Despite an opening goal by winger Memphis Depay against his former Dutch club, United -- who dominated throughout -- failed to capitalise on their chances and goals from Hector Moreno and Luciano Narsingh gave the hosts victory.
However, worse than the defeat was the injury to Shaw, which came just 15 minutes into the match following a crunching Moreno tackle, leaving the England international with a double fracture that requires an operation when he returns to Manchester and could put his participation at Euro 2016 next summer in jeopardy.
La entrada de Héctor Moreno a Luke Shaw http://t.co/ViINYEpZjJ vía @jugadinho
— Forever United (@MUnitedEs) September 15, 2015
Shaw was wheeled off the field breathing through an oxygen mask to loud applause from PSV's fans before being substituted by Marcos Rojo for his first appearance of the season.
Video: Louis van Gaal reaction to Luke Shaw injury #mulive [via @HannahD_94]: pic.twitter.com/6Hgeb8E5lA
— utdreport (@utdreport) September 15, 2015
"It's horrible. When he was going in the dressing room, he was with the oxygen mask, he was crying," United manager Louis van Gaal said after the match.
Asked how long he thought Shaw's recovery would take Van Gaal said: "I am not a doctor, so I can't say. A double fracture, it generally takes six months, but you can never say in advance."
Around half an hour after being wheeled off, though, Shaw took to Twitter to vow that he would make a full recovery.
"Thank you everyone for your messages, words can't describe how gutted I am, my road to recovery starts now, I will come back stronger," he tweeted.
Thank you everyone for your messages , words can't describe how gutted I am , my road to recovery starts now, I will come back stronger.
— Luke Shaw (@LukeShaw23) September 15, 2015
Mexican international Moreno, who broke his own leg in last year's World Cup against the Netherlands, afterwards profusely apologised.
"I just feel really bad because I was involved in the accident," he told journalists.
"I'm really sorry. I think I played the ball.
"I just hope he'll be back as soon as possible."
Shaw also received support from around the world.
@SouthamptonFC thank you , you don't know how much you as a club mean to me , thank you so much I really appreciate it
— Luke Shaw (@LukeShaw23) September 15, 2015
Our thoughts go out to @LukeShaw23, who has suffered a double fracture of the leg. He will have an operation on his return to Manchester.
— Manchester United (@ManUtd) September 15, 2015
I hope Luke Shaw a very fast recovery from tonight. Hug from Cafu.
— Cafu (@officialcafu) September 16, 2015
The pictures look bad. Feel so sorry for #LukeShaw after he started the season so well. #getwellLuke #MUFC #PSV
— Alan Shearer (@alanshearer) September 15, 2015
Defeat hurts, but @LukeShaw23's injury hurts even more. We hope you come back even stronger!
— David de Gea (@D_DeGea) September 15, 2015
Fingers crossed for @LukeShaw23, get well soon
— Aaron Ramsey (@aaronramsey) September 15, 2015
Pictures of the Luke Shaw injury look horrific. Hope I'm wrong but fear the worst.
— Gary Lineker (@GaryLineker) September 15, 2015
Get well soon, @LukeShaw23! pic.twitter.com/rkASRZDBIc
— Ryan Giggs (@RyanGiggs_cc) September 16, 2015
Thinking of you lad @LukeShaw23 hope you have a speedy recovery...
— Ross Barkley (@RBarkley8) September 15, 2015
Get well soon @LukeShaw23 - everyone at @Arsenal wishes you a quick recovery pic.twitter.com/EhgD5rAkXR
— Arsenal (@Arsenal) September 16, 2015
my thoughts are for you! you will come back more stronger good recovery @LukeShaw23
— Anthony Martial (@AnthonyMartial) September 16, 2015
@LukeShaw23 speedy recovery mate, come back stronger!!
— Gareth Bale (@GarethBale11) September 15, 2015
Get well soon, @LukeShaw23 🙏🏽🙏🏽🙏🏽#comebackstronger pic.twitter.com/NMIlQPnoVf
— Jérôme Boateng (@JeromeBoateng) September 15, 2015
All the best to you my friend @LukeShaw23 , and your family , difficult time but you are a beast and you will come back stronger than ever .
— Morgan Schneiderlin (@SchneiderlinMo4) September 16, 2015
Gutted for you mate 😔 hope you have a speedy recovery @LukeShaw23 🙏🏾🙏🏾
— Nathaniel Clyne (@Nathaniel_Clyne) September 15, 2015
Come back soon big man...🙏🏼🙏🏼 #strongerthanever #shaw pic.twitter.com/yfVlzT2i6q
— Prince Boateng (@KPBofficial) September 15, 2015
Horrible to see what happened 🙏👎 I wish u all the best my brother and stay strong you will comeback even stronger 🙏🙏 @LukeShaw23
— Adnan Januzaj (@adnanjanuzaj) September 15, 2015
https://twitter.com/PhilJones4/status/643896694166454272
Sad about the defeat but much sadder about Luke's injury. Come back soon my friend pic.twitter.com/VHO6gusvF2
— Ander Herrera (@AnderHerrera) September 15, 2015
Very disappointing night for us. Wish @LukeShaw23 a speedy recovery, gutted for you, stay strong mate
— Ashley Young (@youngy18) September 15, 2015
Wish @LukeShaw23 speedy recovery !! #Manchesterunited
— Mahela Jayawardena (@MahelaJay) September 16, 2015
https://twitter.com/RomeluLukaku9/status/643870370609676289
My thoughts and prayers are with @LukeShaw23 Hoping for a quick recovery and to be playing alongside him again as soon as possible! 🙏🏽
— Chris Smalling (@ChrisSmalling) September 15, 2015
Wish you well #lukeshaw http://t.co/IowavBbD1Z
— Ruud Gullit (@GullitR) September 15, 2015
Wishing @LukeShaw23 a quick recovery - stay strong. pic.twitter.com/eH7mKRgTMB
— Marouane Fellaini (@Fellaini) September 16, 2015
Hope @Lukeshaw23 makes a full and speedy recovery...hate seeing young athletes getting injured like that😔
— Andy Murray (@andy_murray) September 15, 2015
My thoughts are with @LukeShaw23, Friend i wish you a good recovery! #gwsshaw
— Daley Blind (@BlindDaley) September 16, 2015
https://instagram.com/p/7qyc3aqPyj/
Get well soon, @LukeShaw23 #esmuellert
— Thomas Müller (@esmuellert_) September 16, 2015
Awful seeing Luke Shaw sustain a shocking injury last night. Wishing him a speedy recovery. https://t.co/xXOzSjnRO2
— Michael Owen (@themichaelowen) September 16, 2015
Wishing @LukeShaw23 a speedy recovery. You will be back stronger bro 🙏🏼
— Nathaniel Chalobah (@chalobah) September 16, 2015
I feel very sorry for @lukeshaw23 because of his terrible injury. Get well soon and come back stronger, my friend! pic.twitter.com/bHAkGttnM8
— Bastian Schweinsteiger (@BSchweinsteiger) September 16, 2015
https://twitter.com/Robbie9Fowler/status/643924713446735872
Gutted for Luke shaw , best full back in the league this season ! Hope he makes a speedy recovery !
— Robbie Savage (@RobbieSavage8) September 15, 2015
@LukeShaw23 gutted mate. Stay positive. Jay
— Jay Rodriguez (@JayRodriguez9) September 15, 2015
Always sad when someone gets injured that bad...all the best and speedy recovery to @LukeShaw23
— Pepe Reina (@PReina25) September 15, 2015
Dispite the foul on @LukeShaw23 hope he Will have a good recovery BLESS him 🙏🏾
— PATRICK KLUIVERT (@PatrickKluivert) September 15, 2015
My prayers and thoughts are with @LukeShaw23 stay strong through the recovery bro, come back stronger!
— Anthony Joshua (@anthonyjoshua) September 15, 2015
The result continued Van Gaal's poor record at the Philips Stadium with Ajax, Barcelona, AZ Alkmaar and now with United, winning just twice in 11 attempts.
The former Netherlands coach, who took over the reins at Old Trafford last year, saw his run of bad luck continue in the southern Dutch city with PSV tenaciously clinging on to a narrow lead for an historic win.
The 21-year-old Depay struck in the 41st minute when fellow Dutchman Daley Blind slid him in to slice past two PSV defenders and then find the back of PSV goalkeeper Jeroen Zoet's net with a crisp left-foot finish.
As promised, Depay celebrated his goal in front the fans who used to revere him, but United's fortunes were short-lived when PSV struck back just before half-time.
Mexico defender Moreno's header from a Maxime Lestienne corner glanced off Blind's head, before beating David de Gea and Ashley Young on the line.
PSV laid their cards on the table in the second half, with right wing Luciano Narsingh heading in a beautifully-timed Lestienne cross past De Gea to find the left hand corner of the United goal.
Although Depay impressed throughout the first half, United were rail-roaded by PSV's dogged defence.
PSV's defence was up against the wall but impressed with their rigorous resistence, while United's French multi-million pound signing Anthony Martial several times failed to capitalise in front of goal.
Despite a furious United onslaught in the second half, led by Young, PSV's defensive formation held firm to open their account with maximum points.
The Philips Stadium erupted in huge celebrations at the final whistle with PSV celebrating a successful return to the competition for the first time since the 2008/09 season.
It was also PSV's first Champion's League victory over United since 2000.
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