photoswitchable and dynamic groups that feature allyl or vinyl functionalization. Structure-property relationships of these novel photoresponsive materials will be determined to improve photoresponsive behaviors, determine what makes a high-performance material and its substance uptake/release ability (i.e. petrochemicals). Silsesquioxanes’ use as dynamic materials remains less explored than traditional polymers due to the intricacies of functionalization and silsesquioxanes’ inherent rigidity, despite the prevalence of silicone materials in a variety of household and industrial products. These materials offer advantages over typical photodynamic sponges (i.e. hydrogels, organogels), by overcoming synthetic, structural, and actuation limitations. These include increased environmental stabilities and better mechanical properties due to siloxane cores, excellent control of tunability to work with many target substances, and facile structural assembly. This research will also expand the exploration of improved methods for the capture of cancer-causing persistent “forever chemicals” such as perfluoroalkyl substances (PFAS) for the improvement of human and environmental health. For educational initiatives, university students will participate in scientific endeavors with regional companies to build career development relationships and experience real-world scientific challenges as part of public impact outreach. Mentorship will be given to a diverse set of middle and high school students as they participate in polymer workshops and laboratory research experiences to provide insight on the importance of science and how the proposed research may impact society on an individual and broader scale. These initiatives aim to increase youth involvement in the STEM fields by hands-on interactions, connections, and working with a diverse group of scientists from various backgrounds..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.