Pictochat is unchanged from previous Nintendo DS gaming systems, except for the fact that exiting Pictochat now returns you to the DSi menu as opposed to shutting the system down. Also, with the DSi, you can now use a rainbow pen, which is backwards compatible with the original DS and the DS Lite. The original DS and DS Lite can receive and copy rainbow colors sent by the DSi.
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Pictochat hasn't been changes much by its NDS and NDSL predecessors. Only two changed have been made (that we know of). One change is the rainbow pen. You can use the rainbow pen by clicking on the Pen icon to toggle back in forth between the black pen and the rainbow pen. the other change is that when you exit Pictochat it takes you back to the DSi's homescreen instead of making you shutdown.
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You can toggle color on and off by tapping on the pen tool when it's on already.