Mail - SMTP - Broken Sub-accounts.

Hello All,
I have an email account with an ISP that provides a main account and a number of sub-accounts that I use for family members. All accounts are receiving their email via Mail but only the main account is being allowed to send outbound mail via the SMTP server.
All accounts are expected to log on the the SMTP server authenticated with the username and password of the main account holder in BASE64 and the MAIL FROM field set to that of the main account holder. This have been working without fail for years using Mail until recently.
I have since used telnet, as below, to confirm the above.
HELO
AUTH LOGIN
<main account email address in BASE64>
<main account password in BASE64>
MAIL FROM:<main account email address>
RCPT TO:<[email protected]>
DATA
from:<[email protected]>
subject:Subject
date: 26 March 2008
to:<[email protected]>
Message.
QUIT
Can someone confirm that Mail has been changed in someway in a recent upgrade to cause the above.
Thanks in advance.
Message was edited by: Mathew Bosher

None that I'm aware of and even if possible, this does not fix the problem.
Has your wife's email only account created as a .Mac type account ever downloaded messages from the server?
If not, any error message provided?
To confirm, if the Mail.app is not set to save sent messages on the server for your wife's email only account, are sent messages available in the account's Sent mailbox under Sent in the mailboxes drawer?
If not, I would try deleting and re-creating the account first.

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