I've never had my roms zipped, but Mario vs DK works perfectly for me unzipped with GPSP .09.
It ran in an earlier version but wasn't quite smooth/sound was a little jumpy. Exophase has done some dam fine work with the emu as it runs beautifully now.
32mb roms have to be unzipped but Mario vs DK is only 16 so it should work. Unless you only have a 32mb mstick i'd say you're best off just leaving it unzipped.
EDIT: My rom is the USA version.
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