Photoinduced chemical reactions on natural single crystals and synthesized crystallites of mercury(II) sulfide in aqueous solution containing naturally occurring amino acids

Photoirradiation at >300 nm of aqueous suspensions of several natural crystal specimens and synthesized crystallites of mercury(II) sulfide (HgS) induced deaminocyclization of optically active or racemic lysine into pipecolinic acid (PCA) under deaerated conditions. This is the first example, to the best of our knowledge, of photoinduced chemical reactions of natural biological compounds over natural minerals. It was found that the natural HgS crystals had activity higher than those of synthesized ones but lower than those of other sulfides of transition metals, e.g., CdS and ZnS, belonging to the same II-IV chalcogenides. In almost all of the photoreactions, decompostion of HgS occurred to liberate hydrogen sulfide (H(2)S) and Hg(2+), and the latter seemed to have undergone in-situ reductive deposition on HgS as Hg(0) after a certain induction period (24-70 h) during the photoirradiation, as indicated by the darkened color of the suspensions. The formation of PCA, presumably through combination of oxidation of lysine and reduction of an intermediate, cyclic Schiff base, could also be seen after a certain induction time of the Hg(0) formation. This was supported by the fact that the addition of small amount of Hg(2+) (0.5 wt % of HgS) increased the PCA yield by almost 2-fold. We also tried to elucidate certain aspects of the plausible stereochemical reactions in relation to the chiral crystal structure of HgS. Although, in some experiments, slight enantiomeric excess of the product PCA was observed, the excess was below or equal to the experimental error and no other supporting analytical data could not be obtained; we cannot conclude the enantiomeric photoproduction of PCA by the natural chiral HgS specimen.