Excited-state proton transfer of firefly dehydroluciferin

Itay Presiado, Yuval Erez, Ron Simkovitch, Shay Shomer, Rinat Gepshtein, Luís Pinto Da Silva, Joaquim C.G. Esteves Da Silva, Dan Huppert

Research output: Contribution to journalArticlepeer-review

Abstract

Steady-state and time-resolved emission techniques were used to study the protolytic processes in the excited state of dehydroluciferin, a nonbioluminescent product of the firefly enzyme luciferase. We found that the ESPT rate coefficient is only 1.1 × - 1010 s-1, whereas those of d-luciferin and oxyluciferin are 3.7 × - 1010 and 2.1 × - 1010 s-1, respectively. We measured the ESPT rate in water-methanol mixtures, and we found that the rate decreases nonlinearly as the methanol content in the mixture increases. The deprotonated form of dehydroluciferin has a bimodal decay with short- and long-time decay components, as was previously found for both d-luciferin and oxyluciferin. In weakly acidic aqueous solutions, the deprotonated forms emission is efficiently quenched. We attribute this observation to the ground-state protonation of the thiazole nitrogen, whose pKa value is ∼3.

Original languageEnglish
Pages (from-to)10770-10779
Number of pages10
JournalJournal of Physical Chemistry A
Volume116
Issue number44
DOIs
StatePublished - 8 Nov 2012

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