Are you running Calibre under Windows? If so you might want to look in the resources sub-folder of the Calibre install location and then examine the file calibre-portable.bat. Although that was targetted primarily at those who wanted a portable calibre it also shows how to run with the books on a network share and the metadata database held locally - that can provide a significant performance boost if the bottleneck is database access as sqlite (which is what Calibre uses) is known to be slow running over a network..
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