I am using Avast 4.6 and Win XP Home. I had the same problem when I was using Win98se(no firewall then)
My ISP SMTP sends well, but the other SMTP can’t send. So I ISP’s smtp to send email and it worked well.
I heard about ISP blocking port 25 from SMTP other than theirs.
Today I called SBC (used to be Pacific Bell) and found it really is them that blocked the port 25. I asked them to unblock it and reboot the pc and DSL modem. Now my long-idled other smtp server are sending well, actually both ISP email’s SMtp and the other pop email’s SMTP are sending fine.
Problem solved.
I guess someone else may have the similar problem and blaming Avast and trying do with firewall.