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Verfasst von:Roy, Partha Pratim [VerfasserIn]   i
 Buckup, Tiago [VerfasserIn]   i
Titel:Mapping the ultrafast vibrational dynamics of all-trans and 13-cis retinal isomerization in Anabaena Sensory Rhodopsin
Verf.angabe:Partha Pratim Roy, Youshitoka Kato, Rei Abe-Yoshizumi, Elisa Pieri, Nicolas Ferré, Hideki Kandori and Tiago Buckup
E-Jahr:2018
Jahr:15 November 2018
Umfang:15 S.
Fussnoten:Gesehen am 24.04.2019
Titel Quelle:Enthalten in: Physical chemistry, chemical physics
Ort Quelle:Cambridge : RSC Publ., 1999
Jahr Quelle:2018
Band/Heft Quelle:20(2018), 48, Seite 30159-30173
ISSN Quelle:1463-9084
Abstract:Discrepancies in the isomerization dynamics and quantum yields of the trans and cis retinal protonated Schiff base is a well-known issue in the context of retinal photochemistry. Anabaena Sensory Rhodopsin (ASR) is a microbial retinal protein that comprises a retinal chromophore in two ground state (GS) conformations: all-trans, 15-anti (AT) and 13-cis, 15-syn (13C). In this study, we applied impulsive vibrational spectroscopic techniques (DFWM, pump-DFWM and pump-IVS) to ASR to shed more light on how the structural changes take place in the excited state within the same protein environment. Our findings point to distinct features in the ground state structural conformations as well as to drastically different evolutions in the excited state manifold. The ground state vibrational spectra show stronger Raman activity of the C14-H out-of-plane wag (at about 805 cm−1) for the 13C isomer than that for the AT isomer, which hints at a pre-distortion of 13C in the ground state. Evolution of the Raman frequency after interaction with the actinic pulse shows a blue-shift for the CC stretching and CH3 rocking mode for both isomers. For AT, however, the blue-shift is not instantaneous as observed for the 13C isomer, rather it takes more than 200 fs to reach the maximum frequency shift. This frequency blue-shift is rationalized by a decrease in the effective conjugation length during the isomerization reaction, which further confirms a slower formation of the twisted state for the AT isomer and corroborates the presence of a barrier in the excited state trajectory previously predicted by quantum chemical calculations.
DOI:doi:10.1039/C8CP05469J
URL:Bitte beachten Sie: Dies ist ein Bibliographieeintrag. Ein Volltextzugriff für Mitglieder der Universität besteht hier nur, falls für die entsprechende Zeitschrift/den entsprechenden Sammelband ein Abonnement besteht oder es sich um einen OpenAccess-Titel handelt.

Volltext ; Verlag: https://doi.org/10.1039/C8CP05469J
 Volltext: https://pubs.rsc.org/en/content/articlelanding/2018/cp/c8cp05469j
 DOI: https://doi.org/10.1039/C8CP05469J
Datenträger:Online-Ressource
Sprache:eng
K10plus-PPN:1663533628
Verknüpfungen:→ Zeitschrift

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