Bioluminescent fungi are spread throughout the globe, but details on their mechanism of light emission are still scarce. Usually, the process involves three key components: an oxidizable luciferin substrate, a luciferase enzyme, and a light emitter, typically oxidized luciferin, and called oxyluciferin. We report the structure of fungal oxyluciferin, investigate the mechanism of fungal bioluminescence, and describe the use of simple synthetic a-pyrones as luciferins to produce multicolor enzymatic chemiluminescence. A high-energy endoperoxide is proposed as an intermediate of the oxidation of the native luciferin to the oxyluciferin, which is a pyruvic acid adduct of caffeic acid. Luciferase promiscuity allows the use of simple Α-pyrones as chemiluminescent substrates.
Kaskova, Z. M., Dörr, F. A., Petushkov, V. N., Purtov, K. V., Tsarkova, A. S., Rodionova, N. S., … Yampolsky, I. V. (2017). Mechanism and color modulation of fungal bioluminescence. Science Advances, 3(4). https://doi.org/10.1126/sciadv.1602847