The top-ranked Nadal beat big-hitting Russian Karen Khachanov 6-3, 6-2 to reach the quarterfinals, clinching victory with a clinical smash at the net.
But the former top-ranked Serb, who has won 12 majors, is searching for form and confidence now.
No13 seed Fabio Fognini, a popular player at the best of times and especially so with Italy just a few kilometres down the road from the Monte-Carlo Club, won in Sao Paulo and made the semis in Rio, and he had another work-out on clay in Davis Cup last week.
Still, after so much injury frustration, Djokovic was encouraged about coming through three matches without any relapse. While Djokovic may not put high expectations this week, bearing in mind this is only his second win since the Australian open in January, he has reiterated that he is playing pain-free again.
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That hope was quickly and brutally extinguished by Nadal, however, the Spaniard racing into a 40-0 lead in the next game and taking the second of three break points. "That's the real thing", he said.
"I'm lacking matches. That's why it's important for me to play, to use every opportunity possible", he said.
No 6 David Goffin of Belgium also needed four match points to beat qualifier Stefanos Tsitsipas 7-6 (4), 7-5, while Zverev's older brother, Mischa Zverev also reached the third round by beating No 7 Lucas Pouille 2-6, 6-1, 7-6 (3). He lost 6-2, 7-5 to Frenchman Richard Gasquet.
Coverage of the ATP Monte Carlo Rolex Masters continues on Friday with all four quarter-finals live from 10am on Sky Sports Arena. "I gained more angle", he said.
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"I think (it's an) fantastic decision by him to take Marian Vajda back because it's the coach he won everything with nearly".
In other matches, Kei Nishikori of Japan overcame an early break to beat Daniil Medvedev of Russian Federation 7-5, 6-2, while No 11 Roberto Bautista Agut, Jan-Lennard Struff, Philipp Kohlschreiber and Richard Gasquet also won. "I'll know more in the [coming] days".
Second-seeded Marin Cilic of Croatia also advanced with a 6-3, 7-6 (4) win over Fernando Verdasco of Spain. Bautista Agut raised a hand in apology but still got a warning from the chair umpire. He was saying the ball bounced, and the ball boy just happened to be there.
Bautista Agut was given a code violation and later fined 2,500 euros ($3,085) for unsportsmanlike conduct. The runner-up previous year, Albert Ramos-Vinolas, fell to Philipp Kohlschreiber, and the in-form Argentine Diego Schwartzman, seeded 10, fell to another perennial favourite, Richard Gasquet.
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Other injuries like sprains and repetitive strain injury from building the cars were also allegedly not logged. Log 300 is a log of work-related injuries and illnesses.