I was working on this as a redesign of my portfolio, but it has too many issues. Fun anyway, and I stumbled across something mildly interesting: triggering CSS3 transitions by resizing the window.
What it does: Resize the browser to see some useless CSS3 transitions happen! Maybe not useless, but at least not practical for most purposes... I don't think most users drag the re-sizer around on their browser just to see what happens. So far transitions look smoothest in Firefox 4 but sometimes get stuck when resizing.
Issues: For one, when bookmarking or linking directly to a page it won't show the right page. I tried detecting the hash with JS and applying the 'active' class to the corresponding div but it isn't reliable; sometimes it works and sometimes it only goes part way. It also "breaks the back button" eg: if you click 'About' then 'Portfolio' and use the browser's back button it will change in the address bar but not show the correct div. So, I don't think it's a problem with deep-linking but with the nature of fragment URLs... Could look into it some more, but I'm done with it for now.
Feel free to look at the source code and get some ideas of your own. Please tell me if any of it is useful :)
Update: some code here at forr.st/…