This useful tip comes from Aaron Lu passed along by Harlan Brumm. By default any connection, regardless if it currently exists at the location stored, will appear in the Revit DB Link New or Recently Used Connection list:
If you want to clear out this list at any point I have included the process below:
1. Close Revit 2010.
2. Navigate to the following folder location:
For Windows XP
%USERPROFILE%\Local Settings\Application Data\IsolatedStorage
For Windows Vista
%USERPROFILE%\AppData\Local\IsolatedStorage
3. There should be a number of named folders at this location; navigate down until you find a folder typically called AssemFiles. If you don’t see this simply search for a file called Revit DB LinkConnections.txt.
4. Delete Revit DB LinkConnections.txt.
5. Launch Revit 2010 > Add-Ins > External Tools > Revit DB Link to verify the list is blank.
The file is created \ modified every time you create a new connection and contains the connection information.
After deleting the file the New or Recently Used Connection list should appear blank.