Will this work with PlexConnect ?
No, the Remote app only directly accesses your iTunes library.
It may be possible to write some sort of combination of Project Jasper and PlexConnect to get this functionality though it would require a microphone plugged into the hardware running PlexConnect and some heavy modification of PlexConnect itself (without reading through the PlexConnect code: you'd have to find a way to hook into PlexConnect to interact with what is specifically being served to a specific device...)
It would be a huge project but possible.