Ukraine's military waged new battles with pro-Moscow rebels who rejected Kiev's unilateral ceasefire, while the government raised alarm over the Kremlin's decision to put troops across Russia on combat alert.
The resurgence of violence on Saturday in the 11-week insurgency threatening to splinter the ex-Soviet nation came as Washington slapped sanctions on top separatist leaders and warned the Kremlin against sending forces into Ukraine.
But Russian President Vladimir Putin appeared ready to continue sabre-rattling in the worst East-West stand-off since the Cold War era by ordering units from the Volga to western Siberia to conduct snap military drills.
"There is no ceasefire," a woman named Lila Ivanovna said just four kilometres (two miles) southwest of the battled-scarred rebel stronghold city of Slavyansk.
"They were shooting last night and I heard mortar and machinegun fire at four this morning. Nothing has changed."
Poroshenko declared the week-long unilateral ceasefire on Friday evening while stressing that it "does not mean that we will not fight back against aggression toward our troops."
The order and simultaneous peace plan unveiled by the 48-year-old chocolate baron was branded an "ultimatum" by the Russian foreign ministry.
Russian Foreign Minister Sergei Lavrov said on a visit to Saudi Arabia on Saturday that he was concerned that Kiev's military campaign had only "intensified".
Poroshenko's attempts to resolve the country's worst post-Soviet crisis two weeks into his term have also been complicated by a new deployment of Russian forces along parts of the border where the rebels mount most frequent attacks.
Putin appeared to be stirring tensions further on Saturday by ordering troops stretching from the Volga region in central Russia to the Ural Mountains and parts of Siberia to go on "full combat alert" as part of an unannounced readiness check.
The Russian defence ministry said military exercises in the expansive region whose western-most edge lies 400 kilometres east of Ukraine would involve 65,000 soldiers along with 60 helicopters and 180 jets.
But both Kiev and its Western allies are also anxious about the presence of new Russian forces along the border amid charges of growing flows of heavy weapons crossing into rebel-held parts of the industrial east.
"Such military activities... do not help normalise the situation in Ukraine and discourage out leaders from implementing their peace initiative," the Ukraine foreign ministry said in a statement.
US State Department spokeswoman Jen Psaki noted that most of the equipment being gathered in southwest Russia was no longer used by its military.
"We believe that Russia may soon provide this equipment to separatist fighters," Psaki said.
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