Madrid - you'd have to say logically there would be some argument for a BA/IB joint venture to serve MAN-MAD and the onwards South America services ex-Madrid and in my mind the logical solution would be a twice daily MAN-based Embraer jet which, one assumes, would be most cost effectively operated by
(Locally based) CityFlyer aircraft & crew..
Ukraine - back in the 1990s Kiev, L'vov and Ivano-Frankovsk were served by Ukraine International. Once things are more settled in Kiev, and given their recent rate of growth you'd have to think Ukraine International would sooner or later show some interest in coming to Manchester. There is, after all, still a reasonably sized Ukrainian diaspora in the North-West, a number of whom even travel to/from their "home" country via coach! If Ukraine Int'l (or Jet2?) don't figure this out sooner or later you've got to assume Wizz Air will for flights LPL-Kiev...