in episode 47-48 chapter 132-133..then if you want to from when gin was with kira before they saw hitsugaya you can start from chapter 130 that follows the anime
it quotes "Hitsugaya acts upon his earlier threat and attacks Gin, releasing his ZanpakutÅ and warning Kira to get out of the way (he suggests at least a twelve-kilometer gap). During their fight, Hitsugaya successfully freezes Gin's left arm, causing him to open his eyes and drop his smile for the first time. Upon being trapped by Hitsugaya, he attempts to kill Hinamori as a distraction, but his attack is blocked by Rangiku Matsumoto, who threatens to fight him if he doesn't stop; Gin relents and disappears without saying a word."
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in episode 47-48 chapter 132-133..then if you want to from when gin was with kira before they saw hitsugaya you can start from chapter 130 that follows the anime
you want to check it out, here
http://www.mangareader.net/94-586-1/bleach/chapter...
hope it helps :D
According to http://bleach.wikia.com/wiki/T%C5%8Dshir%C5%8D_Hit...
it quotes "Hitsugaya acts upon his earlier threat and attacks Gin, releasing his ZanpakutÅ and warning Kira to get out of the way (he suggests at least a twelve-kilometer gap). During their fight, Hitsugaya successfully freezes Gin's left arm, causing him to open his eyes and drop his smile for the first time. Upon being trapped by Hitsugaya, he attempts to kill Hinamori as a distraction, but his attack is blocked by Rangiku Matsumoto, who threatens to fight him if he doesn't stop; Gin relents and disappears without saying a word."
Not sure what episode it is in... Sorry!