Barca met seven-times winners AC Milan at the Nou Camp but the stock of the faltering Italians has fallen so much that even an average display from the hosts sealed a 3-1 success in Group H, Lionel Messi scoring a penalty and a cheeky third.
La Liga rivals Atletico put on a better display in their 4-0 cruise past Group G whipping boys Austria Vienna to glide into the knockout stages after four wins from four with two matches to spare.
Miranda grabbed Atletico’s opener after 11 minutes before Raul Garcia rose athletically to head home the second, with Filipe Luis making it three for this term’s potential surprise packages on halftime. Diego Costa missed a penalty but added a fourth on 82 minutes.
Zenit St Petersburg stayed as favourites to take second spot and qualify after Hulk scored the equaliser but also missed a spot-kick in a 1-1 home draw with his former side Porto.
Arsenal grabbed swift revenge for last month’s home loss to Borussia Dortmund by snatching a 1-0 win at last term’s runners-up, Ramsey’s 62nd-minute header the latest in his purple patch of goals as Juergen Klopp’s side were suddenly left fretting.
Arsenal are top of Group F but level on points with Napoli, who overcame Olympique Marseille 3-2 at the San Paolo thanks in part to a cracker from Gokhan Inler, who chested down a clearance on the edge of the area and volleyed home.
Chelsea’s first goal in a 3-0 home win over Schalke 04 was hardly a classic, keeper Timo Hildebrand blasting his clearance against Samuel Eto’o and the ball flying into the net.
The Cameroonian slotted in a cool second after the break and Demba Ba also scored to put the Group E leaders on the verge of qualification, with the Germans second and Basel third after a late equaliser in a 1-1 home draw with Steaua Bucharest.
Despite the Nou Camp defeat, Milan remained second in Group H after Ajax Amsterdam beat Celtic 1-0 in the Netherlands.
European champions Bayern Munich and Manchester City, for the first time, qualified for the last 16 on Tuesday.
(Editing by Ed Osmond)