Changing the database structure (that includes keys & indexes) will not be wise. Furthermore, database and the SAP Business One performance will be influenced by the change that you're planning.
There is a designed solution for the need to add user fields and manage them. The solution will include adding User Field and control its uniqueness via DI API. With this functionality you can add unique fields to the database without any harm done.
Please refer to the SAP Business One HELP on this subject.
You can contact me if you need more info on this issue.
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