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New Paradigms in Bioinorganic Oxidation: Modeling Non-Canonical Effects on Rates and Selectivity

Award Number: R35GM163532
ORGANIZATION: NATIONAL INSTITUTE OF GENERAL MEDICAL SCIENCES
OPDIV: NIH
AWARD CLASS: DISCRETIONARY
AWARD ACTIVITY TYPE: SCIENTIFIC/HEALTH RESEARCH (INCLUDES SURVEYS)
PERIOD OF PERFORMANCE START DATE: 07/15/2026
PERIOD OF PERFORMANCE END DATE: 04/30/2031

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New Paradigms in Bioinorganic Oxidation: Modeling Non-Canonical Effects on Rates and Selectivity - Project Abstract This proposed research involves a broad synthetic modeling program in the Anderson Laboratory at the University of Chicago aimed at understanding and leveraging the principles that govern the oxidative activity of metalloenzymes. Our group has leveraged molecular model complexes to provide significant insights into oxidizing transition metal centers. Our specific goals over the duration of this proposed award are to synthesize and leverage synthetic platforms where emerging hypotheses about bioinorganic oxidations can be rationally and systematically studied. Despite advances over several decades, recent “exceptions” have revealed key holes in our understanding of the oxidative reactivity of bioinorganic oxidants. Specifically, recent results have underscored that secondary effects can be important and even determinative in the rates and selectivity of substrate oxidations. Hydrogen bonding interactions have been the most thoroughly studied influence, but emerging and sparsely tested themes include the importance of stepwise proton or electron transfer driving forces in concerted proton-electron transfer reactivity, the influence of oriented electric fields or electrostatic charge, as well as how carefully choreographed proton and electron transfer pathways mediate the controlled generation of oxidizing intermediates. These factors can have a determinative role in the outcome of biological oxidations of relevance for human health. We aim to investigate these features in detail through a series of molecular synthetic model compounds. Specifically, we have discovered synthetic platforms where we can a) impart highly basic character on transition metal oxo complexes, b) generate large internal electric fields at transition metal active sites through carefully positioned negative charges, and c) load redox-active ligand scaffolds with H-atom equivalents to kinetically activate O2 for oxidative reactivity and catalysis. These systems now prime us to systematically evaluate how the above-mentioned secondary effects dictate oxidative reactivity. We will be able to measure physical parameters such as BDFE’s, pKa’s, and oxidation potentials and correlate them with observed rates for oxidation reactions. The synthetic modularity of our systems enables us to precisely change our complexes as controls to thoroughly test these emerging hypotheses. Taken together, these studies will provide an unprecedentedly clear view on the fundamental parameters that govern biological oxidations with human health relevance. In tandem, this enhanced understanding will lead to useful new synthetic catalysts for odxidations. Key advantages include parallel controls on selectivity, for instance for more acidic C–H bonds instead of homolytically weaker ones. The principles uncovered will also enable more efficient aerobic catalysis, providing more facile and sustainable routes to important oxidative processes. Taken together, this support for our research program will not only enhance the community’s understanding of enzymatic processes that underpin biology and human health, but it will also provide a blueprint for selective and efficient synthetic catalysts.


Issue Date FY	Funding FY	Legal Entity Name	Legal Entity Address	Legal Entity City	Legal Entity State	Legal Entity Zip Code	Legal Entity COUNTY	Legal Entity COUNTRY	Assistance Listing	Award Code	Budget Year	Action Date	Action Type	Action Amount

Issue Date FY: 2026 ( Subtotal = $421,293 )
2026	2026	UNIVERSITY OF CHICAGO	5801 S ELLIS AVE	CHICAGO	IL	60637	COOK	USA	Biomedical Research and Research Training	000	1	7/14/2026	NEW	$421,293
														Subtotal = $421,293

Grand Total All Awards = $421,293

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New Paradigms in Bioinorganic Oxidation: Modeling Non-Canonical Effects on Rates and Selectivity

Award Number: R35GM163532

ORGANIZATION: NATIONAL INSTITUTE OF GENERAL MEDICAL SCIENCES

OPDIV: NIH

AWARD CLASS: DISCRETIONARY

AWARD ACTIVITY TYPE: SCIENTIFIC/HEALTH RESEARCH (INCLUDES SURVEYS)

PERIOD OF PERFORMANCE START DATE: 07/15/2026

PERIOD OF PERFORMANCE END DATE: 04/30/2031

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