Direct Measurement of the Isomerization Barrier of the Isolated Retinal Chromophore

Abstract

Ion mobility spectroscopy (IMS) allows one to differentiate between different isomers of a given molecular ion according to their collisional cross-section. Using two stages of IMS (IMS-IMS) one can select a specific isomer, collisionally heat it and follow its isomerization pathways. Recently it has been shown that this technique allows one to determine internal energy barrier for isomerization. Here we apply the technique to the important case of the retinal protonated Schiff base (RPSB). Photoisomerization of the RPSB is the primary in animal vision. We find that 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. Thus the protein has a significant role in increasing the barrier energy for thermal isomerization relative to the gas phase which lacks interaction with the RPSB counterion and steric constraints. High barrier energy is mandatory for efficient vision processes, otherwise thermal noise would overwhelm the signal originating from the photochemical isomerization.

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Document Details

Document Type
Technical Report
Publication Date
Nov 03, 2015
Accession Number
ADA626920

Entities

People

  • Anastasia V. Bochenkova
  • David E. Clemmer
  • Jonathan M. Dilger
  • Lihi Musbat
  • Mordechai Sheves
  • Yoni Toker

Organizations

  • Naval Surface Warfare Center

Tags

Communities of Interest

  • Energy and Power Technologies

DTIC Thesaurus Topics

  • Advanced Materials
  • Chemical Compounds
  • Chemical Reactions
  • Chemistry
  • Chromophores
  • Collisions
  • Electric Fields
  • Energy
  • Heat Of Activation
  • Imines
  • Isomerization
  • Mass Spectrometry
  • Measurement
  • Mobility
  • Physics
  • Spectrometry
  • Spectroscopy

Readers

  • Chemistry (specifically Chemical Fluorescence)
  • Molecular Photonics/Laser Physics
  • Quantum Chemistry