Henrique Capriles, a former opposition presidential candidate, said he and his team were beaten by National Guard troops as they left a rally that had been broken up by tear gas.
"They cornered us, they beat us... They robbed us all. They took my team's watches, radios, gas masks. When I asked them 'What's wrong with you?' their reaction was to give me a blow to the face. Did they want to kill us?" he told reporters.
Protesters wearing masks and helmets hurled stones and fuel bombs at riot police as they tried to march downtown along a major highway in Caracas toward the government ombudsman's office.
Police, who were blocking the road, responded by firing tear gas, water cannon and buckshot.
According to the opposition 257 people were wounded in yesterday's protests, the first since a weekend announcement of stepped-up pressure on Maduro.
The MUD opposition alliance has not given details of what such increased pressure will involve. But Capriles has said they are considering strikes or long-term street sitdowns.
Supporters of Maduro marched in another part of the capital.
Anti-government violence has spread beyond Caracas. In San Cristobal in the western state of Tachira, two taxis and a bus were set on fire and used to block a highway.
Prosecutors say 60 people have been killed in clashes since the protests erupted on April 1.
Maduro's political opponents vowed earlier to step up protests over his plan to rewrite the constitution, which they see as a bid to cling to power.
"If we allow the fraud that they want to call a constitutional assembly, Venezuela will be lost," said Freddy Guevara, a leading opposition figure at the National Assembly legislature.
Guevara called on supporters to "get ready for an escalation" of protests but urged demonstrators to refrain from violence.
The opposition claims the leftist president has become a dictator and blames him for shortages of food and medicines. Maduro in turn accuses the opposition of attempting a coup with US backing.
Each side accuses the other of sending armed groups to foment violence during the demonstrations.
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