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Russian President Vladimir Putin ordered his military command to put Russia’s nuclear deterrent on high alert on Sunday in the face of a huge Western response to his war on Ukraine, which said it had repelled Russian ground forces nearing its biggest cities.

The United States responded by saying Putin was escalating the war in a “totally unacceptable" way, amid signs that the biggest assault on a European state since World War Two was not producing rapid battlefield victories for Russia.

The Ukrainian president’s office said negotiations with Moscow without preconditions would be held at the Belarusian-Ukrainian border. The Kremlin said talks had started.

As missiles rained down on Ukrainian cities, nearly 400,000 Ukrainian civilians, mainly women and children, have fled into neighbouring countries. Hundreds were stranded in Kyiv on Sunday waiting for trains to take them west, away from the fighting. The capital remains in Ukrainian government hands, with President Volodymyr Zelenskiy rallying his people despite Russian shelling of civilian infrastructure.

Medical oxygen supplies were running low, the WHO said. A blood bank was packed with donors, despite coming under fire that injured two people a day earlier, a doctor said.

Putin, who has described the invasion as a “special military operation", thrust an alarming new element into play when he ordered Russia’s deterrence forces—units that include nuclear weapons—onto high alert.

He cited aggressive statements by NATO leaders and the barrage of economic sanctions imposed on Russia by the West. “As you can see, not only do Western countries take unfriendly measures against our country in the economic dimension —I mean the illegal sanctions that everyone knows about very well—but also the top officials of leading NATO countries allow themselves to make aggressive statements with regards to our country," Putin said on state television.

Putin previously referred to his nuclear arsenal in a speech announcing the start of the invasion on Thursday, saying Russia’s response to any country that tried to hinder it would be immediate and carry “consequences that you have never encountered in your history".

France’s foreign minister retorted the same day that Putin should remember that NATO too was a nuclear alliance. “This is not ‘deterrence’ on Putin’s part—this is a threat," said Patricia Lewis, director of the Chatham House think tank’s international security programme.

Ukrainian foreign minister Dmytro Kuleba said Putin’s order was an attempt to pressure Kyiv during the talks but that it would not be cowed.

US ambassador to the UN Linda Thomas-Greenfield told CBS: “President Putin is continuing to escalate this war in a manner that is totally unacceptable and we have to continue to stem his actions in the strongest possible way."

A US defence official said Washington was trying to assess what Putin’s announcement meant in tangible terms, but that it increased the danger from any miscalculation. The US and the West are providing military assistance for Ukraine.

Western countries on Sunday expanded a ban on Russian airlines using their airspace, giving Russian airliners almost westward exit route.

And in the strongest economic sanctions yet on Moscow, the US and Europe said on Saturday they would banish big Russian banks from the main global payments system SWIFT and announced other measures aimed at limiting Moscow’s use of a $630 billion war chest. Rolling protests have been held around the world against the invasion in recent days, including in Russia, which has clamped down hard.

More than 100,000 people protested in solidarity with Ukraine in Berlin on Sunday.

A Ukrainian state agency said that, before daybreak, Russian troops blew up a natural gas pipeline in Kharkiv, Ukraine’s second largest city, sending a burning cloud up into the darkness. Soon after, Russian soldiers and armoured vehicles rolled into Kharkiv, located in Ukraine’s northwest, and witnesses reported firing and explosions. But city authorities said Ukrainian fighters had repelled the attack. “Control over Kharkiv is completely ours! The armed forces, the police, and the defence forces are working, and the city is being completely cleansed of the enemy," regional Governor Oleh Sinegubov said.

Reuters was unable to corroborate the information.

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