Thursday, November 21, 2024 11/21/2024

Contra-Thermodynamic Catalysis and Fluorine Sculpting; Two Counter Cultural Approaches to Synthesis

Award Number: R35GM139613
ORGANIZATION: NATIONAL INSTITUTE OF GENERAL MEDICAL SCIENCES
OPDIV: NIH
AWARD CLASS: DISCRETIONARY
AWARD ACTIVITY TYPE: SCIENTIFIC/HEALTH RESEARCH (INCLUDES SURVEYS)

Group Awards By:

View Award Abstract

Project Summary/Abstract The objectives of this proposal are two-fold and include the development and conceptual advancement of contra- thermodynamic catalysis and fluorine sculpting. The realization of both objectives will elevate the field of synthesis and positively impact human health through the development of tools for synthesis and chemical biology. While at first blush the directions appear disparate, they both rely heavily on visible light photocatalysis. However, they deviate from one another in the manner in which the excited state photocatalyst is quenched. One by triplet sensitization (Dexter energy transfer), and the other by SET to or from an excited state catalyst. Traditional catalysis has the effect of lowering energy barriers and facilitating reactions but ultimately does not alter the thermodynamics (or spontaneous direction) of the reaction. Our long term objectives are to develop strategies to realize a system that makes formerly impossible, or endergonic, synthesis possible in addition to enabling exergonic synthesis. Achieving this objective, will result in new tools for the study of large molecules, new synthetic methods. Achieving this objective will require the development of reactions which are not subject to the principles of microscopic reversibility, i.e. irreversible reactions that can serve to pump energy into the system, and the ability to harness and store the energy thermodynamic currency that can be used to drive reactions. More tangibly we seek to leverage the cis-to-trans photoisomerization of cycloalkenes to: identify energy pumping reactions, define an energetic currency, and develop strategies to spend the energetic currency to drive reactions that would be otherwise impossible. Realizing these objectives is expected to both enable synthesis via the development of new endergonic (neglecting the photon energy) reactions and methods as well as the development of biological tools that capitalize on the available energy and the spatio-temporal controlled associated with light activated processes. The second direction of this proposal also involves an unorthodox approach to synthesis. Like no other element, fluorine has the ability to modulate the properties of a molecule and its behavior within the human body. Fluorine incorporation into pharmaceuticals has seen exponential growth in recent years, and yet our synthetic capability to obtain organofluorines is surprisingly limited. Owing to fluorine’s location on the periodic table, the selective installation of C–F bonds are exceptionally challenging. Fluorine sculpting is an alternative approach to organofluorine synthesis that begins with a low cost perfluoroarene and selectively carves out the desired high-value organofluorine. It has shown great promise; providing rapid access to organofluorines. Our long term objective is to advance the concept of fluorine sculpting and provide expanded access to organofluorines of unprecedented structural complexity. This newfound ability is expected to result in greater understanding of the role fluorine plays in molecules of interest to human health.


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: 2025 ( Subtotal = $0 )
2025	2024	OKLAHOMA STATE UNIVERSITY	401 WHITEHURST HALL	STILLWATER	OK	74078	PAYNE	USA	Biomedical Research and Research Training	000	4	11/4/2024	NON-COMPETING CONTINUATION	$0
														Subtotal = $0

Issue Date FY: 2024 ( Subtotal = $361,684 )
2024	2024	OKLAHOMA STATE UNIVERSITY	401 WHITEHURST HALL	STILLWATER	OK	74078	PAYNE	USA	Biomedical Research and Research Training	000	4	12/26/2023	NON-COMPETING CONTINUATION	$325,516
2024	2024	OKLAHOMA STATE UNIVERSITY	401 WHITEHURST HALL	STILLWATER	OK	74078	PAYNE	USA	Biomedical Research and Research Training	001	4	5/20/2024	NON-COMPETING CONTINUATION	$36,168
														Subtotal = $361,684

Issue Date FY: 2023 ( Subtotal = $361,684 )
2023	2023	OKLAHOMA STATE UNIVERSITY	401 WHITEHURST HALL	STILLWATER	OK	74078	PAYNE	USA	Biomedical Research and Research Training	001	3	4/6/2023	NON-COMPETING CONTINUATION	$36,168
2023	2023	OKLAHOMA STATE UNIVERSITY	401 WHITEHURST HALL	STILLWATER	OK	74078	PAYNE	USA	Biomedical Research and Research Training	000	3	1/5/2023	NON-COMPETING CONTINUATION	$325,516
														Subtotal = $361,684

Issue Date FY: 2022 ( Subtotal = $361,684 )
2022	2022	OKLAHOMA STATE UNIVERSITY	401 WHITEHURST HALL	STILLWATER	OK	74078	PAYNE	USA	Biomedical Research and Research Training	001	2	6/22/2022	NON-COMPETING CONTINUATION	$36,169
2022	2022	OKLAHOMA STATE UNIVERSITY	401 WHITEHURST HALL	STILLWATER	OK	74078	PAYNE	USA	Biomedical Research and Research Training	000	2	12/30/2021	NON-COMPETING CONTINUATION	$325,515
														Subtotal = $361,684

Issue Date FY: 2021 ( Subtotal = $445,673 )
2021	2021	OKLAHOMA STATE UNIVERSITY	401 WHITEHURST HALL	STILLWATER	OK	74078	PAYNE	USA	Biomedical Research and Research Training	000	1	1/25/2021	NEW	$361,684
2021	2021	OKLAHOMA STATE UNIVERSITY	401 WHITEHURST HALL	STILLWATER	OK	74078	PAYNE	USA	Biomedical Research and Research Training	001	1	8/2/2021	SUPPLEMENT FOR EXPANSION	$83,989
														Subtotal = $445,673

Grand Total All Awards = $1,530,725

Top

All Categories

About

Search

Reports

Data Submission

Award Information

Contra-Thermodynamic Catalysis and Fluorine Sculpting; Two Counter Cultural Approaches to Synthesis

Award Number: R35GM139613

ORGANIZATION: NATIONAL INSTITUTE OF GENERAL MEDICAL SCIENCES

OPDIV: NIH

AWARD CLASS: DISCRETIONARY

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

Federal Websites

Department of Health & Human Services

HHS Operating Divisions

HHS Staff Divisions

Download A Document Viewer