Barrierless photoisomerization of 11-cis retinal protonated Schiff base in solution

A hallmark of the primary visual event is the barrierless, ultrafast, and efficient 11-cis to all-trans photoisomerization of the retinal protonated Schiff base (RPSB) chromophore. The remarkable reactivity of RPSB in the visual pigment rhodopsin has been attributed to potential energy surface modif...

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Main Authors: Bassolino, G, Sovdat, T, Soares Duarte, A, Lim, J, Schnedermann, C, Liebel, M, Odell, B, Claridge, T, Fletcher, S, Kukura, P
Format: Journal article
Language:English
Published: American Chemical Society 2015
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author Bassolino, G
Sovdat, T
Soares Duarte, A
Lim, J
Schnedermann, C
Liebel, M
Odell, B
Claridge, T
Fletcher, S
Kukura, P
author_facet Bassolino, G
Sovdat, T
Soares Duarte, A
Lim, J
Schnedermann, C
Liebel, M
Odell, B
Claridge, T
Fletcher, S
Kukura, P
author_sort Bassolino, G
collection OXFORD
description A hallmark of the primary visual event is the barrierless, ultrafast, and efficient 11-cis to all-trans photoisomerization of the retinal protonated Schiff base (RPSB) chromophore. The remarkable reactivity of RPSB in the visual pigment rhodopsin has been attributed to potential energy surface modifications enabled by evolution-optimized chromophore-protein interactions. Here, we use a combined synthetic and ultrafast spectroscopic approach to show that barrierless photoisomerization is an intrinsic property of 11-cis RPSB, suggesting that the protein may merely adjust the ratio between fast reactive and slow unreactive decay channels. These results call for a re-evaluation of our understanding and theoretical description of RPSB photochemistry.
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spelling oxford-uuid:eb7b6530-0f3d-46fb-8ce0-63a937315f282022-03-27T11:10:00ZBarrierless photoisomerization of 11-cis retinal protonated Schiff base in solutionJournal articlehttp://purl.org/coar/resource_type/c_dcae04bcuuid:eb7b6530-0f3d-46fb-8ce0-63a937315f28EnglishSymplectic Elements at OxfordAmerican Chemical Society2015Bassolino, GSovdat, TSoares Duarte, ALim, JSchnedermann, CLiebel, MOdell, BClaridge, TFletcher, SKukura, PA hallmark of the primary visual event is the barrierless, ultrafast, and efficient 11-cis to all-trans photoisomerization of the retinal protonated Schiff base (RPSB) chromophore. The remarkable reactivity of RPSB in the visual pigment rhodopsin has been attributed to potential energy surface modifications enabled by evolution-optimized chromophore-protein interactions. Here, we use a combined synthetic and ultrafast spectroscopic approach to show that barrierless photoisomerization is an intrinsic property of 11-cis RPSB, suggesting that the protein may merely adjust the ratio between fast reactive and slow unreactive decay channels. These results call for a re-evaluation of our understanding and theoretical description of RPSB photochemistry.
spellingShingle Bassolino, G
Sovdat, T
Soares Duarte, A
Lim, J
Schnedermann, C
Liebel, M
Odell, B
Claridge, T
Fletcher, S
Kukura, P
Barrierless photoisomerization of 11-cis retinal protonated Schiff base in solution
title Barrierless photoisomerization of 11-cis retinal protonated Schiff base in solution
title_full Barrierless photoisomerization of 11-cis retinal protonated Schiff base in solution
title_fullStr Barrierless photoisomerization of 11-cis retinal protonated Schiff base in solution
title_full_unstemmed Barrierless photoisomerization of 11-cis retinal protonated Schiff base in solution
title_short Barrierless photoisomerization of 11-cis retinal protonated Schiff base in solution
title_sort barrierless photoisomerization of 11 cis retinal protonated schiff base in solution
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