Photoresponse of the protonated Schiff-base retinal chromophore in the gas phase
| Autor: | D. B. Rahbek, Rodolphe Antoine, Y. Toker, S. Brøndsted Nielsen, Lars H. Andersen, Hjalte V. Kiefer, Philippe Dugourd, Jyoti Rajput, Anastasia V. Bochenkova |
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| Přispěvatelé: | Department of Physics and Astronomy [Aarhus], Aarhus University [Aarhus], Institut Lumière Matière [Villeurbanne] (ILM), Université Claude Bernard Lyon 1 (UCBL), Université de Lyon-Université de Lyon-Centre National de la Recherche Scientifique (CNRS), Department of Chemistry, Lomonosov Moscow State University, Lomonosov Moscow State University (MSU) |
| Jazyk: | angličtina |
| Rok vydání: | 2013 |
| Předmět: |
Schiff base
Photoisomerization 010401 analytical chemistry General Physics and Astronomy Protonation Retinal Chromophore 010402 general chemistry Photochemistry Photochemical Processes 01 natural sciences 0104 chemical sciences Photoexcitation chemistry.chemical_compound chemistry Fragmentation (mass spectrometry) Isomerism Retinaldehyde [CHIM]Chemical Sciences Gases Physical and Theoretical Chemistry Protons Isomerization Schiff Bases |
| Zdroj: | Physical Chemistry Chemical Physics Physical Chemistry Chemical Physics, Royal Society of Chemistry, 2013, 15 (45), pp.19566. ⟨10.1039/C3CP51759D⟩ Toker, J, Rahbek, D B, Kiefer, H V, Rajput, J, Antoine, R, Dugourd, P, Nielsen, S B, Bochenkova, A V & Andersen, L H 2013, ' Photoresponse of the protonated Schiff-base retinal chromophore in the gas phase ', Physical Chemistry Chemical Physics, vol. 15, pp. 19566-19569 . https://doi.org/10.1039/c3cp51759d |
| ISSN: | 1463-9076 1463-9084 |
| DOI: | 10.1039/C3CP51759D⟩ |
| Popis: | The fragmentation, initiated by photoexcitation as well as collisionally-induced excitation, of several retinal chromophores was studied in the gas phase. The chromophore in the protonated Schiff-base form (RPSB), essential for mammalian vision, shows a remarkably selective photoresponse. The selectivity of the gas-phase chromophore is triggered by a series of fast trans to cis isomerizations followed by a Diels–Alder cyclization with subsequent slow statistical fragmentation, leading to one specific fragment ion. The pattern of the final statistical fragmentation may be altered by chemical modifications of the chromophore. We propose that isomerizations play an important role in the photoresponse of gas-phase retinal chromophores and guide internal conversion through conical intersections. The role of protein interactions is then to control the specificity of the photoisomerization in the primary step of vision and possibly to diminish thermal noise by suppressing spontaneous isomerization by heat. The fragmentation, initiated by photoexcitation as well as collisionally-induced excitation, of several retinal chromophores was studied in the gas phase. The chromophore in the protonated Schiff-base form (RPSB), essential for mammalian vision, shows a remarkably selective photoresponse. The selectivity of the gas-phase chromophore is triggered by a series of fast trans to cis isomerizations followed by a Diels-Alder cyclization with subsequent slow statistical fragmentation, leading to one specific fragment ion. The pattern of the final statistical fragmentation may be altered by chemical modifications of the chromophore. We propose that isomerizations play an important role in the photoresponse of gas-phase retinal chromophores and guide internal conversion through conical intersections. The role of protein interactions is then to control the specificity of the photoisomerization in the primary step of vision and possibly to diminish thermal noise by suppressing spontaneous isomerization by heat. |
| Databáze: | OpenAIRE |
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