UV Excited-State of Biochromophore Negative Ions

A. V. Bochenkova, B. Klaerke, D. B. Rahbek, J. Rajput, Y. Toker, L. H. Andersen

Research output: Contribution to journalArticlepeer-review


Members of the green fluorescent protein (GFP) family may undergo irreversible phototransformation upon irradiation with UV light. This provides clear evidence for the importance of the higher-energy photophysics of the chromophore, which remains essentially unexplored. By using time-resolved action and photoelectron spectroscopy together with high-level electronic structure theory, we directly probe and identify higher electronically excited singlet states of the isolated para- and meta-chromophore anions of GFP. These molecular resonances are found to serve as a doorway for very efficient electron detachment in the gas phase. Inside the protein, this band is found to be resonant with the quasicontinuum of a solvated electron, thus enhancing electron transfer from the GFP to the solvent. This suggests a photophysical pathway for photoconversion of the protein, where GFP resonant photooxidation in solution triggers radical redox reactions inside these proteins.
Original languageEnglish
Pages (from-to)9955-9959
Number of pages5
JournalAngewandte Chemie
Issue number37
StatePublished - 15 Jul 2014


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