Insect Collections as an Untapped Source of Bioactive Compounds-Fireflies (Coleoptera: Lampyridae) and Cardiotonic...

Natural history collections provide an invaluable basis for systematics, ecology, and conservation. Besides being an important source of DNA, museum specimens may also contain a plethora of natural products. Especially, dried insect collections represent a global repository with billions of inventoried vouchers. Due to their vast diversity, insects possess a great variety of defensive compounds, which they either produce autogenously or derive from the environment. Here, we present a case study on fireflies (Coleoptera: Lampyridae), which produce bufadienolides as a defense against predators. These toxins belong to the cardiotonic steroids, which are used for the treatment of cardiac diseases and specifically inhibit the animal enzyme Na⁺/K⁺-ATPase. Bufadienolides have been reported from only seven out of approximately 2000 described firefly species. Using a non-destructive approach, we screened 72 dry coleopteran specimens for bufadienolides using HPLC-DAD and HPLC-MS. We found bufadienolides including five novel compounds in 21 species of the subfamily Lampyrinae. The absence of bufadienolides in the phylogenetically related net-winged beetles (Lycidae) and the lampyrid subfamilies Luciolinae and Lamprohizinae indicates a phylogenetic pattern of bufadienolide synthesis. Our results emphasize the value of natural history collections as an archive of chemical information for ecological and evolutionary basic research and as an untapped source for novel bioactive compounds.