This is certainly not possible at the moment as there is a lot of code that assumes books are stored in a file system owned by Calibre..
Whether it will become possible at some point in the future when the work that is going on in the database layer has been completed I have no idea (this work has as its a primary goal allowing multiple Caolibre clients to work of the same Calibre database). Even if it does become technically possible it will almost certainly require someone with the appropriate technical skills and an interest in doing it to put in some development effort.
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