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Matthew Hudson-Smith will attempt to become Britain's first Olympic men's 400m champion in 100 years on Wednesday, while women's golf star Nelly Korda begins the defence of her title.
Victory would represent a huge achievement for Hudson-Smith who was at a personal low after being isolated in the United States during the Covid pandemic, racking up huge medical bills as he recovered from a torn hamstring and Achilles.
The 29-year-old has arrived in Paris in peak form, clocking a blistering 43.74sec at last month's London Diamond League -- the fastest time in the world this year.
Hudson-Smith qualified for the final by easing to victory in his semi-final on Tuesday.
However, one of his major threats is the man who beat him in the Commonwealth Games final, Zambia's Muzala Samukonga, an unpredictable runner who looked good in the heats.
Also on the track, Moroccan hero Soufiane El Bakkali will defend his 3000m steeplechase crown and bid to become only the third Arab to win double Olympic gold.
"Thanks to all the experience I have, I know how to manage pressure," said the two-time world champion, who eased through his heat in first place.
The women's pole vault and men's discus medals will be decided in the field events at the Stade de France.
World number one Korda starts her attempt to be the first double Olympic golf champion but will need to arrest a recent drop in form.
The American became the first LPGA Tour player to win six titles in a single season since 2013 in the space of just seven tournaments earlier this year, but then suffered three successive cuts.
"The game of golf is a funny game," Korda told reporters ahead of the first round.
"Sometimes you feel on top of the world and in a matter of a couple seconds, you just feel like you're on the bottom of the sea."
Japan's US Open champion Yuka Saso, two-time Olympic medallist Lydia Ko and home hope Celine Boutier are also among the medal favourites at Le Golf National.
In the boxing ring, Taiwan's Lin Yu-ting is aiming to follow in the footsteps of Imane Khelif, after the pair were at the centre of a gender controversy, by reaching a gold-medal bout.
Algerian Khelif, who beat Janjaem Suwannapheng of Thailand in the semi-finals of the 66kg division on Tuesday, is guaranteed at least silver in Paris.
The International Boxing Association disqualified Khelif and Lin from last year's world championships after failing gender eligibility tests.
The IOC cleared the two experienced female boxers to compete and Lin faces Turkey's Esra Yildiz Kahraman in the semi-finals of the women's 57kg event in the first fight of the evening at Roland Garros.
The team pursuit golds are up for grabs in the velodrome, with new world-record holders Australia going up against Britain in the men's final, while New Zealand were the fastest qualifiers for the women's first round.
The final day of skateboarding at the Place de la Concorde sees 51-year-old Briton Andrew Macdonald compete in the men's park, the day after 14-year-old Arisa Trew of Australia won the women's final.
China will be hoping for a late gold rush in weightlifting, which gets under way, to aid their battle at the top of the medals table with the United States.
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