Should nail polish be removed before making ablution?
Yes, it should be removed because it prevents water from reaching the nails.
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 speaking while relieving oneself?
It is disliked for one relieving himself to speak while doing so, except out of necessity. And Allah the Almighty knows best.
Is it valid to perform the obligatory prayer while sitting?
Praise be to Allah, and peace and blessings be upon our Master, the Messenger of Allah.
Standing (Al-Qiyam) while having the ability to do so is one of the pillars (Arkan) of the prayer; the obligatory (Faridah) prayer is not valid without it. However, whoever is unable to stand may pray sitting down. As for voluntary (Nafilah) prayers, it is permissible to pray them sitting even if one is able to stand, but the one sitting receives half the reward of the one who prays standing. And Allah the Exalted knows best.