Li Na's hopes of a French Open-Wimbledon double have ended as the Chinese was beaten by wildcard Sabine Lisicki but Serena Williams, the last player to achieve the feat, continued her comeback in ominous fashion.
Novak Djokovic and Roger Federer continued their swashbuckling progress through the draw and fifth seed Robin Soderling fought back from two-sets down to beat former champion Lleyton Hewitt in an enthralling match.
Li, who became the darling of the world's most populous nation by triumphing at Roland Garros earlier this month, squandered two match points in a 3 sets loss to the German.
Australian former world number one Hewitt, still a dogged competitor despite the injuries that have seen him drop out of the top 100, looked set to pull off the biggest shock of the tournament but Soderling won in 5 after nearly four hours of baseline combat.
Second seed Djokovic continued his perfect start with a crushing straight sets victory over South African Kevin Anderson, while third seed Federer also looked a class apart as he continued his bid for a seventh Wimbledon title and 17th grand slam crown with a straight sets win over Frenchman Adrian Mannarino in the late match under the Centre Court roof.
Defending women's champion Williams dispensed with the tears as she reached the third round with an ultimately easy victory over Romanian teenager Simona Halep.
The 29-year-old, who wept after beating Aravane Rezai on Tuesday as the emotional turmoil of a horrendous 11 months out caught up with her, eventually found her A-game in a 3 sets victory out on Court Two.