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Excited-State Proton Transfer in Oxyluciferin and Its Analogues
- Source :
- Journal of Physical Chemistry Letters, Journal of Physical Chemistry Letters, American Chemical Society, 2020, 11 (9), pp.3653-3659. ⟨10.1021/acs.jpclett.0c00839⟩, Journal of Physical Chemistry Letters, 2020, 11 (9), pp.3653-3659. ⟨10.1021/acs.jpclett.0c00839⟩
- Publication Year :
- 2020
- Publisher :
- American Chemical Society (ACS), 2020.
-
Abstract
- One of the most characterized bioluminescent reactions involves the firefly luciferase that catalyzes the oxidation of the luciferin producing oxyluciferin in its first excited state. While relaxing to the ground state, oxyluciferin emits visible light with an emission maximum that can vary from green to red. Oxyluciferin exists under six different chemical forms resulting from a keto/enol tautomerization and the deprotonation of the phenol or enol moieties. The optical properties of each chemical form have been recently characterized by the investigations of a variety of oxyluciferin derivatives, indicating unresolved excited-state proton transfer (ESPT) reactions. In this work, femtosecond pump-probe spectroscopy and time-resolved fluorescence spectroscopy are used to investigate the picosecond kinetics of the ESPT reactions and demonstrate the excited state keto to enol conversion of oxyluciferin and its derivatives in aqueous buffer as a function of pH. A comprehensive photophysical scheme is provided describing the complex luminescence pathways of oxyluciferin in protic solution.
- Subjects :
- 010304 chemical physics
Chimie/Chimie théorique et/ou physique
010402 general chemistry
Photochemistry
01 natural sciences
Luciferin
Tautomer
Enol
Fluorescence spectroscopy
0104 chemical sciences
[CHIM.THEO]Chemical Sciences/Theoretical and/or physical chemistry
[CHIM.THEO] Chemical Sciences/Theoretical and/or physical chemistry
chemistry.chemical_compound
Deprotonation
chemistry
Excited state
0103 physical sciences
General Materials Science
Physical and Theoretical Chemistry
Luminescence
Ground state
Subjects
Details
- ISSN :
- 19487185
- Volume :
- 11
- Database :
- OpenAIRE
- Journal :
- The Journal of Physical Chemistry Letters
- Accession number :
- edsair.doi.dedup.....03044d62763b57cd32aae357e5806158