Best fix of the patch and it wasn't even announced!
Update for all the questions:
1) Yes it works in real-time during an active game. We tried it in the raid without any trouble. You can transfer or retrieve items and synths.
2) You can't change your active gun while playing. No idea why you'd want to but you can't.
3) Transferring between characters works as long as you first transfer the item to the vault and then to the 2nd character.
4) Transferring materials will produce a dialog asking how many you want to transfer. You can now split groups if needed.
5) For me at least this effectively great increases vault space since I can get rid of duplicates and centralize materials. No need to carry materials on every character. A lot of (extra) exotics are going to die today.
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Glad you're happy. The team did some great work on this one.