I would certainly include in the interview questions on how to diagnose and troubleshoot deadlocks in the database management system of your choice. In the same area, a developer for such system must also have solid understanding of isolation levels.
If you plan to use any sort of ORM (such as Hibernate or open JPA) consider making that a significant portion of your interview since the time to learn how to use one should not be underestimated and newbies will most likely cause more trouble than solve problems at the first.
Consider having the developer tracing and diagnosing a problem during the interview. I've seen candidates that could talk about SQL Server databases but didn't know about SQL Server's Profiler tool. Anyone working on such project needs to be proficient with this kind of tool (for the DBMS of your choice, of course.).
I also assume that since your project is web related you will be using some sort of application server. Having the candidate explaining how to track and debug concurrency problems such as racing conditions in the application itself is not a bad idea since a system with many users is likely to be multi threaded.
If you are interviewing for a Java position make sure the developer understands different types of references too (soft, weak, phantom). This is very handy to control and limit extensive resource allocation that is likely required by such applications, although finding someone that answers these questions might not be easy.
Good luck!
Eduardo