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

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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.