RUI: competition kinetics of peroxidation with quantitative NMR spectroscopy

The National Science Foundation Division of Chemistry awarded $350,000 to the California State University Fresno Foundation on September 1, 2026, under the Mathematical and Physical Sciences program (CFDA 47.049) to fund a Research in Undergraduate Institutions (RUI) project investigating peroxidation kinetics using quantitative nuclear magnetic resonance spectroscopy.

Professors Hubert Muchalski and Viswanathan V. Krishnan in the Department of Chemistry and Biochemistry at California State University, Fresno, are developing a new analytical method for measuring peroxidation rates—the major chemical process responsible for degradation of petroleum products, foods, biomolecules, and materials. The research employs fluorine-19 NMR spectroscopy to study peroxyl radical clock assays and will investigate the effects of solvent and temperature on oxygen partition coefficients and beta-fragmentation rates. The team will develop a real-time 19F NMR method for direct observation, identification, and quantification of peroxidation markers, capabilities not currently available through chromatography-based techniques. These methods will support the development of antioxidant inhibitors. The project incorporates quantitative heteronuclear NMR spectroscopy into the undergraduate curriculum by developing new laboratory experiments and educational modules, positioning chemistry students to gain hands-on experience in organic, physical, and analytical chemistry.

Performance occurs in Fresno, California, with a period of performance from September 1, 2026, through August 31, 2029.

Abstract

In this RUI project, professors hubert muchalski and viswanathan V krishnan of the department of chemistry and biochemistry at california state university, fresno, are developing a new approach for studying the mechanism of peroxidation, the major chemical process responsible for the degradation of hydrocarbon-rich petroleum products, foods, biomolecules, and materials. The goal of this research is to leverage fluorine nuclear magnetic resonance spectroscopy to develop a new analytical method for measuring peroxidation rates, a key step in developing inhibitors, also known as antioxidants. Because the project lies at the interface of organic, physical, and analytical chemistry, the research is well suited as a platform for the training and education of students in chemistry. Peroxidation (or autooxidation) is a process in which organic molecules containing weak C?H bonds undergo a radical chain reaction with molecular oxygen. The peroxyl radical clock methodology has emerged as a practical approach for kinetic studies of peroxidation and for measuring inhibition rates of radical-trapping antioxidants. This RUI project will explore the qualitative and quantitative capabilities of 19F NMR spectroscopy to develop an allylbenzene-type peroxyl radical clock assay, investigating the effects of solvent and temperature on its parameters?the oxygen partition coefficient and the rate of beta-fragmentation. The team will also develop a 19F NMR method for direct (REAL-TIME) observation, identification, and quantification of peroxidation markers, which are not currently possible with chromatography-based analytical techniques. These research aims will serve as a vehicle for incorporating quantitative heteronuclear NMR spectroscopy into the undergraduate curriculum by developing new laboratory experiments and educational modules. 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.- subawards are not planned for this award.