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I am not sure, I´ve never used Paint.NET myself.As it seems to be mainly a photo editing software from what I have seen I´d say it should be possible but is not ideal for spriting. Personally I prefer the free edition of Graphics Gale for spriting.
CinnyricinclusHobbyist General Artist
When I first started spriting, everything I knew was from this tutorial ^^ you actually were the reason I started spriting... I saw your awesome sprites and I was like "I wanna be able to make those!" so I started practicing and I'm slowly getting there
Graphics Gale is in fact a lot more comfortable to use than Paint and it is free to download so you could still try (if you can download and install things on the computer you use of course)