Mechanistic Organic Photochemistry: Dark Processes and Toxicity Priming

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With support from the Chemical Structure, Dynamics and Mechanisms-B (CSDM-B) Program of the Chemistry Division, Professor Alexander Greer at the City University of New York, Brooklyn College is analyzing photochemical reactions involving oxygen gas and subsequent processes that arise in their downstream reactions. These studies focus on deconvoluting primary from secondary, tertiary, and quaternary photo-oxidation processes. The work is relevant to topics in synthetic chemistry, physical organic chemistry, and photochemistry. These studies also seek to improve the control of bacterial disinfection, and deepen understanding of organic radical and oxidation chemistry, as well as materials oxidation based on the use of novel artificial surfaces. The project has potential broad impacts to society by providing insight into environmental particulates, materials aging, and water disinfection. The project will support graduate, undergraduate, and high school students to train them in the photo-sciences and provide professional development. Furthermore, Professor Greer will cultivate STEM (science, technology, engineering and mathematics) talent to engage a wider audience in the photo-sciences by developing the American Society of Photobiology’s program of Online Resources for Educators & Students.With this award, the Greer research group will use phase separation of photosensitized oxidation reactions to sort out particular reactive oxygen intermediates that are formed. Steps in sequential light and post-illumination processes are expected to become mechanistically accessible through the use of bi- and triphasic reactions. The research aims to resolve sequential light and post-illumination processes and determine specific primary through quaternary reaction mechanisms. The work will uncover downstream photochemical reactions to deconvolute two-stage light-dark (L-D) and four-stage L-D-L-D events to gain insight into multi-stage oxidative events. The reactive oxygen intermediates formed in these events may be rationally manipulated and their reactivity tuned, which is relevant to many topics. The research is relevant to selective oxidation of natural and synthetic molecules with broader implications for guiding efforts in oxidative anti-microbial targeting, while minimizing damage to non-target sites and 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.