We evolved sensors for heat because heat can cook flesh. Spicy stuff is a chemical that just happens to activates this sensor. Plants have it to ward off predators. Joke’s on the plants.
For more detail, those heat sensors are called TRPV channels and they locate on pain neurons. On exposed flesh and mucous membranes TRPV’s are also sensitive to acid and salt to a degree. Textbook answer for spicy is that it’s caused by an oil called capsaicin but it’s actually a family of capsaicinoids that might contribute to the different kinds of heat you’d get from jalapenos vs habaneros vs black pepper etc
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