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1. Before he left he made sure he had his keys with him.

2. Before he left he had made sure he had his keys with him.

3. After she got her degree, she became a teacher.

4. After she had gotten her degree she became a teacher.


Are they all correct?

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Yes.

But we usually don't use Past Perfect when there are words like before and after, as these make the sequence of events clear with just Simple Past.