Excited-state intermolecular proton transfer of firefly Luciferin IV. temperature and pH dependence

Yuval Erez, Itay Presiado, Rinat Gepshtein, Dan Huppert

Research output: Contribution to journalArticlepeer-review

Abstract

Time-resolved emission as well as steady-state UV-vis techniques were employed to study the photoprotolytic processes that d-luciferin, the natural substrate of the firefly luciferase, undergoes in both acidic aqueous solutions and ice. The emission spectrum of d-luciferin in a 20 mM HCl aqueous solution or higher has an additional emission band at 590 nm red-shifted with respect to the strongest emission band positioned at 530 nm of the deprotonated NRO -* form in a pH-neutral aqueous solution. We attribute this emission band to the zwitterion form designated as +HNRO-. The time-resolved emission signals show that the NRO-* emission band at 530 nm and the zwitterion emission band at 590 are strongly quenched by a recombination process with a proton in an acidic solution and in ice. In ice, the quenching rate is 10 times faster than in the liquid state. We attribute the fast quenching rate to the high value of the proton diffusion constant in ice.

Original languageEnglish
Pages (from-to)1617-1626
Number of pages10
JournalJournal of Physical Chemistry A
Volume115
Issue number9
DOIs
StatePublished - 10 Mar 2011

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