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Steve: Bucky, you've known me your whole life, your name is "James Buchanan Barnes".
Bucky: SHUT UP!
Steve: I'm not gonna fight you, you're my friend.
Bucky: You're my mission, YOU'RE MY MISSION!
Steve: Then finish it, Because I'm with you to the end of the line.
~ Captain America reasoning with Bucky that he is his friend.

Just because another character is a villains does not always mean Pure Goods are enemies with them. A friend of a villains is a pure good hero who have a friend who is a villain. It is also possible that their friend could brainwashed (though this may not always be the case if villains are in their normal senses and may refuse to side with pure good heroes if this happens).

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