In the rebellious region of Donetsk, the four members of the Organisation for Security and Cooperation in Europe's mission in east Ukraine arrived at a hotel in the early morning hours.
Looking tired and tense, they declined to speak with journalists. Four more kidnapped OSCE observers are still being held.
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The EU agreement lies at the heart of the conflict on the eastern edge of Europe that pits the Kremlin against Western powers and ethnic Russians against Ukrainian speakers in the splintered but strategic nation.
The West is currently scrambling to salvage a temporary ceasefire and nascent peace talks which pro-Russian militias that control large swathes of the industrial east.
Yesterday, Poroshenko extended the truce -- broken on repeated occasions but still having succeeded in tempering the worst of the violence in the Russified eastern rustbelt -- for a few hours until today at 1900 GMT.
Kiev and separatist commanders have also set up a third round of indirect negotiations in the eastern hub of Donetsk that could agree another extension.
"I am ready to make peace with anybody," Poroshenko told CNN.
"I hate the idea of not to use the last opportunity to bring peace to the region," the 48-year-old chocolate baron added in English.
Poroshenko observed that Russian leader Vladimir Putin's position is sometimes "very pragmatic. Sometimes it is very emotional. I try to find the time when he is more pragmatic than emotional."
The Kremlin for its part said Putin assured German Chancellor Angela Merkel that he fully backed the resumption of meaningful dialogue between the warring sides.
The east witnessed sporadic fighting throughout the day Thursday that included a rebel attack on an irregular troops unit stationed in the heart of Donetsk. The National Guard said none of its personnel had been killed or wounded.
In Donetsk, a pro-Russian separatist leader announced the freeing of four OSCE observers who had been kidnapped by rebels in east Ukraine on May 26.
"They have been freed without conditions. They are a Dane, a Turk, a Swiss national and I believe an Estonian," said Oleksandr Borodai, the "prime minister" of the self-proclaimed Republic of Donetsk, which has declared independence from the Kiev government after a disputed referendum.
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