Moscow University Chemistry Bulletin, volume 76, issue 6, pages 407-416

Role of the Protein Environment in Photoisomerization of Type I and Type II Rhodopsins: a Theoretical Perspective

Publication typeJournal Article
Publication date2021-11-01
Quartile SCImago
Q4
Quartile WOS
Impact factor0.6
ISSN00271314, 19350260
General Chemistry
Abstract
Abstract Primary photoisomerization reactions of the retinal protonated Schiff base (RPSB) inside type I and type II rhodopsins are ultrafast and exhibit high quantum yields. Specific protein environments are thought to facilitate photoisomerization of RPSB; however, the detailed mechanisms of tuning the reaction timescales and specificity are far from being understood. Here, by using molecular dynamics simulations and large-scale XMCQDPT2-based QM/MM modeling, we gain insight into the role played by the protein environment in specific photoisomerization of RPSB from all- trans to 13- cis in microbial rhodopsin KR2 and from 11- cis to all- trans in bovine visual rhodopsin. By analyzing the calculated vibronic band shapes, we explore the early-time excited-state dynamics of RPSB in both types of rhodopsins. We show that the protein environment changes vibrational modes, which become excited following the S 0 –S 1 transition, by pre-twisting the chromophore about a certain double bond in the ground electronic state. This reduces a barrier that hinders intramolecular rotation in the excited state, thus facilitating photoisomerization across the specific double bond. Moreover, pre-twisting of RPSB also provides conditions for initial in-phase excitation of the fundamental vibrational modes involved in the reaction coordinate, enabling vibrationally coherent barrierless excited-state decay in the photochemistry of vision.
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Kusochek P. A., Logvinov V. V., Bochenkova A. V. Role of the Protein Environment in Photoisomerization of Type I and Type II Rhodopsins: a Theoretical Perspective // Moscow University Chemistry Bulletin. 2021. Vol. 76. No. 6. pp. 407-416.
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Kusochek P. A., Logvinov V. V., Bochenkova A. V. Role of the Protein Environment in Photoisomerization of Type I and Type II Rhodopsins: a Theoretical Perspective // Moscow University Chemistry Bulletin. 2021. Vol. 76. No. 6. pp. 407-416.
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TY - JOUR
DO - 10.3103/S0027131421060110
UR - https://doi.org/10.3103%2FS0027131421060110
TI - Role of the Protein Environment in Photoisomerization of Type I and Type II Rhodopsins: a Theoretical Perspective
T2 - Moscow University Chemistry Bulletin
AU - Kusochek, P A
AU - Logvinov, V V
AU - Bochenkova, A V
PY - 2021
DA - 2021/11/01 00:00:00
PB - Pleiades Publishing
SP - 407-416
IS - 6
VL - 76
SN - 0027-1314
SN - 1935-0260
ER -
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@article{2021_Kusochek,
author = {P A Kusochek and V V Logvinov and A V Bochenkova},
title = {Role of the Protein Environment in Photoisomerization of Type I and Type II Rhodopsins: a Theoretical Perspective},
journal = {Moscow University Chemistry Bulletin},
year = {2021},
volume = {76},
publisher = {Pleiades Publishing},
month = {nov},
url = {https://doi.org/10.3103%2FS0027131421060110},
number = {6},
pages = {407--416},
doi = {10.3103/S0027131421060110}
}
MLA
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Kusochek, P. A., et al. “Role of the Protein Environment in Photoisomerization of Type I and Type II Rhodopsins: a Theoretical Perspective.” Moscow University Chemistry Bulletin, vol. 76, no. 6, Nov. 2021, pp. 407-416. https://doi.org/10.3103%2FS0027131421060110.
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