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...
Main Authors: | , , , , , , , , , |
---|---|
Format: | Journal article |
Language: | English |
Published: |
American Chemical Society
2015
|
_version_ | 1797101933054394368 |
---|---|
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. |
first_indexed | 2024-03-07T05:58:53Z |
format | Journal article |
id | oxford-uuid:eb7b6530-0f3d-46fb-8ce0-63a937315f28 |
institution | University of Oxford |
language | English |
last_indexed | 2024-03-07T05:58:53Z |
publishDate | 2015 |
publisher | American Chemical Society |
record_format | dspace |
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 |
work_keys_str_mv | AT bassolinog barrierlessphotoisomerizationof11cisretinalprotonatedschiffbaseinsolution AT sovdatt barrierlessphotoisomerizationof11cisretinalprotonatedschiffbaseinsolution AT soaresduartea barrierlessphotoisomerizationof11cisretinalprotonatedschiffbaseinsolution AT limj barrierlessphotoisomerizationof11cisretinalprotonatedschiffbaseinsolution AT schnedermannc barrierlessphotoisomerizationof11cisretinalprotonatedschiffbaseinsolution AT liebelm barrierlessphotoisomerizationof11cisretinalprotonatedschiffbaseinsolution AT odellb barrierlessphotoisomerizationof11cisretinalprotonatedschiffbaseinsolution AT claridget barrierlessphotoisomerizationof11cisretinalprotonatedschiffbaseinsolution AT fletchers barrierlessphotoisomerizationof11cisretinalprotonatedschiffbaseinsolution AT kukurap barrierlessphotoisomerizationof11cisretinalprotonatedschiffbaseinsolution |