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Taylor Fritz blasted his way to a 6-3, 6-2 win over Australian Nick Kyrgios while Cameron Norrie fought back to beat former world No. 1 Andy Murray 3-6, 6,-3 6-4 in an all-British clash.
The Croatian, whose last semifinal appearance at a major was at the 2018 Australian Open when he reached the final, encountered stiff resistance from Rublev but his 33 aces made the difference.
The 2014 US Open champion, seeded 20th, dominated proceedings from the start and finished off the contest in an hour and 45 minutes to reach the last eight stage on the Parisian clay for the third time in his career.
Sania and Lucie beat Italian duo of Jasmine Paolini and Martina Trevisan, 4-6 6-2 6-1 in their opening round.
Bopanna and Middelkoop won the second round with a 6-3, 6-4 scoreline against Andrey Golubev and Fabrice Martin in one hour and six minutes.
Mohammedan are searching for their maiden title, while Gokulam Kerala are aiming to become the first team in the I-League era to defend their crown.
Three-time major winner Murray was set to face Djokovic for the 37th time in a highly anticipated clash on clay at the ATP Masters 1000 event in the Spanish capital.
Rublev galloped to an early lead and barely gave his opponent a chance as he closed out the match with a powerful forehand winner for his first win over Djokovic and 11th career title.
Russian players will not be allowed to compete at Wimbledon this year due to Moscow's invasion of Ukraine, according to a report in sports industry news site Sportico on Tuesday.
Fritz upset Nadel 6-3, 7-6 (5) on Sunday to win the BNP Paribas Open and snap the 21-time major champion's 20-match winning streak this year.