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Banister, I did a new installation of UNA, and had forgotten all the configuration stuff from my prior installs. Anyway, I encountered the same problem. I resolved it when I noticed in the Studio > Settings Module > Cache > "Email to send site messages from" that it required the email to send site messages from as no-reply@mysite.com email.
It appeared that the SMTP Mailer module was in conflict with this already set email setting in the Settings Module. I was not getting the site to send out confirmation emails until I removed the SMTP module. Then it worked, I sent a confirmation email to myself from a profile I created.
It might be possible to remove the email from the Settings Module, in order to use the SMTP module, I have not tried that yet. However, this worked for me, so you might try it.