If you have confirmed that the provider is set to appear in AppointNow but they still are not showing in MyTooth, its possible one of two problems could be occurring.
First:
While in MyTooth, its possible that the provider is there, you just cannot see them due to the default filtering.
When in the 'Providers Schedule' sub menu in MyTooth, make sure 'Booking Online' is set to All and verify the provider still does not appear. 
Second:
It could be that the provider has not synced over from your PMS yet.
To resolve this you can manually request a sync of data via the UI or wait over night and it should sync automatically.
Simply navigate to 'Denticon Authentication Settings' or 'Cloud 9 Authentication Settings' and click on 'Resync'