E.L.
My daughter (6) does the same thing to her little brother (4). I think it's so adorable, but I also ask her to stop when she's telling him what to do the way a mom would. I tell her that he already has a mommy, he needs her to be his sister. I tell her that he needs to learn things for himself, so he'll be as great as she is. I would just keep reminding her, if I were you, and encourage her to help her brother with special "big sister" jobs, like reading, drawing, etc.
Our daughters sound very similar! Very maternal, yes - they will make great mommies someday! :-)