find out what the event format is, big 100km races often have feed stops where you can refill bottles, pick up bannanas and flapjack etc.
As for fuel, dont try anything new or unusal on the day, if you train eating harribo, take that on the day. Energy drinks and gells gave me stomach cramp, so I stick with flapjack and jelly beans.
Tyre pressure, whatever feels good and works, higher PSI's will reduce rolling resistance on hard/smooth ground, softer will increace grip and comfort at the expense of speed. But dont play about on the day, if youve been training at 35-40psi stick to that, i did a sportive and droped my pressures by 10psi for comfort (100 down form 110) and it felt horrible, the tires went all squidgy in the corners.