The Fifth Archdaemon

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I am helping a friend to DM his first pathfinder campaign, and while going over the Doppleganger creature in preparation for an encounter, i thought of something:

The doppelganger has a listed immunity to charm and sleep, and i was wondering: is this immunity only to magical sleep effects? or can a doppelganger be put to sleep by non-magical means like some kind of alchemical gas attack?