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.

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Acknowledgments

This work was supported by XSEDE Grant (CHE-110018), Research Corporation grant (CCSA 23223), and the Office of Research and Sponsored Programs, University of Wisconsin Eau Claire. We gratefully acknowledge the computational support from the in-house Blugold Supercomputing Cluster and Learning and Technology Services of the University of Wisconsin Eau Claire. We also thank Dr. Fredrick King of University of Wisconsin Eau Claire for his helpful discussions.

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Correspondence to Sudeep Bhattacharyya.

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This work contains results from a Physical Chemistry-I class project assigned to undergraduate students. Clorice R. Reinhardt is the main contributory undergraduate author. 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 are students of 2014 Fall Physical Chemistry-1.

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Reinhardt, C.R., Jaglinski, T.C., Kastenschmidt, A.M. et al. Insight into the kinetics and thermodynamics of the hydride transfer reactions between quinones and lumiflavin: a density functional theory study. J Mol Model 22, 199 (2016). https://doi.org/10.1007/s00894-016-3074-1

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Keywords

  • Density functional theory
  • Dispersion forces
  • Dispersion corrections
  • Gibbs’ free energy calculations
  • Flavin
  • Flavoenzymes
  • Marcus theory
  • Redox reactions
  • Quantum chemical studies
  • Quinones
  • Reorganization energy
  • π–π stacking interactions