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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.
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Submitted on : Thursday, November 8, 2012 - 1:34:35 PM
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Isabelle Navizet, Y.-J. Liu, N. Ferré, D. Roca-Sanjuan, R. Lindh. The chemistry of bioluminescence: an analysis of chemical functionalities.. ChemPhysChem, Wiley-VCH Verlag, 2011, 12 (17), pp.3064-76. ⟨10.1002/cphc.201100504⟩. ⟨hal-00749782⟩



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