Moonlighting Metals: Insights into Regulation of Cyclization Pathways in Fungal Δ6-Protoilludene Sesquiterpene Synthases

Maureen B. Quin, Stephen N. Michel, Claudia Schmidt-Dannert

Research output: Contribution to journalArticlepeer-review

9 Scopus citations


Fungal 1,11 cyclizing sesquiterpene synthases are product specific under typical reaction conditions. However, in vivo expression of certain Δ6-protoilludene synthases results in dual 1,11 and 1,10 cyclization. To determine the factors regulating this mechanistic variation, in-depth in vitro characterization of Δ6-protoilludene synthases was conducted. Divalent metal ions determine cyclization specificity and this product variability. Promiscuity in metal binding is mediated by secondary metal-binding sites away from the conserved D(D/E)XX(D/E) motif in sesquiterpene synthases. Phylogenetic analysis revealed a divergent evolution of Basidiomycota trans-humulyl cation producing sesquiterpene synthases, results that indicate a wider diversity in function than previously predicted. This study provides key insights into the function and evolution of 1,11 cyclizing fungal sesquiterpene synthases.

Original languageEnglish (US)
Pages (from-to)2191-2199
Number of pages9
Issue number15
StatePublished - Oct 1 2015

Bibliographical note

Publisher Copyright:
© 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.


  • GC/MS
  • biosynthesis
  • kinetics
  • natural products


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