When your Android device is connected to your VPN, Android BubbleUPnP cannot detect any UPnP/DLNA device (renderers, libraries) nor BubbleUPnP Server, because
on most VPN, SSDP multicast discovery do not work.
With BubbleUPnP Server, you can only access media servers when there is not SSDP discovery (usual case is via the Internet but also apply to VPN).
So you must manually connect to 'BubbleUPnP Server' in More > Settings > Internet access with BubbleUPnP Server. Use the Setup wizard (or click on an 'Unset' entry) and
for 'Server address' use the local ip address of BubbleUPnP on your VPN. That would be the 'LAN Ip address' field displayed in the 'Status' tab:
For example, if the 'LAN Ip address' field is 10.0.0.4, use
http://10.0.0.4:58050 for the 'Server address' field.
Set the 'Login' and 'Password' fields to the value you set in the BubbleUPnP Server 'Network and security' tab.
Then in the Library tab, you should see your media server available as Library.