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Coudln't find the answer in the many FAQs, when I purchase Piosolver Basic , can I later on upgrade to another version?
Yes, the upgrades cost the difference in prices + ~24$.
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Pio preflop takes a very long amount of time to stop after clicking the stop button, is this normal?
It depends what do you mean by "very long amount of time". From the sound of it it's not normal, the most useful report here would be a log:
-Tools->Configuration->enable logging
-reproduce
-send us log.txt
-switch the logging off (the file grows big quite fast so it's good not to have it on all the time)