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

Result code in 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>

Result on the web

<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>

Result language

angličtina

Original language name

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

Original language description

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

Czech name

—

Czech description

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Type

J_imp - Article in a specialist periodical, which is included in the Web of Science database

CEP classification

—

OECD FORD branch

10608 - Biochemistry and molecular biology

Project

<a href="/en/project/GM21-09692M" target="_blank" >GM21-09692M: Clarifying quantum limits in biomolecules by utilizing entangled photons generated from protein bound cofactor modeled on orange carotenoid protein</a><br>

Continuities

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

Publication year

2025

Confidentiality

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

Name of the periodical

Journal of the American Chemical Society

ISSN

0002-7863

e-ISSN

1520-5126

Volume of the periodical

147

Issue of the periodical within the volume

29

Country of publishing house

US - UNITED STATES

Number of pages

13

Pages from-to

25571-25583

UT code for WoS article

001526051900001

EID of the result in the Scopus database

2-s2.0-105010205026