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So I downloaded SQL Server 2008 R2 Express and installed it. I uninstalled 2005 version.
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If you did it in this order, your new 2008 Rs instance will not be called .\SqlExpress as that name was already taken by the 2005 installation. The trick is to find out the instance name of your SQL Server which you can do by looking at the SQL Server Configuration Manager.
Also, make sure you're not attaching the database to SQL Server using Management Studio *and* try to access it thorugh the App_Data folder. Each option keeps a lock on the database which prevents the other from accessing the files. So, either use App_Data, or use a folder outside your web site's folder such as C:\Databases.
Cheers,
Imar