DPI can certainly be used to detect VPNs, but my broader point is, if you want real assurance, you need to get a VPN working; you can't rely on TCP/IP reassembly glitches, because they're largely addressable by the serious DPI vendors.
I suggest you consult a book like "The TCP/IP Guide" to get an overview of the main data protocols and how they work. In this day and age, everybody ought to know something about the basic protocols which form the bedrock of our networked society.