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Bufadienolides (lucibufagins) from an ecologically aberrant firefly (Ellychnia corrusca)

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Abstract

The winter firefly (Ellychnia corrusca) is common throughout the eastern United States and Canada. It is notable among fireflies (Coleoptera: Lampyridae) for its adult activity during the winter and early spring months, and for its lack of a light-producing organ. Multiple lines of evidence suggest that E. corrusca is chemically protected, specifically its unusual phenology which results in prolonged exposure to predators, its aposematic coloration, its reflex bleeding upon disturbance, and its relatedness to toxic firefly genera. Chemical investigation of this species revealed the presence of large quantities (>500 μg/beetle) of steroidal pyrones known as lucibufagins. The structures of these lucibufagins were determined using 1D and 2D NMR spectroscopy along with UHPLC-HRMS. Four of these compounds were previously detected in fireflies of the genus Photinus, while the remaining four, which contain a highly modified D-ring of the steroid core, are previously unknown. Analysis of reflex bleeding showed that the hemolymph contained the lucibufagins and that it was primarily released via a band of cuticular pores along the costal margin of the elytra. In addition, our analysis of the eggs, larva, and pupa established that all immature stages possess lucibufagins, thus representing the first instance of a firefly species for which all life stages have been investigated chemically.

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Acknowledgements

Thanks to Dr. Kris Kolonko of the SAInT Center at Siena College for aiding in acquisition of UHPLC-HRMS. Funding from Siena College and Trinity College supported this research, which was also aided by a Research Starter Grant from the American Society of Pharmacognosy to SD. Thanks to David Posner and other members of the Deyrup research group for supporting this project. Summer research by ZA, MG, NH, and FR was supported by Siena Summer. Scholars grants from CURCA (Siena College). We are grateful for field site access provided by the Town of Andover, Connecticut; Camp Johnson, Bolton, Connecticut; and the Siismets and Smedley families. We appreciate field assistance contributed by other members of the Smedley lab, Kaitlyn O’Donnell, Dr. Fred Oliver, and various Trinity students. RR and KT were supported by the Trinity College Faculty Research Committee. Logistical aid was provided by Erin Mostoller and Vinnie Salvador. National Science Foundation Grant MRI-1039588 supported the electron microscopy. We thank Dr. James Lloyd and Lynn Faust for helpful discussion, and Dr. Marc Branham and Oliver Keller for their collaboration on the DNA barcoding.

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Authors and Affiliations

  1. Department of Biology, Trinity College, Hartford, CT, 06106, USA

    Scott R. Smedley, Riley G. Risteen, Kathareeya K. Tonyai & Julia C. Pitino

  2. Electron Microscopy Facility, Trinity College, Hartford, CT, 06106, USA

    Yunming Hu

  3. Department of Chemistry and Biochemistry, Siena College, Loudonville, NY, 12211, USA

    Zenab B. Ahmed, Brian T. Christofel, Maha Gaber, Nicole R. Howells, Connor F. Mosey, Faizan U. Rahim & Stephen T. Deyrup

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  1. Scott R. Smedley
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Correspondence to Stephen T. Deyrup.

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Smedley, S.R., Risteen, R.G., Tonyai, K.K. et al. Bufadienolides (lucibufagins) from an ecologically aberrant firefly (Ellychnia corrusca). Chemoecology 27, 141–153 (2017). https://doi.org/10.1007/s00049-017-0240-6

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