Injury‐Triggered Blueing Reactions of Psilocybe “Magic” Mushrooms

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 ¹³C 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.     

Towards a “Chemical” Hamiltonian

An analysis of the LCAO Hamiltonian is performed in terms of a “mixed” formulation of the second quantization for nonorthogonal orbitals, compressing the different interactions to one- and two-center terms as far as possible by performing appropriate projections. For this purpose an operator of atomic charge is also introduced, the expectation values of which are the Mulliken gross atomic populations on the individual atoms. The LCAO Hamiltonian is decomposed into terms having different physical meaning and significance: (i) sum of effective atomic Hamiltonians; (ii) the electrostatic interactions in the point-charge approximation; (iii) the electrostatic effects connected with the deviation of the actual charge distribution from the pointlike one; (iv) two-center overlap effects; (v) finite basis (“counterpoise”) correction terms related to the individual atoms; and (vi) similar finite basis correction terms with respect to the two-center interactions. Only terms of types (i) to (iv), containing no three- or four-center integrals, are considered as having physical significance. Based on the analysis of the Hamiltonian, an energy partitioning scheme is developed, and explicit expressions are given for one- and two-center (and basis extension) components of the SCF energy. The approach is also applied to the problem of intermolecular interactions, and an explicit formula is given permitting calculation of the “counterpoise” part of the supermolecule energy by properly taking into account that it depends not only on the extension of the basis, but also on the occupation of the additional orbitals in the intervening molecule—a factor completely overlooked in the usual scheme of calculations.