A straight is ranked by its highest card:
So in the case of A-2-3-4-5, you are using the ace as a LOW, so you would have a 5 high straight.
A 2-3-4-5-6 straight beats the straight mentioned above because it has a 6 high, which tops a 5-high.
The best straight is 10-J-Q-K-A, which uses the ace as a HIGH.
Hope this cleared up any confusion.
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