Same Luciferin in Different Luciferases Emitting Different-Color Light. A Theoretical Study on Beetle Bioluminescence

Bioluminescent beetles, firefly, click beetle, and railroad worm, naturally emit different-color light via the identical luciferin and bioluminescence (BL) mechanisms. Railroad worm especially emits two colors of light in its dorsal-lateral and cephalic lanterns. Four computational models of bioluminophore (oLu) in luciferases of red-emitting, yellow-green-emitting, red-emitting with additional loop, and red-emitting without C-terminal were built in this paper. To unveil the details of this luciferase effect at the molecular and electronic-state levels, second-order multiconfigurational perturbation calculations were performed following molecular dynamic simulations and time-dependent density functional calculations for the above four oLu-luciferase systems. Via a systematic analysis on properties of oLu at the first singlet state (S₁-oLu) in different luciferases, one clearly see the details of the microenvironment and secondary structure of luciferase affecting the excited-state property of S₁-oLu, which ultimately result in the variant color of light emission. Typically, the increase in charge transfer of S₁-oLu leads to the longer wavelength BL.