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In the tiebreak, Williams was struggling until nerves got the better of Li as she made a series of unforced errors and the top seed took advantage to close it out with a second-service ace after 58 minutes.
CNN: Serena to play Henin in Australian Open final
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It left him needing to serve out the set and Djokovic made what would be his final push as he attempted to recover the break, but Nadal held his nerve like a champion at 5-4, 30-30, with an ace and a service winner.
BBC: Rafael Nadal wins US Open to seal career Grand Slam
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That one point never arrived as Nadal played his most brilliant tennis of the evening: forehand winner, service winner, backhand winner, ace and a strong serve to finish off the game.
WSJ: With 'Outrageous' Australian Open Win, Novak Djokovic Sets Sights on Paris
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Federer opened the second set with a double-fault but normal service was quickly resumed and a thumping ace down the 'T' helped him take game one with little reason for concern.
BBC: Federer claims historic Paris win
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Chela nicks the first two points of Murray's service game but Murray hits back with an ace.
BBC: French Open day four as it happened
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Not much to cheer for after that, though: Williams won the next three points with a 111 mph ace, a 100 mph ace, and a 101 mph service winner.
NPR: Ex-No. 1 Jankovic Advances At Rainy French Open
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Suddenly her erratic service began to work and she fired her first ace on the way to capturing the second set almost emphatically as her opponent had taken the first.
BBC: Determined Dominique in final
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Murray responded to lead 0-30 in Federer's next service game, but two marvellous drop shots, an ace and stunning cross-court forehand put the world number one within a game of levelling.
BBC: Roger Federer beats Andy Murray at ATP Tour Finals
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Federer backed that up with a majestic service game, which he held to love with one booming ace and the most delightful sliced backhand which died as soon as it touched the red dirt.
BBC: Federer claims historic Paris win