TY - JOUR
T1 - Ultrafast Carotenoid to Retinal Energy Transfer in Xanthorhodopsin Revealed by the Combination of Transient Absorption and Two-Dimensional Electronic Spectroscopy
AU - Segatta, Francesco
AU - Gdor, Itay
AU - Réhault, Julien
AU - Taioli, Simone
AU - Friedman, Noga
AU - Sheves, Mordechai
AU - Rivalta, Ivan
AU - Ruhman, Sanford
AU - Cerullo, Giulio
AU - Garavelli, Marco
N1 - Publisher Copyright:
© 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
PY - 2018/8/14
Y1 - 2018/8/14
N2 - By comparing two-dimensional electronic spectroscopy (2DES) and Pump-Probe (PP) measurements on xanthorhodopsin (XR) and reduced-xanthorhodopsin (RXR) complexes, the ultrafast carotenoid-to-retinal energy transfer pathway is revealed, at very early times, by an excess of signal amplitude at the associated cross-peak and by the carotenoid bleaching reduction due to its ground state recovery. The combination of the measured 2DES and PP spectroscopic data with theoretical modelling allows a clear identification of the main experimental signals and a comprehensive interpretation of their origin and dynamics. The remarkable velocity of the energy transfer, despite the non-negligible energy separation between the two chromophores, and the analysis of the underlying transport mechanism, highlight the role played by the ground state carotenoid vibrations in assisting the process.
AB - By comparing two-dimensional electronic spectroscopy (2DES) and Pump-Probe (PP) measurements on xanthorhodopsin (XR) and reduced-xanthorhodopsin (RXR) complexes, the ultrafast carotenoid-to-retinal energy transfer pathway is revealed, at very early times, by an excess of signal amplitude at the associated cross-peak and by the carotenoid bleaching reduction due to its ground state recovery. The combination of the measured 2DES and PP spectroscopic data with theoretical modelling allows a clear identification of the main experimental signals and a comprehensive interpretation of their origin and dynamics. The remarkable velocity of the energy transfer, despite the non-negligible energy separation between the two chromophores, and the analysis of the underlying transport mechanism, highlight the role played by the ground state carotenoid vibrations in assisting the process.
KW - Förster energy transfer
KW - carotenoids
KW - electronic spectroscopy
KW - ground state vibrations
KW - retinal proteins
UR - http://www.scopus.com/inward/record.url?scp=85051442730&partnerID=8YFLogxK
U2 - 10.1002/chem.201803525
DO - 10.1002/chem.201803525
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C2 - 30048017
AN - SCOPUS:85051442730
SN - 0947-6539
VL - 24
SP - 12084
EP - 12092
JO - Chemistry - A European Journal
JF - Chemistry - A European Journal
IS - 46
ER -