Career: developing redox-active hydrogen bonding to control assembly processes for overcoming synthetic challenges

The National Science Foundation Division of Chemistry awarded Drury University $441,176 on August 1, 2026, through a Project Grant (CFDA 47.049, Mathematical and Physical Sciences) to develop redox-active hydrogen bonding methods for controlling chemical assembly processes and catalysis.

Professor John Kiernicki of the Department of Chemistry will investigate electron transfer reactions as a mechanism for in situ tuning of hydrogen bonding interactions, enabling dynamic control of chemical equilibrium pathways in synthetic catalysis. The research focuses on modulating the strength and persistence of hydrogen bonds through subtle redox-driven changes to electron density in hydrogen bond donors and acceptors, drawing inspiration from allosteric regulation mechanisms in biological catalysis. The project includes an education component targeting greater access for community college transfer students to mentored undergraduate research, with structured integration into research labs, peer and mentor support networks, and hands-on training.

The award supports work performed at Drury University in Springfield, Missouri, over a performance period of August 1, 2026, through July 31, 2029.

Abstract

In this career project, professor john kiernicki of the department of chemistry at drury university is studying new methods to influence chemical equilibria that are governed by hydrogen bonding interactions. Chemical equilibrium lies at the heart of the catalytic processes for the advanced manufacturing of value-added products from commodity chemicals and methods capable of controlling these dynamic processes can enable more efficient catalysis. For years, synthetic chemists have taken cues from biology for catalyst design, and both metal and non-metal catalysts alike have been biologically inspired. Hydrogen bonding interactions are omnipresent in biological catalysis and the presence and/or strength of such interactions are readily modulated by control mechanisms?allosteric regulation, enzyme mobility, charge transfer?that are not readily available to synthetic chemists. This project will explore electron transfer reactions as a method for in situ tuning of hydrogen bonding interactions to enable a new avenue for controlling chemical equilibrium pathways. Professor kiernicki?S education plan targets greater access for community college transfer students to mentored undergraduate research. Rapid integration into a research lab for transfer students will ensure a seamless transition to the four-year institution, the development of a strong support network of mentors and peers, and will ensure the opportunity for hands-on research training. Hydrogen bonds are electrostatic by nature, and, as such, subtle changes to the electron density of the hydrogen bond donor and/or acceptor can greatly impact the strength and persistence of the bond. This project will investigate the role of redox events adjacent to a hydrogen bonding interaction as an in situ method to fine-tune the acidity or basicity of the interaction. Intramolecular hydrogen bonding model systems will be employed to enable precise enthalpic descriptions of changes in hydrogen bond strength while guiding the design of bimolecular systems that promote assembly/disassembly processes. An improved understanding of regulating bimolecular hydrogen bonding interactions will directly translate to improved catalyst design for the capture/orientation of substrates, and ultimately the release of products to enable improved catalytic turnover. 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.