Elena Rybakina and Tamara Zidansek were both surprise second-round losers at The Rosmalen Grass Court Championships as numerous top seeds fell on Thursday.
Third favourite Rybakina struggled to find her rhythm and fell to a 6-2 6-4 loss against world number 42 Shelby Rogers.
The American will face Kirsten Flipkens in the quarter-finals in the Netherlands after she eased past Ann Li in straight sets.
Aryna Sabalenka, the favourite at the tournament, had little difficulty in negotiating past Arianne Hartono 6-2 6-3 and she will meet Alison van Uytvanck in the next round.
The Belgian picked up the scalp of compatriot Elise Mertens, the eighth seed, with a 6-2 6-3 win over the world number 29.
Fourth seed Zidansek was another to fall as she suffered a 6-1 6-1 loss to Catherine McNally, while Veronika Kudermetova profited from Anna Blinkova retiring with the match heading for one set each.
Belinda Bencic, the second favourite, will next challenge Kudermetova after she bucked the trend of the day with a battling 7-6 (7-2) 6-4 win over Anna Kalinskaya.
Seventh seed Ekaterina Alexandrova had no trouble in advancing, meanwhile, as she saw off Anhelina Kalinina 6-4 6-2.
Maria Sakkari found herself 1-0 down against world number 109 Rebecca Marino before rain stopped play at the Nottingham Open, but the top seed responded to claim a 1-6 6-3 6-3 win.
Third seed Camila Giorgi had no such luck against Hannah Dart as she was eliminated 5-7 6-4 7-6 (7-3), while Alison Riske and Ajla Tomljanovic beat Caroline Garcia and Katie Boulter respectively in straight sets.
Djokovic keeps Serbia on track as Ruud seals Norway win
Novak Djokovic marked his return to action with a dominant 6-0 6-1 victory over Greece's Ioannis Xilas to put Serbia in control of the Davis Cup tie.
The 24-time major winner was playing his first match since his US Open third-round defeat by Alexei Popyrin at Flushing Meadows a fortnight ago.
And Djokovic, who helped his nation win the Davis Cup in 2010, looked close to his best as he dropped just a single game, while converting five of the seven break points he forced.
Wrapping up a dominant victory in just 45 minutes, he put Serbia 2-0 to the good in the World Group I tie.
Elsewhere in that group, Casper Ruud helped Norway wrap up a 3-1 win over Portugal.
The three-time major finalist, who put his nation 2-1 to the good alongside Viktor Durasovic in the doubles rubber, was a 7-6 (7-3) 6-2 victor over Jaime Faria in their singles clash.
Later in the day, Argentina booked their place in the final eight after Maximo Gonzalez and Andres Molteni saw off Finland in the doubles decider.
Nadal unsure of future involvements after Laver Cup withdrawal
Rafael Nadal says he cannot commit himself to future tournaments after his withdrawal from the Laver Cup.
Nadal shared news on Thursday that he would not make an appearance at the annual event in Berlin, stating that it would not be in the best interests of Team Europe if he were to participate.
The Spaniard was last in action playing doubles at the Paris Olympics with Carlos Alcaraz, and while he says he is in a good space mentally, he was not able to confirm when he would next make a professional appearance on a tennis court.
He said: "Mentally, I’m good, no problems. I'm at home enjoying other things, training as much as I can every day.
"No drama, obviously these are decisions [the Laver Cup withdrawal] that are being made, and this was a possibility - it's been a while without competing. There will be someone else who can do better.
"Right now I’m not in a position to put myself down for anything.
"I said [I would play] until the Olympics and then we would see, and I'm in that period of rest."
Nadal has endured a difficult 2024 so far, playing just 21 competitive singles matches with a record of 13-8.
He has only one grand slam victory to his name this year, beating Jack Draper in the Australian Open, but he lost in the first round of the French Open to eventual finalist Alexander Zverev.
Alcaraz sends Spain into Davis Cup last eight
Carlos Alcaraz has led Spain to the quarter-finals of the Davis Cup Finals after a straight-sets win over Ugo Humbert.
The 21-year-old needed just one hour and 21 minutes to cruise through with a 6-3 6-3 victory, hitting 21 winners to his opponent's 14 as he backed up Roberto Bautista's win earlier on.
Bautista had to come from behind to edge past Arthur Fils, beating him 2-6 7-5 6-3, and converting 40% of his break points, bettering the Frenchman's 27%.
Spain are through in Group B, but elsewhere in Group D, US Open semi-finalist Jack Draper's return was unable to inspire Great Britain to victory.
Dan Evans was beaten by Tomas Martin Etcheverry earlier on Friday before Draper's first match since New York ended in a straight-sets 7-6 (7-4) 7-5 defeat to Francisco Cerundolo.
Despite making fewer unforced errors than the Argentinian (23 to 39), the British number one struggled to find an edge, though Evans and Neal Skupski claimed a consolation win in the doubles to make it 2-1.
They sit second in the group, missing the chance to qualify for the last eight, and now needing a win against Canada, who have been in fine form so far.
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