After his run to the Monte Carlo Masters semi-final last week, Dan Evans had to settle for an early exit in Barcelona, where Rafael Nadal had to dig deep to win his opening match while Novak Djokovic had a more straightforward return in Belgrade.
Evans - who has risen to a joint career-best 26th in the world after his Monte Carlo run - was unable to continue his superb recent form on clay as he lost 6-4 5-7 6-3 to Frenchman Corentin Moutet.
Seeded 16th, and on course for a last-eight date with Nadal, Evans was unable to reproduce last week's form in Spain as Moutet advanced to a third-round meeting with Diego Schwartzman with a victory that took three hours and 11 minutes.
Evans failed to consolidate an early break and lost four of the next five games to concede the opening set, but fought back to force a decider, despite needing treatment to his left hand while serving in the eighth game of the second set.
After three consecutive breaks in the third set Moutet resorted to an underarm serve to hold for a 4-1 lead and although Evans broke back to trail 4-3, the 30-year-old immediately lost serve again and Moutet served out for the win.
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Meanwhile Nadal, who is seeking a record 12th title at the Barcelona Open, had to overcome a slow start to defeat world No 111 Ilya Ivashka of Belarus 3-6 6-2 6-4.
The Spaniard lost the first two games and struggled to hold his serve in the third before recovering quickly after losing the first set and cruised in the second, and then broke early in the third.
As he attempts to win the title for a seventh time in the last 10 renewals, Nadal will next face another former champion in Japan's Kei Nishikori, who defeated Cristian Garin of Chile 7-6 (7-5) 4-6 6-1.
Nadal cannot face his Monte Carlo conqueror Rublev until the final on Sunday in Spain, but the Russian, who halted Nadal's quest for a 12th title in the Principality last week, continued his fine season by defeating Federico Gaio 6-4, 6-3.
Second-seeded Stefanos Tsitsipas, who beat Rublev in the Monte Carlo final, cruised past wild-card entry Jaume Munar of Spain 6-0, 6-2, sixth-seeded Pablo Carreno Busta defeated Australian Jordan Thompson 6-4, 6-0 and Felix Auger-Aliassime of Canada rallied to beat Italian Lorenzo Musetti 4-6 6-3 6-0.
Fabio Fognini was disqualified for alleged verbal abuse, having been defaulted while trailing 6-0 4-4 to qualifier Bernabe Zapata Miralles of Spain, after a line judge told the chair umpire that the ninth-seeded Italian had used foul language.
Fognini denied wrongdoing and was upset as he left the court, breaking his racket after hitting it at the net post on his way out.
"What happened to me was inexplicable," he told Spanish media. "I'm going to investigate it. I paid for something that I didn't do."
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At the Serbia Open, Djokovic returned to winning ways as he defeated Kwon Soon-woo 6-1 6-3 to reach the quarter-finals in Belgrade.
The world No 1 will next face fellow Serb Miomir Kecmanovic, who had earlier battled past French qualifier Arthur Rinderknech 6-3 3-6 6-3.
"I played very well from the very beginning and I thought it was a pretty flawless performance," Djokovic said, quoted on the ATP Tour website.
"I moved well, I was mixing up the pace quite well, making him play. I served well in the important moments, (and) overall I just felt great."
In Wednesday's later matches, number two seeded Italian Matteo Berrettini beat compatriot Marco Cecchinato 6-4 6-3 while Serbian fifth seed Filip Krajinovic confidently saw off wildcard Nikola Milojevic 6-1 6-1.
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