Injury-triggered blueing reactions of Psilocybe "magic" mushrooms.

Lenz C, Wick J, Braga D, Garcia-Altares M, Lackner G, Hertweck C, Gressler M, Hoffmeister D (2020) Injury-triggered blueing reactions of Psilocybe "magic" mushrooms. Angew Chem Int Ed 59(4), 1450-1454. PubMed Open Access PDF

Abstract

Upon injury, psychotropic psilocybin-producing mushrooms instantly develop an intense blue color whose structure and mode of formation has remained elusive. Here, we report on two enzymes from Psilocybe cubensis that represent the two-step cascade to prepare psilocybin for oxidative oligomerization. The phosphatase PsiP removes the 4-O-phosphate group to yield psilocin, while PsiL oxidizes its 4-hydroxy group. The PsiL reaction was monitored by in situ 13C NMR spectroscopy, which indicated that oxidative coupling of psilocyl residues occurs primarily via C-5. MS and IR spectroscopy indicated formation of a heterogeneous mixture of preferentially psilocyl 3- to 13-mers and suggest multiple oligomerization routes, depending on oxidative power and substrate concentration. The results also imply that psilocybin's phosphate ester serves a reversible protective function.

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doi: 10.1002/anie.201910175 PMID: 31725937