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They are going to have to have their own device profile in your itunes to be able to synch it wired or wirelessly.
You can just email the file to them. iBooks supports Open In for epubs at least within safari and I'd assume from within the mail client as well (though I haven't specifically attempted that).
iBooks supports synching through iCloud. I am not 100% sure, but I am pretty sure that includes sideloaded content and not just itunes purhcased books. Though that won't support pushing epubs out to the devices that weren't purchased through itunes, only last read and I think bookmark synching from files. So you'll still have to get the epub on the device...which again you can just email it to the other device and open it on there to load it in to iBooks and then last read and bookmarking can/will be synched through iCloud.
Though the synching will only be with the book loaded on devices using the same appleID.
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