Theoretical Chemistry Accounts

, 132:1327 | Cite as

A time-dependent DFT/molecular dynamics study of the proton-wire responsible for the red fluorescence in the LSSmKate2 protein

  • Carlos Randino
  • Marc Nadal-Ferret
  • Ricard Gelabert
  • Miquel Moreno
  • José M. Lluch
Regular Article
First Online:
Received:
Accepted:
Part of the following topical collections:
  1. 8th Congress on Electronic Structure: Principles and Applications (ESPA 2012)

Abstract

Fluorescent proteins (FP) have become a major topic in the recent biochemical research due to their applications as in vivo markers in biological systems. In particular, Red fluorescent proteins (RFP) present some advantages since they require less harmful radiations to be excited and show less light-scattering. In this paper, we are focusing on the LSSmKate2 protein, a RFP that, together with LSSmKate1 and mKeima, is well known for the outstanding difference between absorption and emission wavelengths, which is usually referred as Large Stokes Shift (LSS). It is commonly accepted that an excited state proton transfer accounts for the fluorescence observed in the three proteins. In this work, a molecular dynamics simulation of the LSSmKate2 protein has been carried out, and from different snapshots, a series of excited states have been calculated and analyzed. Our molecular dynamics simulation has proved the availability of the two-link proton-wire suggested by Piatkevich et al. and has furnished a new one-link relay, more prone to take place. The statistical treatment of the excited states can reproduce the electronic absorption spectrum in a reasonable way, and the analysis of the involved orbitals confirms that one absorption wavelength maximum corresponds to an acidification of the chromophore, regardless of the hydrogen-bonded acceptor residue. All this work constitutes an important step in what should be a thorough and complete study of the photochemistry of the LSSproteins.

Keywords

Red fluorescent proteins LSSmKate2 protein Electronic absorption spectrum Time-dependent density functional theory Molecular dynamics simulation 
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Notes

Acknowledgments

This work was supported by the “Ministerio de Economía y Competitividad” through project CTQ2011-24292 and by the “Generalitat de Catalunya” through project 2009SGR409. Use of computational facilities at the “Centre de Serveis Científics i Acadèmics de Catalunya (CESCA)” is gratefully acknowledged. C.R. acknowledges the “Ministerio de Economía y Competitividad” for a fellowship within the FPU program. M.N.-F. thanks the “Secretaria d’Universitats i Recerca (SUR)” of the “Departament d’Economia i Coneixement (DEC)” of the “Generalitat de Catalunya” and the European Social Fund (ESF) for a fellowship within the FI-DGR program.

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Copyright information

© Springer-Verlag Berlin Heidelberg 2013

Authors and Affiliations

  • Carlos Randino
    • 1
  • Marc Nadal-Ferret
    • 1
  • Ricard Gelabert
    • 1
  • Miquel Moreno
    • 1
  • José M. Lluch
    • 1
    • 2
  1. 1.Departament de QuímicaUniversitat Autònoma de BarcelonaBarcelonaSpain
  2. 2.Institut de Biotecnologia i de BiomedicinaUniversitat Autònoma de BarcelonaBarcelonaSpain

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