You could use a Verify Email API to check email addresses, like this one
http://verify-email.org/using-api.html or this one
http://emailpie.com/.
simple api that checks if an email address if valid and exists. It checks the format of the address then tries to contact the server to make sure the address exists.
Here's some others:
http://blog.mashape.com/list-of-25-email-validation-apis/
To use with AppInventor, simply do a Web.Get to the URL (with the email address in it) as specified, and see what the response is in Web.GotText.
If the response says it's valid, proceed with submit. If not valid, don't submit.