Insight into the Kinetics and Thermodynamics of the Hydride Transfer Reactions Between Quinones and Lumiflavin: a Density Functional Theory Study

Overview

Journal J Mol Model

Publisher Springer

Specialty Molecular Biology

Date 2016 Aug 6

PMID 27491848

Citations 2

Authors

Clorice R Reinhardt

Tanner C Jaglinski

Ashly M Kastenschmidt

Eun H Song

Adam K Gross

Alyssa J Krause

Jonathan M Gollmar

Kristin J Meise

Zachary S Stenerson

Tyler J Weibel

Andrew Dison

Mackenzie R Finnegan

Daniel S Griesi

Michael D Heltne

Tom G Hughes

Connor D Hunt

Kayla A Jansen

Adam H Xiong

Sanchita Hati

Sudeep Bhattacharyya

Affiliations

Soon will be listed here.

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.

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