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Yaroslava Shvedova was dumped out of the first round of the Brasil Tennis Cup by Melinda Czink.
Shvedova, who was thought to be the main threat to top seed Venus Williams - who is in action on Tuesday - in Florianopolis, lost 2-6 6-4 6-2 to the Hungarian.
The Kazakh looked in cruise control after the first set, but the world No 100 battled back to level and then was dominant in the third, winning eight of the final 10 games of the match.
Shvedova was being tipped as a future top 10 player last year but her recent form has been hugely disappointing, winning just seven matches in her last 12 tournaments.
Sixth seed Anabel Medina Garrigues of Spain was another first round casualty as she contrived to lose 5-7 7-6 (9-7) 6-1 to Romania's Monica Niculescu.
Garrigues had three match points at 6-3 up in the second set tie break, lost the lot, and collapsed completely in the decider.
Fourth seed Chanelle Scheepers of South Africa almost went the same way as the others.
But the fourth seed held her nerve to spectacular effect in the deciding set with Venezuela's Adriana Perez, winning 2-6 6-4 6-0.
Williams will be facing veteran Mirjana Lucic-Baroni - who as a teenager in 1999 memorably reached the Wimbledon semi-finals - in the opening round.