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Antione closed this, as a not python error, as
if you do not pass a valid certificate to openssl s_client
it will not read the system certificates, which is clearly
utterly surprising and nuts.
The problem, as I see it, is that fixing this clear
absurdity may not fix a different underlying problem. So this
one may need reopening when the real error us revealed. 
See if John Nagel's code works ...