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Manchester City and Arsenal suffered shock defeats in the tenth round.
Rodri, a first-time winner of the award, was instrumental in helping his team win an unprecedented fourth successive Premier League trophy last season.
Arsenal were held 1-1 by Brighton after Declan Rice was sent off.
Every team will play eight games against different opponents in the new format of Europe's elite club competition.
Manchester City scored three times in less than four minutes after conceding a shock early goal to crush Ipswich and remain perfect in their quest for a fifth consecutive league title.
Chelsea, in their first Premier League outing under new manager Enzo Maresca, were largely outclassed by their more composed visitors.
Erik ten Hag's team looked on course to repeat their shock victory over City in the FA Cup final when Alejandro Garnacho put United ahead after 82 minutes, but City midfielder Bernardo Silva netted a minute from time to send the match to penalties.
Mainoo and Garnacho scored in the 2-1 win for United at Wembley
Guardiola did not elaborate beyond saying he was naturally tired after another mammoth effort that ended in a remarkable sixth title in seven years for City.
In one of the closest title races in Premier League history, Arsenal could have taken the championship had City dropped points. But the Londoners' 2-1 win in their game against Everton was in vain, leaving them two points behind.
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