Structure Elucidation and Spectroscopic Analysis of Chromophores Produced by Oxidative Psilocin Dimerization

Abstract

Psilocin (1) is the dephosphorylated and psychotropic metabolite of the mushroom natural product psilocybin. Oxidation of the phenolic hydroxy group at the C‐4 position of 1 results in formation of oligomeric indoloquinoid chromophores responsible for the iconic blueing of bruised psilocybin‐producing mushrooms. Based on previous NMR experiments, the hypothesis included that the 5,5’‐coupled quinone dimer of 1 was the primary product responsible for the blue color. To test this hypothesis, ring‐methylated 1 derivatives were synthesized to provide stable analogs of 1 dimers that could be completely characterized. The chemically oxidized derivatives were spectroscopically analyzed and compared to computationally derived absorbance spectra. Experimental evidence did not support the original hypothesis. Rather, the blue color was shown to stem from the quinoid 7,7’‐coupled dimer of 1.

Cultivation, chemistry, and genome ofPsilocybe zapotecorum

“…Homologs of the laccase, PsiL, and the phosphatase, PsiP, which are involved in conversion of psilocybin to chromophoric oligomers, were also found in separate loci in P. zapotecorum . 24…”

“…This trauma-induced bluing is a enzymatic reaction that’s’ mechanism has been characterized in detail in P. cubensis . 24,25 With regards to P. zapotecorum , it is not known whether the color shade and intensity observed is due to higher concentrations of psilocybin, higher activity of psilocin oligomerization enzymes, or multiple compounding factors.…”

“…This trauma-induced bluing is a enzymatic reaction that's' mechanism has been characterized in detail in P. cubensis. 24,25 With regards to P. zapotecorum, it is not known whether the color shade and intensity observed is due to higher concentrations of psilocybin, higher activity of psilocin oligomerization enzymes, or multiple compounding factors. Tryptamine concentrations do not appear to be elevated compared to other psilocybin containing mushrooms [Stijve and de Maijer (0.6-3 mg/g psilocybin, 0.5-10 mg/g psilocin, up to 0.2 mg/g baeocystin), Heim and Hofmann (0.5 mg/g psilocybin, 0 mg/g psilocin, 2 year old specimens)].…”

Indole Alkaloids from Psychoactive Mushrooms: Chemical and Pharmacological Potential as Psychotherapeutic Agents

“…Both psilocybin and psilocin are chemically unstable; however, it is believed that the phosphate group on psilocybin also improves the stability of the active metabolite, preventing degradation in the mushrooms, biomass, and extracts [20,56]. Some procedures and solvents favor the phosphate ester hydrolyzation in psilocybin, and the subsequent enzymatic oxidation of psilocin leading the develop of the characteristic blue colorations in the mushroom extracts by formation of quinoid oligomers [57,58]. In this context, the key steps to guarantee their stability during extraction are enzyme inactivation and dehydration.…”

Fungal Hallucinogens: Chemistry, Synthesis, Behavior, Toxicity and Detection Methods in Forensic Perspective

“…They appear as green crystals when extracted 17 . Psilocin islipid soluble and hence it is diluted by acidified aqueous solution and very slightly soluble in water 18 . Its melting point is found to be 173-176 o C. Its molecular weight is to be 204.3g/mol 19 .…”