Violence erupted when thousands of opposition protesters tried to march on central Caracas, a pro-government bastion where red-clad Maduro supporters were massing for a counter- demonstration.
The marchers were forced back by lines of soldiers and police deployed to contain what the opposition has vowed will be the "mother of all protests."
On the capital's northwest side, a 19-year-old man was shot in the head and badly wounded by motorcycle-riding gunmen who also threw tear gas canisters into a crowd of protesters, witnesses told AFP.
This is the largest day of demonstrations in more than two weeks of violent protests that have left five people dead and more than 200 arrested since moves by Maduro to tighten his grip on power escalated the country's political and economic crisis.
"We have to end this dictatorship. We're fed up. We want elections to get Maduro out, because he's destroyed this country," said protester Ingrid Chacon, a 54-year-old secretary.
Venezuela's crisis escalated on March 30, when the Supreme Court tried to take over the powers of the National Assembly.
The assembly has been the only lever of power Maduro's camp does not control since the opposition won a landslide in legislative elections in 2015.
Pressure on Maduro has increased as falling prices for Venezuela's crucial oil exports have aggravated an economic crisis, creating severe shortages of food and medicine in the state-led economy.
The center-right opposition has called for the military -- a pillar of Maduro's power -- to abandon him.
But the defense minister, General Vladimir Padrino Lopez, has pledged the army's "unconditional loyalty," while Maduro blasted Borges for inciting a "coup."
The president has sought to rally his troops this week, sending the army into the streets and ordering pro-government militias to be expanded to half a million members, "each with a rifle."
"The hour of combat has arrived," Maduro said.
Yesterday he activated a military, police and civilian operation called the "Zamora Plan" aimed at combatting a supposed coup attempt -- which the president says is being orchestrated by Venezuela's opposition and the United States.
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