In:
Angewandte Chemie, Wiley, Vol. 135, No. 5 ( 2023-01-26)
Abstract:
Large Stokes shift (LSS) red fluorescent proteins (RFPs) are highly desirable for bioimaging advances. The RFP mKeima, with coexisting cis‐ and trans ‐isomers, holds significance as an archetypal system for LSS emission due to excited‐state proton transfer (ESPT), yet the mechanisms remain elusive. We implemented femtosecond stimulated Raman spectroscopy (FSRS) and various time‐resolved electronic spectroscopies, aided by quantum calculations, to dissect the cis ‐ and trans ‐mKeima photocycle from ESPT, isomerization, to ground‐state proton transfer in solution. This work manifests the power of FSRS with global analysis to resolve Raman fingerprints of intermediate states. Importantly, the deprotonated trans ‐isomer governs LSS emission at 620 nm, while the deprotonated cis ‐isomer's 520 nm emission is weak due to an ultrafast cis ‐to‐ trans isomerization. Complementary spectroscopic techniques as a table‐top toolset are thus essential to study photochemistry in physiological environments.
Type of Medium:
Online Resource
ISSN:
0044-8249
,
1521-3757
DOI:
10.1002/ange.202212209
Language:
English
Publisher:
Wiley
Publication Date:
2023
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