During the rally, the Venezuelan leader announced that the coup d'etat in his country had failed, and during the month of destabilization the opposition has failed to achieve anything.
The AFP news agency said canisters were fired at demonstrators at several other points on the Colombia border where a total of 14 trucks had assembled. The country now faces widespread food and medicine shortages and hyperinflation of over one million percent which makes even the most basic goods unattainable.
Violence broke out as indigenous leaders in southern Venezuela said they had attempted to stop a military convoy heading toward the border with Brazil, believing the soldiers were attempting to block the entrance of foreign aid as per Mr Maduro's order.
Guaido has said that worldwide aid for the country, reeling from a long political and economic crisis, would enter Saturday despite an armed government blockade.
Gonzalez said soldiers shot and killed a 34-year-old indigenous Venezuelan woman and injured 17 others. That statement, however, has been refuted by news that two trucks carrying aid from Brazil are stuck at the Venezuelan border.
At least five Venezuelan troops have abandoned their posts at the country's border with Colombia as confrontations with protesters over incoming humanitarian aid grow more violent by the day.
British billionaire Richard Branson is pictured before the "Venezuela Aid Live" concert which he organized to raise money for the Venezuelan relief effort, at Tienditas International Bridge in Cucuta, Colombia, on February 22, 2019.
The clash occurred in southeastern Bolivar state near to the border with Brazil, which Maduro ordered closed on Thursday.More news: Meghan wants to open baby shower presents with Harry, guest reveals
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Maduro said on state television that his forces had managed to repel an invasion and said he was breaking off diplomatic relations with Colombia.
Riding by the bridge on his bike, college student Frander Duenas said he hoped to sneak into Colombia to see Branson's Venezuela Aid Live because he's a fan of the musicians performing.
While in Venezuela border clashes and military desertions raised tensions, on the sleepy Caribbean island of Curacao a handful of expatriates applied pressure on a separate front, waving flags and singing. After Guaido invoked Venezuela's charter on January 23 to declare himself head of state, the U.S. urged other nations to recognize the 35-year-old as president.
With inflation running at more than 2 million percent a year and currency controls restricting imports of basic goods, many Venezuelans lack vital medicines, and a growing share of the country's roughly 30 million people is suffering from hunger and malnutrition. The leaders greeted the crowd before the concert ended.
"Egregious violation of human rights by Maduro and those who are following his orders will not go unpunished", White House press secretary Sarah Huckabee Sanders said Friday night.
"We trust in God to open the way. and to destroy the enemy", he said, before leading a recitation of the Hail Mary and the Lord's Prayer.
"Trump should worry about the poor in his own country", Maduro said this week.
Maduro, who has support from China, Russia and the military high command, accuses the United States of plotting a military intervention.
Moscow has blasted Washington for using aid as a "convenient pretext for conducting military action".