Pluteus salicinus, shown here, has a bluing form that has been shown to contain psilocybin and psilocin. The presence of a bluing reaction in mushrooms frequently indicates the presence of these hallucinogenic compounds, though what produces the bluing is unknown. Mushrooms can contain psilocybin and still not produce a bluing reaction. In addition compounds like boletol produce a bluing reaction in mushrooms that contain no hallucinogens. The darkening reaction on the stems of some deadly Galerinas can be mistaken for a bluing reaction, so caution and a sound knowledge of how to identify mushrooms is always in order if you are going to consume wild mushrooms.
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