Multistep 11-cis to All-trans Retinal Photoisomerization in Bestrhodopsin, an Unusual Microbial Rhodopsin

Kód výsledku v IS VaVaI

<a href="https://www.isvavai.cz/riv?ss=detail&h=RIV%2F10974938%3A_____%2F25%3A25_88_11" target="_blank" >RIV/10974938:_____/25:25_88_11 - isvavai.cz</a>

Výsledek na webu

<a href="https://doi.org/10.1021/jacs.5c06216" target="_blank" >https://doi.org/10.1021/jacs.5c06216</a>

DOI - Digital Object Identifier

<a href="http://dx.doi.org/10.1021/jacs.5c06216" target="_blank" >10.1021/jacs.5c06216</a>

Jazyk výsledku

angličtina

Název v původním jazyce

Multistep 11-cis to All-trans Retinal Photoisomerization in Bestrhodopsin, an Unusual Microbial Rhodopsin

Popis výsledku v původním jazyce

Rhodopsins constitute a broad class of retinalbinding photoreceptors. Microbial rhodopsins are canonically activated through an all-trans to 13-cis photoisomerization, whereas animal rhodopsins are mostly activated through an 11-cis to alltrans isomerization. Bestrhodopsins constitute a special microbial rhodopsin subfamily, with bistable rhodopsin domains that can be photoswitched between a far red-absorbing state D661 and a greenabsorbing state P540. Its photochemistry involves a peculiar alltrans to 11-cis isomerization for the D661 to P540 photoreaction and vice versa. Here, we present the P. antarctica bestrhodopsin 11-cis to all-trans photoreaction as determined by femtosecond-tosubmillisecond transient absorption, femtosecond stimulated Raman and flash-photolysis spectroscopy. The primary photoreaction involves ultrafast isomerizations in 240 fs from the 11-cis reactant to a mixture of highly distorted all-trans and 13-cis photoproducts. The 13-cis fraction then thermally isomerizes to a distorted all-trans RSB in 120 ps. We propose bicycle pedal models for the branched photoisomerizations with corotation of the C11�C12 and C13�C14 double bonds. One reactant fraction undergoes bicycle pedal motion aborted at the C13�C14 double bond, resulting in all-trans retinal. The other fraction undergoes a full bicycle pedal motion of both C11�C12 and C13�C14, resulting in 13-cis retinal. The primary products are trapped high up the ground-state potential energy surface with a low energetic barrier that facilitates thermal isomerization from 13-cis to all-trans retinal in 120 ps. All-trans retinal then structurally and energetically relaxes with subsequent time constants of 0.7 and 62 μs and 4.4 ms, along with counterion protonation, completing the P540 to D661 photoreaction

Název v anglickém jazyce

Multistep 11-cis to All-trans Retinal Photoisomerization in Bestrhodopsin, an Unusual Microbial Rhodopsin

Popis výsledku anglicky

Rhodopsins constitute a broad class of retinalbinding photoreceptors. Microbial rhodopsins are canonically activated through an all-trans to 13-cis photoisomerization, whereas animal rhodopsins are mostly activated through an 11-cis to alltrans isomerization. Bestrhodopsins constitute a special microbial rhodopsin subfamily, with bistable rhodopsin domains that can be photoswitched between a far red-absorbing state D661 and a greenabsorbing state P540. Its photochemistry involves a peculiar alltrans to 11-cis isomerization for the D661 to P540 photoreaction and vice versa. Here, we present the P. antarctica bestrhodopsin 11-cis to all-trans photoreaction as determined by femtosecond-tosubmillisecond transient absorption, femtosecond stimulated Raman and flash-photolysis spectroscopy. The primary photoreaction involves ultrafast isomerizations in 240 fs from the 11-cis reactant to a mixture of highly distorted all-trans and 13-cis photoproducts. The 13-cis fraction then thermally isomerizes to a distorted all-trans RSB in 120 ps. We propose bicycle pedal models for the branched photoisomerizations with corotation of the C11�C12 and C13�C14 double bonds. One reactant fraction undergoes bicycle pedal motion aborted at the C13�C14 double bond, resulting in all-trans retinal. The other fraction undergoes a full bicycle pedal motion of both C11�C12 and C13�C14, resulting in 13-cis retinal. The primary products are trapped high up the ground-state potential energy surface with a low energetic barrier that facilitates thermal isomerization from 13-cis to all-trans retinal in 120 ps. All-trans retinal then structurally and energetically relaxes with subsequent time constants of 0.7 and 62 μs and 4.4 ms, along with counterion protonation, completing the P540 to D661 photoreaction

Druh

J_imp - Článek v periodiku v databázi Web of Science

CEP obor

—

OECD FORD obor

10608 - Biochemistry and molecular biology

Projekt

<a href="/cs/project/GM21-09692M" target="_blank" >GM21-09692M: Stanovení kvantových limitů v biomolekulách pomocí entanglovaných fotonů generovaných z navázaného kofaktorů, modelováno na OCP proteinu.</a><br>

Návaznosti

P - Projekt vyzkumu a vyvoje financovany z verejnych zdroju (s odkazem do CEP)

Rok uplatnění

2025

Kód důvěrnosti údajů

S - Úplné a pravdivé údaje o projektu nepodléhají ochraně podle zvláštních právních předpisů

Název periodika

Journal of the American Chemical Society

ISSN

0002-7863

e-ISSN

1520-5126

Svazek periodika

147

Číslo periodika v rámci svazku

29

Stát vydavatele periodika

US - Spojené státy americké

Počet stran výsledku

13

Strana od-do

25571-25583

Kód UT WoS článku

001526051900001

EID výsledku v databázi Scopus

2-s2.0-105010205026