title: The chemistry of bioluminescence: an analysis of chemical functionalities.
abstract: Firefly luciferase is one of the most studied bioluminescent systems, both theoretically and experimentally. Herein we review the current understanding of the bioluminescent process from a chemical functionality perspective based on those investigations. Three key components are emphasized: the chemiluminophore, the electron-donating fragment, and how these are affected by the substrate-enzyme interaction. The understanding is based on details of how the peroxide -O-O- bond supports the production of electronically excited products and how the charge-transfer (CT) mechanism, with the aid of an electron-donating group, lowers the activation barrier to support a reaction occurs in living organisms. For the substrate-enzyme complex it is demonstrated that the enzyme can affect the hydrogen-bonding around the CT-controlling group, resulting in a mechanism for color modulation. Finally, we analyse other luciferin-luciferase systems and compare them to the key chemical functionalities of the fragments of the luciferin-luciferase complex with respect to similarities and differences.
authors: Molecular Science Institute School of Chemistry, University of the Witwatersrand, PO Wits Johannesburg 2050, South Africa. isabelle.navizet@wits.ac.za
authors: Isabelle
authors: I
authors: Navizet
authors: Ya-Jun
authors: YJ
authors: Liu
authors: Nicolas
authors: N
authors: Ferré
authors: Daniel
authors: D
authors: Roca-Sanjuán
authors: Roland
authors: R
authors: Lindh
mesh_terms: D052160:Benzothiazoles / Q000737:chemistry; D049454:Firefly Luciferin / Q000737:chemistry*; D049409:Luciferases, Firefly / Q000737:chemistry / Q000378:metabolism*; D008163:Luminescent Measurements; D008962:Models, Theoretical
chemical_list: D052160:Benzothiazoles; D049454:Firefly Luciferin; D049409:Luciferases, Firefly; C005465:benzothiazole