Well, let me think about this and go down the list. Green Goblin was a science experiment gone wrong, and he used tech. Doc Ock was a science experiment gone wrong and tech-based. Sandman was a science experiment gone wrong, and that's it. Venom was... an alien. New Goblin was a science experiment gone wrong, and he used tech. In the Amazing series we had Lizard who was a science experiment gone wrong, Electro who was a science experiment gone wrong, Methgoblin who was something gone wrong, and used tech. Rhino was tech.
That was fun, haha.