title: Insight into the kinetics and thermodynamics of the hydride transfer reactions between quinones and lumiflavin: a density functional theory study.
abstract: The kinetics and equilibrium of the hydride transfer reaction between lumiflavin and a number of substituted quinones was studied using density functional theory. The impact of electron withdrawing/donating substituents on the redox potentials of quinones was studied. In addition, the role of these substituents on the kinetics of the hydride transfer reaction with lumiflavin was investigated in detail under the transition state (TS) theory assumption. The hydride transfer reactions were found to be more favorable for an electron-withdrawing substituent. The activation barrier exhibited a quadratic relationship with the driving force of these reactions as derived under the formalism of modified Marcus theory. The present study found a significant extent of electron delocalization in the TS that is stabilized by enhanced electrostatic, polarization, and exchange interactions. Analysis of geometry, bond-orders, and energetics revealed a predominant parallel (Leffler-Hammond) effect on the TS. Closer scrutiny reveals that electron-withdrawing substituents, although located on the acceptor ring, reduce the N-H bond order of the donor fragment in the precursor complex. Carried out in the gas-phase, this is the first ever report of a theoretical study of flavin's hydride transfer reactions with quinones, providing an unfiltered view of the electronic effect on the nuclear reorganization of donor-acceptor complexes.
authors: Department of Chemistry, University of Wisconsin-Eau Claire, Eau Claire, WI, 54702, USA.
authors: Clorice R
authors: CR
authors: Reinhardt
authors: Department of Chemistry, University of Wisconsin-Eau Claire, Eau Claire, WI, 54702, USA.
authors: Tanner C
authors: TC
authors: Jaglinski
authors: Department of Chemistry, University of Wisconsin-Eau Claire, Eau Claire, WI, 54702, USA.
authors: Ashly M
authors: AM
authors: Kastenschmidt
authors: Department of Chemistry, University of Wisconsin-Eau Claire, Eau Claire, WI, 54702, USA.
authors: Eun H
authors: EH
authors: Song
authors: Department of Chemistry, University of Wisconsin-Eau Claire, Eau Claire, WI, 54702, USA.
authors: Adam K
authors: AK
authors: Gross
authors: Department of Chemistry, University of Wisconsin-Eau Claire, Eau Claire, WI, 54702, USA.
authors: Alyssa J
authors: AJ
authors: Krause
authors: Department of Chemistry, University of Wisconsin-Eau Claire, Eau Claire, WI, 54702, USA.
authors: Jonathan M
authors: JM
authors: Gollmar
authors: Department of Chemistry, University of Wisconsin-Eau Claire, Eau Claire, WI, 54702, USA.
authors: Kristin J
authors: KJ
authors: Meise
authors: Department of Chemistry, University of Wisconsin-Eau Claire, Eau Claire, WI, 54702, USA.
authors: Zachary S
authors: ZS
authors: Stenerson
authors: Department of Chemistry, University of Wisconsin-Eau Claire, Eau Claire, WI, 54702, USA.
authors: Tyler J
authors: TJ
authors: Weibel
authors: Department of Chemistry, University of Wisconsin-Eau Claire, Eau Claire, WI, 54702, USA.
authors: Andrew
authors: A
authors: Dison
authors: Department of Chemistry, University of Wisconsin-Eau Claire, Eau Claire, WI, 54702, USA.
authors: Mackenzie R
authors: MR
authors: Finnegan
authors: Department of Chemistry, University of Wisconsin-Eau Claire, Eau Claire, WI, 54702, USA.
authors: Daniel S
authors: DS
authors: Griesi
authors: Department of Chemistry, University of Wisconsin-Eau Claire, Eau Claire, WI, 54702, USA.
authors: Michael D
authors: MD
authors: Heltne
authors: Department of Chemistry, University of Wisconsin-Eau Claire, Eau Claire, WI, 54702, USA.
authors: Tom G
authors: TG
authors: Hughes
authors: Department of Chemistry, University of Wisconsin-Eau Claire, Eau Claire, WI, 54702, USA.
authors: Connor D
authors: CD
authors: Hunt
authors: Department of Chemistry, University of Wisconsin-Eau Claire, Eau Claire, WI, 54702, USA.
authors: Kayla A
authors: KA
authors: Jansen
authors: Department of Chemistry, University of Wisconsin-Eau Claire, Eau Claire, WI, 54702, USA.
authors: Adam H
authors: AH
authors: Xiong
authors: Department of Chemistry, University of Wisconsin-Eau Claire, Eau Claire, WI, 54702, USA.
authors: Sanchita
authors: S
authors: Hati
authors: Department of Chemistry, University of Wisconsin-Eau Claire, Eau Claire, WI, 54702, USA. bhattas@uwec.edu.
authors: Sudeep
authors: S
authors: Bhattacharyya
keywords: Density functional theory; Dispersion corrections; Dispersion forces; Flavin; Flavoenzymes; Gibbs’ free energy calculations; Marcus theory; Quantum chemical studies; Quinones; Redox reactions; Reorganization energy; π–π stacking interactions