Theoretical Modulation of the Color of Light Emitted by Firefly Oxyluciferin

One of the major mysteries regarding firefly bioluminescence is its pH-dependent multicolor variation. At basic pH, the emission is on the yellow-green region, whereas at acid pH, the light emission is observed on the red region of the visible spectrum. Theoretical calculations using density functional theory, molecular mechanics, and semiempirical methods were made to investigate the effect exerted by intermolecular forces on light emission, and their modulation by polarity, and the differences in the conformation of the active site at basic and acid pH. Red emission is achieved by the weakening of the interactions of the emitter with ionic and hydrophobic molecules, by the polarization of the benzothiazole microenvironment, by ionization of the enzyme-emitter complex and by changes of the hydrogen bond network. Arg220, Glu346, Ala350, Leu344 and adenosine-5'-monophosphate have blue-shifting effects, while His247, Phe249, Gly341, Thr253, and Ile288 exert a redshifting one. (C) 2011 Wiley Periodicals, Inc. J Comput Chem 32: 2654-2663, 2011