Direct measurement of the isomerization barrier of the isolated retinal chromophore

Angew Chem Int Ed Engl. 2015 Apr 13;54(16):4748-52. doi: 10.1002/anie.201411894. Epub 2015 Mar 10.

Abstract

Isomerizations of the retinal chromophore were investigated using the IMS-IMS technique. Four different structural features of the chromophore were observed, isolated, excited collisionally, and the resulting isomer and fragment distributions were measured. By establishing the threshold activation voltages for isomerization for each of the reaction pathways, and by measuring the threshold activation voltage for fragmentation, the relative energies of the isomers as well as the energy barriers for isomerization were determined. The energy barrier for a single cis-trans isomerization is (0.64±0.05) eV, which is significantly lower than that observed for the reaction within opsin proteins.

Keywords: chromophores; gas-phase reactions; ion mobility spectroscopy; isomerization; proteins.

MeSH terms

  • Isomerism
  • Protons
  • Retina / chemistry*
  • Retina / metabolism
  • Rhodopsin / chemistry
  • Rhodopsin / metabolism
  • Schiff Bases / chemistry*
  • Spectrophotometry

Substances

  • Protons
  • Schiff Bases
  • Rhodopsin