Corrected entry: Towards the end of the movie, when Captain America combats the aliens in the building with the civilians held hostage, he throws his shield and is left to fight them hand to hand. A grenade is dropped and in the meantime, his shield is nowhere to be seen. Cap rushes to the window in one shot and in the next he is holding his shield in time to protect himself from the blast.
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Correction: If you look closely after Cap defends himself with that aliens body and does the back flip/roll he picks up the shield from the ground to protect himself from the blast.