Who gets the $ in a T.O.D. acct, designated to my brother, in the event I get divorced. Would my brother still get the money, and not my spouse?

Once you are divorced, its as if your spoue pre-deceased you.  However, if those funds are in your name currently, then those funds are counted as your assets and may be included in the calculation of equitable distribution unless you can prove that those assets were not yours, and that they are being held by you.