World War II
On one of their missions Cap and Bucky chased Heinrich Zemo into Hydra castle, by passing his traps and his elite Hydra soldiers. During the fight, the Baron tasered Bucky unconscious and took him to his secret lab while Captain America chased after them to save his friend.
Bucky had seemingly died on his and Captain America's mission to chase after the Red Skull. However, he survived with only loosing his left arm and was taken to Belarus and experimented on by the Red Skull, who brainwashed him into the Winter Soldier and given a cybernetic left arm.
In later years, he was used to assassinate anyone who deemed a threat to Hydra, thus becoming something of a legend around him in espionage circles as the mysterious Winter Soldier. Between missions, he was kept in cryogenic suspension, ensuring that he remained a valuable asset for more than half a century which slowed his aging as a result.
Bucky lived long enough to meet his old War buddy Steve Rogers. Cap attempted to help Bucky regain his memories of who he really is and break free from Hydra's control. While this may have worked however, Bucky was horrified by the monster he had become and ultimately went into hiding, this became the Captains greatest regret for being unable to save old partner in time.
In modern times, the Winter Soldier infiltrated the Avengers Tower and got hold of the Red Skull for revenge, who was being imprisoned by the Avengers at the time. He used the Aven-Jet as a distraction to escape in the sewers, where Captain America followed him. Steve tried to convince the Winter Soldier to give the Skull back, as he had valuable information on Thanos, but Bucky knocked him out and escaped by climbing on a train. Captain America caught up with them, but the Winter Soldier escaped in a drone, and caused an explosion in the train tracks to slow Rogers down.
Falcon used a tracker that had been put in the Red Skull to pin the Winter Soldier's location to a missile silo in New Jersey. After pinning the Red Skull to one of the missile, the Winter Soldier found the tracker, and, having realized the Avengers would come for him, Bucky launched all the missiles in the base. Captain America and Falcon tracked down one of the missiles headed to Belarus, the place where the Winter Soldier had been created, as the rest of the team dealt with the other missiles. On the missile, Captain America was confronted by the Winter Soldier after trying to free the Red Skull.
Captain America tried to make the Winter Soldier understand that if he let the missiles hit their targets, he would only finally become what the Red Skull wanted, a villain. With less than half a minute for impact, the Winter Soldier escaped the missile. Captain America would manage to disarm it with the help of the Falcon.
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