Mechanistic model for the firefly luciferin regeneration in biomimetic conditions: a model for the in vivo process?

Author(s)

Salatino, Carla T. ; Melo, Diego U. ; Yoshitake, Ariane M. ; Sgarbi, Lucas S. ; Homem-de-Mello, Paula ; Bartoloni, Fernando H. ; Ciscato, Luiz F. M. L.

• Document type: Journal article
• Source: ORGANIC & BIOMOLECULAR CHEMISTRY; v. 15, n. 16, p. 3479-3484, APR 28 2017.
• Web of Science Citations: 2

Abstract

The emission of light by fireflies involves the enzymatic oxidation of firefly luciferin and ends up in the formation of 2-cyano-6-hydroxybenzothiazole, and this is recycled back to luciferin by condensation with cysteine. In this work, we suggest a mechanism for this transformation that operates under mild conditions that are similar to in vivo environments (i.e. biomimetic); the rate-determining step consists of an intermolecular nucleophilic attack from the cysteine thiolate on the nitrile, catalysed by a specific base, followed by a complex sequence of intramolecular reactions which are highly dependent on the medium pH. (AU)

• FAPESP's process: 12/02428-5 - Cyclic organic peroxides: synthesis and mechanism of reduction
• Grantee: Luiz Francisco Monteiro Leite Ciscato
• Support type: Regular Research Grants
• FAPESP's process: 12/13807-7 - New tools for the study of electron transfer reactions in PS II model systems
• Grantee: Fernando Heering Bartoloni
• Support type: Regular Research Grants