Indeed so. Let’s look at what you wrote:
so it should simply load the smb:// path from the mysql library
that’s the “from” part of the path substitution
and replacing it with /mnt…
that’s the “to” part of the path substitution.
Your path substitution is this way:
<pathsubstitution>
<substitute>
<from>/mnt/Media/</from>
<to>smb://192.168.1.111/Media/</to>
</substitute>
<substitute>
<from>/mnt/usbshare2/</from>
<to>smb://192.168.1.111/usbshare2/</to>
</substitute>
</pathsubstitution>
Rather than me copy what has already been written, take a look at this post, which concisely explains what you need to do next.