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Title: 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:
ORCiD logo [1]; ORCiD logo [1]; ORCiD logo [2]; ORCiD logo [1]
  1. Stanford Univ., CA (United States)
  2. SLAC National Accelerator Lab., Menlo Park, CA (United States). Stanford Synchrotron Radiation Lightsource (SSRL)
Publication Date:
Research Org.:
SLAC National Accelerator Lab., 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

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. doi: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. doi:10.1126/science.aax1898.
@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 = {2020},
month = {1}
}

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