Injury‐Triggered Blueing Reactions of Psilocybe "Magic" Mushrooms. (4th December 2019)

• Record Type: Journal Article
• Authors: Lenz, Claudius; Wick, Jonas; Braga, Daniel; García‐Altares, María; Lackner, Gerald; Hertweck, Christian; Gressler, Markus; Hoffmeister, Dirk
• Is Part Of: Angewandte Chemie. Volume 132:Number 4(2020)
• Page Start: 1466
• Page End: 1470
• Publication Date: 2019-12-04
• Subjects: Enzyme -- Laccase -- Naturstoffe -- Phosphatase -- Psilocybin; Chemistry -- Periodicals; 540
• DOI: 10.1002/ange.201910175
• Languages: English
• ISSNs: 0044-8249

Abstract

Abstract: Upon injury, psychotropic psilocybin‐producing mushrooms instantly develop an intense blue color, the chemical basis and mode of formation of which has remained elusive. We report two enzymes from Psilocybe cubensis that carry out a two‐step cascade to prepare psilocybin for oxidative oligomerization that leads to blue products. 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 13 C NMR spectroscopy, which indicated that oxidative coupling of psilocyl residues occurs primarily via C‐5. MS and IR spectroscopy indicated the 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 phosphate ester of psilocybin serves a reversible protective function. Abstract : Diese Pilze machen blau : Halluzinogene Psilocybe ‐Pilze färben sich bei Verletzung blau. Es wird gezeigt, dass die Phosphatase PsiP und die Laccase PsiL Psilocybin abbauen und das Bläuen initiieren. MALDI‐MS und In‐situ‐NMR‐Spektroskopie zeigen, dass der blauen Farbe eine Mischung von chinoiden Psilocyl‐Oligomeren zugrunde liegt, die primär über Kohlenstoff 5 gekoppelt sind.