Modelling the Repair of Carbon-Centered Protein Radicals by Phenolic Antioxidants
department or school: Pharmaceutical Sciences, Faculty of
department or school: Non UBC
data provider: DSpace
identifier citation: Antioxidants 13 (11): 1368 (2024)
creator: Walton-Raaby, Max
creator: Floen, Tyler
creator: Mora-Diez, Nelaine
issued: 2024-11-29T21:10:21Z
issued: 2024-11-08
description: Oxidative stress is a biological process that has been linked to many diseases, hence understanding how to prevent and repair it is essential to medicine. The thermodynamics and kinetics of the repair reactions of radically damaged leucine (a lateral chain in a simplified protein environment) by twenty phenolic antioxidants are studied at the M06-2X(SMD)/6-31++G(d,p) level of theory in water and pentyl ethanoate. The two repair mechanisms modelled are formal-hydrogen atom transfer (f-HAT) and single electron transfer (SET). Although all f-HAT reactions are thermodynamically favourable, only one of the phenols produced rate constants in the diffusion limit, exhibiting biological relevance. SET is not suspected to be an important repair pathway for the phenols studied. We show that the Bell–Evans–Polanyi principle, which relates thermodynamics and kinetics properties for a reaction, breaks down when comparing between the solvents, protein repair sites, and the phenolic antioxidants. While thermodynamic data can be used as valuable screening tools, the kinetic calculation of rate constants in solution is crucial for enhancing the biological relevance of theoretical studies.
aggregated CHO: https://circle.library.ubc.ca/rest/handle/2429/89756
note: Citation: Walton-Raaby, M.; Floen, T.;Mora-Diez, N. Modelling the Repairof Carbon-Centered Protein Radicalsby Phenolic Antioxidants.Antioxidants 2024, 13, 1368. https://doi.org/10.3390/antiox13111368Academic Editor: Ruth EdgeReceived: 12 October 2024Revised: 1 November 2024Accepted: 5 November 2024Published: 8 November 2024Copyright: © 2024 by the authors.Licensee MDPI, Basel, Switzerland.This article is an open access articledistributed under the terms andconditions of the Creative CommonsAttribution (CC BY) license (https://creativecommons.org/licenses/by/4.0/).ArticleModelling the Repair of Carbon-Centered Protein Radicals byPhenolic AntioxidantsMax Walton-Raaby 1,2,† , Tyler Floen 1,3,† and Nelaine Mora-Diez 1,*1 Department of Chemistry, Thompson Rivers University, Kamloops, BC V2C 0C8, Canada;max.walton-raaby@uwaterloo.ca (M.W.-R.); tfloen@student.ubc.ca (T.F.)2 Department of Chemistry, University of Waterloo, Waterloo, ON N2L 3G1, Canada3 Faculty of Pharmaceutical Sciences, University of British Columbia, Vancouver, BC V6T 1Z3, Canada* Correspondence: nmora@tru.ca† These authors contributed equally to the calculations reported and the preparation of the first draft.Abstract: Oxidative stress is a biological process that has been linked to many diseases, hence under-standing how to prevent and repair it is essential to medicine. The thermodynamics and kinetics ofthe repair reactions of radically damaged leucine (a lateral chain in a simplified protein environment)by twenty phenolic antioxidants are studied at the M06-2X(SMD)/6-31++G(d,p) level of theory inwater and pentyl ethanoate. The two repair mechanisms modelled are formal-hydrogen atom transfer(f-HAT) and single electron transfer (SET). Although all f-HAT reactions are thermodynamicallyfavourable, only one of the phenols produced rate constants in the diffusion limit, exhibiting biologi-cal relevance. SET is not suspected to be an important repair pathway for the phenols studied. Weshow that the Bell–Evan…
has type: Article
is shown at: 10.14288/1.0447374
language: eng
peer review status: Reviewed
provider: Vancouver : University of British Columbia Library
publisher: Multidisciplinary Digital Publishing Institute
publisher DOI: 10.3390/antiox13111368
rights: CC BY 4.0
rights URI: https://creativecommons.org/licenses/by/4.0/
scholar level: Faculty
subject: DFT
subject: M06-2X
subject: SMD
subject: antioxidants
subject: phenols
subject: leucine
subject: repair
subject: rate constants
subject: HAT
subject: SET
subject: thermodynamics
subject: kinetics
type: Text
identifier URI: http://hdl.handle.net/2429/89756