Acetyl-l-carnitine seems to sharpen the mind a little and reduce the need for coffee, and is popular with the nootropic/life extension crowd. Commonly combined with lipoic acid which also anecdotally helps a little.
Rhodiola rosea or schizandra are slightly stimulating adaptogens which some people respond very well to. There's a double blind placebo controlled study on pubmed on doctors after night duty who had improved alertness and decision making on rhodiola. I can attest to its effect when I've been sleep deprived. Always worth checking there's no reason not to take such things though, like interactions with medications you might be on. The effects wear off if taken every day so best to use intermittently.
SAD type lamps for a 15min burst on rising and during the day helps keep you more alert by switching off your melatonin production. A dawn simulating lamp can make waking up easier and regulate your cycles, and i guess trying some press ups on waking could do some good :)