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French Open champion Rafael Nadal will face his 2012 Wimbledon nemesis, Lukas Rosol, on Thursday, knowing he will have to up his game to avoid another second-round exit at the hands of the Czech world number 52.
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Maria Sharapova, buoyant after her triumph at the French Open, takes on Swiss qualifier Timea Bacsinszky. The fifth seed is seeking a second Wimbledon crown 10 years after her first. Third seed Simona Halep, runner-up at the French Open and a quarter-finalist at the Australian Open this year, will hope to extend her fine Grand Slam form against qualifier Lesia Tsurenko of Ukraine.
Top seed and five-time champion Serena Williams will be a daunting opponent for South African world No 94 Chanelle Scheepers on Court One.
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After a first-round defeat at the All England Club last year, and failure at the same stage at Halle two weeks ago, the World No 1 ended a three-match grasscourt losing streak with a nervous four-set win over Martin Kilzan on Tuesday to set up the Rosol rematch on Centre Court.
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"He's a player that can play very well on this surface," Nadal, champion in 2008 and 2010, said.
"I lost (in 2012) because he's a good player. He's an aggressive player. I know if I want to have chances to win, I need to play very well."
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Seven-time champion Roger Federer will be confident of making it four wins out of four against qualifier Gilles Muller of Luxembourg.
The pair have met before on the hard courts of Indian Wells, Bangkok and the US Open, their last contest dating back to 2008.
Fifth-seeded Australian Open champion Stanislas Wawrinka, who could face the Swiss 17-time Grand Slam winner in the quarter-finals, meets Lu Yen-Hsun from Taiwan for the first time.