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Photoelectron spectroscopy of isolated luciferin and infraluciferin anions in vacuo: competing photodetachment, photofragmentation and internal conversion

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Abstract

The electronic structure and excited-state dynamics of the ubiquitous bioluminescent probe luciferin and its furthest red-shifted analogue infraluciferin have been investigated using photoelectron spectroscopy and quantum chemistry calculations. In our electrospray ionization source, the deprotonated anions are formed predominantly in their phenolate forms and are directly relevant to studies of luciferin and infraluciferin as models for their unstable oxyluciferin and oxyinfraluciferin emitters. Following photoexcitation in the range 357–230 nm, we find that internal conversion from high-lying excited states to the S1(1ππ*) state competes efficiently with electron detachment. In infraluciferin, we find that decarboxylation also competes with direct electron detachment and internal conversion. This detailed spectroscopic and computational study defines the electronic structure and electronic relaxation processes of luciferin and infraluciferin and will inform the design of new bioluminescent systems and applications.

Graphical abstract: Photoelectron spectroscopy of isolated luciferin and infraluciferin anions in vacuo: competing photodetachment, photofragmentation and internal conversion

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Publication details

The article was received on 17 Jul 2017, accepted on 09 Aug 2017 and first published on 09 Aug 2017


Article type: Paper
DOI: 10.1039/C7CP04815G
Citation: Phys. Chem. Chem. Phys., 2017, Advance Article
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    Photoelectron spectroscopy of isolated luciferin and infraluciferin anions in vacuo: competing photodetachment, photofragmentation and internal conversion

    J. L. Woodhouse, M. Assmann, M. A. Parkes, H. Grounds, S. J. Pacman, J. C. Anderson, G. A. Worth and H. H. Fielding, Phys. Chem. Chem. Phys., 2017, Advance Article , DOI: 10.1039/C7CP04815G

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