Former Socceroos assistant coach Mark van Bommel says his PSV Eindhoven players can fight it out for Barcelona star Lionel Messi's shirt if they win at the Nou Camp - but they better not ask him for it at halftime.
Ousmane Dembele also scored for Barcelona, who were already 3-0 up when they were reduced to 10 men as defender Samuel Umtiti was sent off with a second yellow card for a hard foul in the 79th.
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Barcelona were largely frustrated during the opening half an hour by a resilient PSV side who carried a real threat on the break through the likes of Hirving Lozano and Steven Bergwijn.
PSV were without New Zealand signing Ryan Thomas, who is now nursing a long-term injury.
The mood was briefly dampened when France defender Umtiti was dismissed in the 79th minute for a second yellow card, ruling him out of Barca's next Champions League game away to Tottenham Hotspur on October 3. He scored five goals and assisted two as part of a red-hot Liverpool attack in the group stages last season, so he will be hoping to continue that form on this season. But Mauro Icardi equalised with a perfectly struck volley in the 86th and Matias Vecino headed in the victor in injury time to send the San Siro wild.