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

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 un...

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Bibliographic Details
Published in:Organic & biomolecular chemistry 2017-04, Vol.15 (16), p.3479-3484
Main Authors: Salatino, Carla T, Melo, Diêgo U, Yoshitake, Ariane M, Sgarbi, Lucas S, Homem-de-Mello, Paula, Bartoloni, Fernando H, Ciscato, Luiz F M L
Format: Article
Language:English
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Summary: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.
ISSN:1477-0520
1477-0539
DOI:10.1039/c7ob00603a