in the episode where she beat up heue
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He likes her towards the bggining, he admits he will protect her,.
They arrive in episode 124, but Gaara and Kimmimaro start fighting in episode 126.
Naruto end of episode 56 and start of episode 57
He first appears in episode 64 but his fight with Natsu doesn't really start till episode 65 then it's finished in episode 67.
Byakuran and Tsuna start battling in episode 200 and the fight ends in episode 202.