Yes, 8.8.8.8/8.8.4.4 are google's DNS, they are hard coded so by changing the route once they cannot be seen the chromecast will default to the router gateway (or routed to the gateway depending on what you do). The chromecast was a pain in the butt with a VPN. I believe I had to initially set it up without the VPN in place, get it working on my network and then switch everything over to the VPN.
Just read your post again...I think to use the Chromecast on unblockus you would have to change the DNS settings on your router as there is no way (that I am aware of without rooting) to change the Chromecast. So there are two things to do, set the router DNS settings to whatever Unblockus uses and the static route to reroute the hard coded DNS settings in the Chromecast. In this case yes, everything else will run through unblockus. Now I remember why I stopped using unblockus, couldn't get Centre Ice from Rogers to work with it.
I guess something to try is route 8.8.8.8 directly to Unblockus. I would need to check on this a little more.
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