If they brought it out for DS, it would only consist of older GB and GBC games, and perhaps ALttP for GBA. There's no way Nintendo would bring out something like a demo of TP or WW on DS only for a Collector's Edition. You wouldn't even see OoT or MM on a Collector's Edition for the DS. I also don't believe they would ever bring out a version of FS with just single player. The whole basis of the game was to use multiplayer. Although it would be nice to actually be able to play the game w/out multiplayer, it would take away from its original intention. What they could do is just port the game and have the wireless connection pick up other players. And what would be especially better is if they could make it pick up players without the game cartridge, but it would probably be too much content to send to the other DS.
Link's Awakening DX, Oracle of Ages, Oracle of Seasons, and Minish Cap would be the idea DS Collector's Edition, or at least the most likely one. If they could fit it in, ALttP GBA would make it even better and also likely, especially where the new DSi doesn't support GBA compatibility, but there might be an issue there with the amount of space they could fit on one cartridge.
Speaking of the DSi, since it is supposed to have downloadable content, chances are that content is going to be older GB, GBC, and GBA games. So in my opinion, they will be releasing all of these games on that service instead of one big Collector's Edition cartidge.