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Top seed Ana Ivanovic suffered a shock defeat to Tsvetana Pironkova at the Rome International.
Ivanovic was beaten 6-4 5-7 6-2 by the Bulgarian qualifier, who troubled the world number three throughout with her powerful hitting.
The Serbian was able to save five set points from 2-5 and 0-40 down in the opening set, but Pironkova eventually held her nerve to take it at the sixth attempt.
Ivanovic grabbed the decisive break in the 11th game of the second set, but the third was one-way traffic as Pironkova booked her place in the third round with the biggest win of her career.
Her previous best victory came over Venus Williams at the 2006 Australian Open.
"I definitely made a lot of unforced errors off both sides. It felt tough, it was quite hard out there," Ivanovic said.
"I struggled to find my rhythm or find something inside to fight. I struggled to find my intensity today.
"I felt coming into this tournament that I was in good shape, I was working hard and doing well so I'm very disappointed. I really didn't play that well today."
Wimbledon champion Williams had no problems reaching round three in Rome, as she defeated Samantha Stosur 6-4 6-1.
The American seventh seed will meet Vera Zvonereva next after the Russian scraped through 7-5 4-6 7-5 against Iveta Benesova.
Venus' sister Serena, seeded fifth, wasted little time against Ukrainian Alona Bondarenko, hammering the doubles specialist 6-2 6-0.
Second seed Maria Sharapova also progressed in the tournament, seeing off the challenge of Dominika Cibulkova 6-2 3-6 6-4.
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