Two days later, the larger-than-life Mob Wives star was dead at the age of 55.
Speaking exclusively to PEOPLE, Dr. Mehmet Oz recalled the "raw" and "authentic" Jan. 29 taping that would be Raiola's final interview.
"She was scared. Which is always a sign that … people know more about their bodies than any test will tell you," says Oz, 55. "What the patient tells you is more accurate than what you can guess. She had been beaten down over the last year."
Raiola, a lifelong smoker, was diagnosed with throat cancer last March, tossing out her cigarettes the minute she left her doctor's office.
After successful surgeries, she developed a tumor in one lung, which was removed. She was declared healthy in October, but in December, stage 4 cancer was discovered in the other lung and her brain.
"When that happens, emotionally, the up and down, it tires you out. The exhaustion took a toll on her," Oz tells PEOPLE. "The third cancer had metastasized to the brain and the adrenal gland. That’s a much worse scenario. They put her on aggressive chemo, which failed. In the setting of that, she came on [the show] to get people to appreciate that this dumb cigarette addiction she picked up as a young woman, she wanted people to see the anguish in her face, as she was clear about the fact that cigarettes killed her."
On air, Raiola revealed she was stopping chemotherapy in favor of the newer, experimental immunotherapy, which Oz calls "a Hail Mary pass."
Oz says she never got to try the treatment because of a lung problem physicians found the morning of her first appointment.
"Chemo kills off cells. Because the cancer cells grow faster than yours, then it kills them more quickly … but it’s an older treatment," Oz explains. "A wiser treatment is to turn your immune system on. Your immune system should always catch a cancer. Everybody reading the article has cancer, but their immune system is strong enough to catch that cancer and kill it. But when it's weakened from poor nutrition and cigarettes, it doesn’t catch it, and the cells prosper. The ability to use the immunotherapy to jump start the immune system would be valuable."
Oz also delved into Raiola's declaration that she had left her estranged husband Neil Murphy, who has PEOPLE learned stayed by her hospital bedside until her death.
"I felt like he never stepped up to the plate, so I was done with it," Raiola said on the show. "Now, it's too late. I would rather be by myself. I would rather be alone."
I will always love you forever please watch over the grandkids I know you will pic.twitter.com/HU99EHM4nf— Neil Murphy (@MrBigAngVH1) February 18, 2016
"What really matters at the end of the day is the family. The family had kept her afloat. Taken her to the doctors. Done everything," Oz says. "Part of the reason she left her husband is she realized she was taking care of him. She was done focusing on him, she needed to focus on her. ... It had been recent. It was a firm decision. ... These are difficult decisions to make, but when your life is at risk, you make those difficult decisions you have been putting off."
(Murphy, a Staten Island sanitation worker, tweeted an old photo of the couple after her passing, promising, "I will always love you forever.")
But Oz wants Raiola's many fans to recognize that the reason she chose to bravely tell her story on national TV despite her declining health was to spread awareness of the dangers of smoking.
"The chance of stopping cigarettes is less than 10 percent on your own, but you can double that with medical support: medications or therapy," he says. "Within hours of stopping cigarettes, your blood pressure drops, your lung function improves, and you see dramatic reductions in other risks. It takes years for other risks to go away, but you see benefits really quickly."
For more on how to quit smoking, visit Dr. Oz's website.