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Ukraine, Georgia and Moldova have signed partnership agreements with the European Union, in a move strongly opposed by Russia.
The pact – which would bind the three countries more closely to the West both economically and politically – is at the heart of the crisis in Ukraine.
Ukrainian President Petro Poroshenko said he saw the signing as the start of preparations for EU membership.
A ceasefire with pro-Russian rebels in the east is due to end on Friday.
