For a set of even billions of assets, the chances of random collisions are negligibly small -- nothing that you should worry about. Considering the birthday paradox, given a set of 2^64 (or 18,446,744,073,709,551,616) assets, the probability of a single MD5 collision within this set is 50%. At this scale, you'd probably beat Google in terms of storage capacity.
However, because the MD5 hash function has been broken (it's vulnerable to a collision attack), any determined attacker can produce 2 colliding assets in a matter of seconds worth of CPU power. So if you want to use MD5, make sure that such an attacker would not compromise the security of your application!
Also, consider the ramifications if an attacker could forge a collision to an existing asset in your database. While there are no such known attacks (preimage attacks) against MD5 (as of 2011), it could become possible by extending the current research on collision attacks.
If these turn out to be a problem, I suggest looking at the SHA-2 series of hash functions (SHA-256, SHA-384 and SHA-512). The downside is that it's slightly slower and has longer hash output.
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