Vibronic Dynamics of the Ultrafast all-trans to 13-cis Photoisomerization of Retinal in Channelrhodopsin-1

J Am Chem Soc. 2016 Apr 13;138(14):4757-62. doi: 10.1021/jacs.5b12251. Epub 2016 Mar 30.

Abstract

Channelrhodopsins are light-gated ion channels with extensive applications in optogenetics. Channelrhodopsin-1 from Chlamydomonas augustae (CaChR1) exhibits a red-shifted absorption spectrum as compared to Channelrhodopsin-2, which is highly beneficial for optogenetic application. The primary event in the photocycle of CaChR1 involves an isomerization of the protein-bound retinal chromophore. Here, we apply highly time-resolved vibronic spectroscopy to reveal the electronic and structural dynamics associated with the first step of the photocycle of CaChR1. We observe vibrationally coherent formation of the P1 intermediate exhibiting a twisted 13-cis retinal with a 110 ± 7 fs time constant. Comparison with low-temperature resonance Raman spectroscopy of the corresponding trapped photoproduct demonstrates that this rapidly formed P1 intermediate is stable for several hundreds of nanoseconds.

Publication types

  • Research Support, Non-U.S. Gov't

MeSH terms

  • Chlamydomonas / chemistry
  • Isomerism
  • Photochemical Processes
  • Plant Proteins / chemistry
  • Retinaldehyde / chemistry*
  • Rhodopsin / chemistry*
  • Spectrum Analysis, Raman

Substances

  • Plant Proteins
  • Rhodopsin
  • Retinaldehyde