I generally do not link an old-school dictator like Gaddafi with innovation but here is one in my book from the Al Jazeera live blog:
He also provides another account of security forces using high-caliber, possibly anti-aircraft guns against protesters.
In other posts the doctors mentioned seeing bullets “as big as their fists” in the dead and wounded that they are treating.
I am unaware of any other incidents in recent times when the army began directing high caliber high velocity weapons like this against (unarmed) protesters. I have seen water cannons, tear gas, and then escalating to small arms fire but using these sorts of weapons against civilians from your own nation is truly an innovation by Mr. Gaddafi.
As a commenter noted on my last post Gaddafi is on the United Nations Human Rights Council as you can see here. I would be interested in how directing anti-aircraft weaponry against unarmed protesters plays in the UN – probably not a big deal there, I would imagine.