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It's your car, run whatever fuel you feel comfortable with. In my opinion, a N/A 4 cylinder with 9.5:1 compression, fixed valve timing and a 6300ish redline will never need anything over 91 if it's running correctly. Mine lives happily on 87, the only difference I noticed by running 92 (what we have in Bellingham) is that my wallet gets lighter.
I'm not aware of any ROM tunes for a 5S. You'll have to look into a piggyback or stand alone.
Cam's are worth it. There's a good post on Celica tech with dyno plots (at work don't have the link) of a before and after cam install on a 5S Call around your local area, you might be surprised how inexpensive regrinds can be.
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