Abstract
Fungal bioluminescence is a fascinating natural process, standing out for the continuous conversion of chemical energy into light. The structure of fungal oxyluciferin (light emitter) was proposed in 2017, being different and more complex than other oxyluciferins. The complexity of fungal oxyluciferin arises from diverse equilibria such as keto/enol tautomerization or deprotonation equilibria of four titratable groups. For this reason, still some crucial details of its structure remain unexplored. To obtain further structural information, a combined experimental and computational study of natural and three synthetic fungal oxyluciferin analogues has been performed. Here, we state the most stable chemical form of fungal oxyluciferin regarding its keto and enol tautomers, in the ground and excited states. We propose the (3Z,5E)-6-(3,4-dihydroxyphenyl)-4-hydroxy-2-oxohexa-3,5-dienoic acid form as the light emitter (fluorescent state) in water solution. Moreover, we show that chemical modifications on fungal oxyluciferin can affect the relative stability of the conformers. Furthermore, we show the clear effect of pH on emission. General conclusions about the role of these titratable groups in emission modulation have been drawn, such as the key role of dihydroxyphenyl deprotonation. This study is key to further analyze the properties of fungal bioluminescence and propose novel synthetic analogues.
Talk to us
Join us for a 30 min session where you can share your feedback and ask us any queries you have
Schedule a callDisclaimer: All third-party content on this website/platform is and will remain the property of their respective owners and is provided on "as is" basis without any warranties, express or implied. Use of third-party content does not indicate any affiliation, sponsorship with or endorsement by them. Any references to third-party content is to identify the corresponding services and shall be considered fair use under The CopyrightLaw.
