Electrostatic control of photoisomerization pathways in proteins
Abstract
Rotation around a specific bond after photoexcitation is central to vision and emerging opportunities in optogenetics, super-resolution microscopy, and photoactive molecular devices. Competing roles for steric and electrostatic effects that govern bond-specific photoisomerization have been widely discussed, the latter originating from chromophore charge transfer upon excitation. We systematically altered the electrostatic properties of the green fluorescent protein chromophore in a photoswitchable variant, Dronpa2, using amber suppression to introduce electron-donating and electron-withdrawing groups to the phenolate ring. Through analysis of the absorption (color), fluorescence quantum yield, and energy barriers to ground- and excited-state isomerization, we evaluate the contributions of sterics and electrostatics quantitatively and demonstrate how electrostatic effects bias the pathway of chromophore photoisomerization, leading to a generalized framework to guide protein design.
- Authors:
-
[1];
[1];
[2];
[1]
- Stanford Univ., CA (United States)
- SLAC National Accelerator Lab., Menlo Park, CA (United States). Stanford Synchrotron Radiation Lightsource (SSRL)
- Publication Date:
- Research Org.:
- SLAC National Accelerator Laboratory (SLAC), Menlo Park, CA (United States)
- Sponsoring Org.:
- USDOE Office of Science (SC)
- OSTI Identifier:
- 1604560
- Grant/Contract Number:
- AC02-76SF00515; GM118044
- Resource Type:
- Accepted Manuscript
- Journal Name:
- Science
- Additional Journal Information:
- Journal Volume: 367; Journal Issue: 6473; Journal ID: ISSN 0036-8075
- Publisher:
- AAAS
- Country of Publication:
- United States
- Language:
- English
- Subject:
- 59 BASIC BIOLOGICAL SCIENCES
Citation Formats
Romei, Matthew G., Lin, Chi-Yun, Mathews, Irimpan I., and Boxer, Steven G. Electrostatic control of photoisomerization pathways in proteins. United States: N. p., 2020.
Web. doi:10.1126/science.aax1898.
Romei, Matthew G., Lin, Chi-Yun, Mathews, Irimpan I., & Boxer, Steven G. Electrostatic control of photoisomerization pathways in proteins. United States. https://doi.org/10.1126/science.aax1898
Romei, Matthew G., Lin, Chi-Yun, Mathews, Irimpan I., and Boxer, Steven G. Thu .
"Electrostatic control of photoisomerization pathways in proteins". United States. https://doi.org/10.1126/science.aax1898. https://www.osti.gov/servlets/purl/1604560.
@article{osti_1604560,
title = {Electrostatic control of photoisomerization pathways in proteins},
author = {Romei, Matthew G. and Lin, Chi-Yun and Mathews, Irimpan I. and Boxer, Steven G.},
abstractNote = {Rotation around a specific bond after photoexcitation is central to vision and emerging opportunities in optogenetics, super-resolution microscopy, and photoactive molecular devices. Competing roles for steric and electrostatic effects that govern bond-specific photoisomerization have been widely discussed, the latter originating from chromophore charge transfer upon excitation. We systematically altered the electrostatic properties of the green fluorescent protein chromophore in a photoswitchable variant, Dronpa2, using amber suppression to introduce electron-donating and electron-withdrawing groups to the phenolate ring. Through analysis of the absorption (color), fluorescence quantum yield, and energy barriers to ground- and excited-state isomerization, we evaluate the contributions of sterics and electrostatics quantitatively and demonstrate how electrostatic effects bias the pathway of chromophore photoisomerization, leading to a generalized framework to guide protein design.},
doi = {10.1126/science.aax1898},
journal = {Science},
number = 6473,
volume = 367,
place = {United States},
year = {Thu Jan 02 00:00:00 EST 2020},
month = {Thu Jan 02 00:00:00 EST 2020}
}
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