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"We have received a preparatory order from President Nicolas Maduro to shoulder arms and defend our country," Padrino said during a ceremony to mobilize a special rapid response force.
Maduro has ordered the army to conduct a round of military drills later this month in response to US President Donald Trump's threat of military action in the crisis-stricken nation.
Maduro has been accused of seeking to consolidate power by packing a controversial new assembly with his allies as inflation spirals out of control and food shortage situation worsens.
On the heels of that statement, Trump's Vice President Mike Pence embarked on a four-nation tour of Latin America to drum up support for a more aggressive push against Maduro and his administration, Global Times reported.
The presidents of Colombia, Argentina, and Chile, all of whom met separately with Pence, rejected the possibility of military intervention in South America.
Padrino objected to Pence's description of Venezuela as a "failed state" that has strayed from democratic principles, pointing to the fact that opposition political parties have gone to the offices of the National Electoral Council to register their candidates for upcoming regional elections in October.
The Trump administration slapped sanctions on Venezuelan President Nicolas Maduro after a July 30 vote that allowed the President to replace the opposition-held National Assembly with a new 545-member Constituent Assembly filled with his supporters.