Is it permissible for someone to make a supplication to Allah to marry an already married, or an engaged woman?
No, it isn`t, and the person who does so is sinful before Allah, The Almighty.
Is it permissible for a guardian (Big brother) to unlawfully stop his sister from getting married?
If the guardian denies her right in getting married for an unlawful reason, she should go to court in order to settle that matter, and the guardian is considered sinful in this case.
What is the ruling on praying behind an undesirable Imam?
It is permissible to pray behind an Imam who is undesirable for committing religious violations, and it is disliked for such an Imam to lead the prayer. Still, If he was undesirable for a personal, or a worldly matter, then such argument doesn’t hold water. And Allah Knows Best.
Should a woman who broke her fast because of delivery make up for missed fasting days before the next Ramadhaan, and what is the expiation due on her in case she delayed making up for them ?
She should make up for missed fasting days before the start of next Ramadan if possible, but if she didn`t while being able to, then she is obliged to make up for them along with feeding a needy person for each delayed day of the missed fasting days. However, if she wasn`t able to make up for the missed fasting days before the start of next Ramadan, she has to fast a day for every day that she missed, and no ransom is due on her. And Allah Knows Best.