Since February, Germany has taken the lead in trying to convince Putin to engage with the West.
Miguel Macedo resigned following an investigation into alleged corruption linked to residence permits.
An informal vote on independence for Catalonia has shown more than 80% in favour, officials say.
More help said urgently needed, despite significant contributions from the UK, China, Cuba and the U.S.
In TV address, Petro Poroshenko said Sunday's polls could derail the "entire peace process."
Partial poll results suggested no candidate had won an overall majority in the first round.
Russia has agreed to resume gas supplies to Ukraine over the winter in a deal brokered by the EU.
Thousands rally against move they see as undermining democracy.
In address, sought to inspire Europe to find its vigor and greatness.
Analysts say Ukraine is too unstable to be seen as viable for membership.
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