Mapping the ultrafast vibrational dynamics of all-transand 13-cisretinal isomerization in Anabaena Sensory Rhodopsin
| Autor: | Partha Pratim Roy, Youshitoka Kato, Nicolas Ferré, Rei Abe-Yoshizumi, Tiago Buckup, Hideki Kandori, Elisa Pieri |
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| Přispěvatelé: | Universität Heidelberg [Heidelberg], Nagoya Institute of Technology (NIT), Institut de Chimie Radicalaire (ICR), Aix Marseille Université (AMU)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), ANR-14-CE35-0015,FEMTO-ASR,Anabaena Sensory Rhodopsin: A biological model system to decipher the quantum mechanics of photochemical reactions through conical intersections(2014), Universität Heidelberg [Heidelberg] = Heidelberg University |
| Rok vydání: | 2018 |
| Předmět: |
Double bond
Retinaldehyde/chemistry General Physics and Astronomy Stereoisomerism Context (language use) 02 engineering and technology 010402 general chemistry Photochemistry Vibration 01 natural sciences symbols.namesake Bacterial Proteins Bacterial Proteins/chemistry Sensory Rhodopsins/chemistry Sensory Rhodopsins Physical and Theoretical Chemistry Anabaena/chemistry chemistry.chemical_classification biology 021001 nanoscience & nanotechnology Anabaena 0104 chemical sciences [CHIM.THEO]Chemical Sciences/Theoretical and/or physical chemistry chemistry 13. Climate action Rhodopsin Excited state Retinaldehyde biology.protein symbols Diterpenes 0210 nano-technology Raman spectroscopy Ground state Isomerization |
| Zdroj: | Physical Chemistry Chemical Physics Physical Chemistry Chemical Physics, Royal Society of Chemistry, 2018, 20 (48), pp.30159-30173. ⟨10.1039/c8cp05469j⟩ Physical Chemistry Chemical Physics, 2018, 20 (48), pp.30159-30173. ⟨10.1039/c8cp05469j⟩ |
| ISSN: | 1463-9084 1463-9076 |
| Popis: | 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 C[double bond, length as m-dash]C 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. |
| Databáze: | OpenAIRE |
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