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Local vibrational coherences drive the primary photochemistry of vision

Nature Chemistry volume 7, pages 980986 (2015) | Download Citation

Abstract

The role of vibrational coherence—concerted vibrational motion on the excited-state potential energy surface—in the isomerization of retinal in the protein rhodopsin remains elusive, despite considerable experimental and theoretical efforts. We revisited this problem with resonant ultrafast heterodyne-detected transient-grating spectroscopy. The enhanced sensitivity that this technique provides allows us to probe directly the primary photochemical reaction of vision with sufficient temporal and spectral resolution to resolve all the relevant nuclear dynamics of the retinal chromophore during isomerization. We observed coherent photoproduct formation on a sub-50 fs timescale, and recovered a host of vibrational modes of the retinal chromophore that modulate the transient-grating signal during the isomerization reaction. Through Fourier filtering and subsequent time-domain analysis of the transient vibrational dynamics, the excited-state nuclear motions that drive the isomerization reaction were identified, and comprise stretching, torsional and out-of-plane wagging motions about the local C11=C12 isomerization coordinate.

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Acknowledgements

P.J.M.J. thanks J.M. Morrow and B.S.W. Chang for many helpful discussions and shared laboratory equipment during the early stages of this work. L. Chen is acknowledged for excellent technical assistance. This research was supported by the Natural Sciences and Engineering Research Council of Canada (R.J.D.M.), the Max Planck Society (R.J.D.M.), the Canadian Institute for Advanced Research (R.J.D.M. and O.P.E.) and the Canada Excellence Research Chair program (O.P.E.). O.P.E. is the Anne & Max Tanenbaum Chair in Neuroscience at the University of Toronto.

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Affiliations

  1. Institute for Optical Sciences and Departments of Chemistry and Physics, University of Toronto, 80 St George Street, Toronto, Ontario M5S 3H6, Canada

    • Philip J. M. Johnson
    • , Alexei Halpin
    •  & R. J. Dwayne Miller
  2. Department of Biochemistry, University of Toronto, 1 King's College Circle, Toronto, Ontario M5S 1A8, Canada

    • Takefumi Morizumi
    •  & Oliver P. Ernst
  3. Max Planck Institute for the Structure and Dynamics of Matter, Atomically Resolved Dynamics Division, Building 99 (CFEL), Luruper Chaussee 149, Hamburg 22761, Germany

    • Valentyn I. Prokhorenko
    •  & R. J. Dwayne Miller
  4. Department of Molecular Genetics, University of Toronto, 1 King's College Circle, Toronto, Ontario M5S 1A8, Canada

    • Oliver P. Ernst

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Contributions

P.J.M.J., A.H. and V.I.P. constructed the instruments. T.M. prepared and characterized the sample. P.J.M.J. and A.H. performed the measurements. P.J.M.J and V.I.P. analysed the data. P.J.M.J. wrote the manuscript with editing from all authors. O.P.E. and R.J.D.M. supervised the project.

Competing interests

The authors declare no competing financial interests.

Corresponding author

Correspondence to R. J. Dwayne Miller.

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https://doi.org/10.1038/nchem.2398

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