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There are lots of ways Caesar Clown can knock out Luffy, since he literally has complete control over 1/3 of all known matter.
Besides using complex poisons like laughing gas, neural toxins, sleeping gas, insecticide etc., he could simply remove all oxygen, or replace it with carbon dioxide.
I wouldn't be surprised if he could create vacuum by drawing out gas from an area, like Luffy's lungs.
Now I'm thinking he probably has the Logia with the broadest range of effects, having control of not just an element, but an entire state of matter itself. The only other Logias that could match him is probably control over solids and liquids. Even so, those two states of matter are less harmful towards the human body itself.
If Caesar Clown really wants to destroy a body, he could probably fill someone's lungs with combustible gases and implode the person. Or maybe fill it with extremely toxic and corrosive uranium hexafluoride.
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