You have get already very good tips. I could add this ones for completion:
Review your backups and contingency plans (and measure your restore times).
Usually you will want a mysql.conf for production mode, and a different one for full restore (with different parameters). A full restore of a so big database with the mysql defaults, can take looooooooong.
As an anecdote, in the most big mysql system I've ever touched, there was a "performance problem", when I got the credentials and started to review, 3 different sysadmins, had scheduled 3 different full backups daily, using dumps. Some of them at office hours.
Yes, this is just plainly stupid, but it's an example of real life.
On a big database system, backups (and restores) is something who is convenient to design with care, to monitor, and to measure/adapt periodically.
If you go to master/slave(s) usually you can make backups from some slave, without disrupt the master operations.
Also, you maybe interested in play with things like mysqlproxy to split reads/writes, so you can have writes going to master, but reads spread across multiple slaves.
I assume you're already using 64bits, and that you know already about mysql tuning variables.