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Williams sank to her knees after firing a backhand winner on her second match point. She became the eighth woman to win 11 or more titles a year and the first since Martina Hingis had 12 in 1997.
The defending champion won the first seven games of Friday's match, then actually fell down a break early in the second set, before quickly regaining it on the way to a 6-0, 6-3 victory over fifth-seeded Li Na.
Each took a step forward Friday, shaky at moments and sensational in others, in second-round victories. The top-seeded Djokovic faced two early set points, while defending champion Murray had to go four sets.
The fifth-seeded Li defeated Sweden's Sofia Arvidsson 6-2, 6-2 in the day's first match. Shortly afterward, heavy rain came and Li's only concern was finding an umbrella to cover herself on the walk to the car.
Defending champion Andy Murray could face top-seeded Novak Djokovic only in the U.S. Open semifinals, while Nadal and Federer — who have never played each other at Flushing Meadows — might meet in the quarterfinals.
The world's top-ranked player has never won Cincinnati, losing in the finals four times. Djokovic lost to Roger Federer in the title match last year.
Week 2 begins Monday with a schedule that includes participants such as Kenny de Schepper and Adrian Mannarino, Ivan Dodig and Jerzy Janowicz, Karin Knapp and Monica Puig.