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Calibre does use a relational database. The actual program is just not a client-server model (albeit the content server is).
The primary problem with Dropbox (or any network storage to a lesser extent) is possible write conflicts. As mentioned, the library isn't designed to be accessed by multiple instances of Calibre at the same time.
I run Firefox Portable from Dropbox. That's probably more complicated and harder on the file system than Calibre.
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