Hi there,
The from attribute in the web.config only serves as a default / fallback for cases where you don't specify one in code. Take a look at the example on page 319 and you'll see something like this:
Replace the name and address with your own data to make this dynamic.
Not sure why you would want to change the SMTP server (used to send the messages) based on the user, but you can do it by specifying an alternative server when constructing the SmtpClient:
Code:
Dim mySmtpClient As SmtpClient = New SmtpClient("your.host.here")
Hope this helps,
Imar