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In the prerecorded talk through Zoom, the two discuss "how the VP's time at Howard University shaped her career, her love of basketball and the need to remain vigilant to stop the spread of COVID-19 and promote the efficacy of the vaccine," according to the NBA.
The conversation will kick off coverage of the 70th annual All-Star Game at 8 p.m. ET, which airs Sunday on TNT and ESPN Radio, live from State Farm Arena in Atlanta.
Typically, the All-Star Game is part of a larger All-Star weekend, which gathers the best players in the NBA.
This year, though, the court will see all the All-Star action on a single night -- including the game itself, a skills challenge, the three-point contest and slam dunk halftime competition.
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Starting alongside LeBron are Giannis Antetokounmpo of the Bucks, Stephen Curry of the Warriors, Luka Doncic of the Mavericks and Nikola Jokic of the Nuggets as starters.
Durant, who is injured and won't play, is starting with Bradley Beal of the Wizards, Joel Embiid of the 76ers, Kyrie Irving of the Nets, Kawhi Leonard of the Clippers and Jayson Tatum of the Celtics.
CNN Wire contributed to this report.