Chilis are spicy due to the chemical called Capsaicin. It is specifically a chemical meant to deter mammals from eating it so that more of the fruit is available for birds to eat and thus allowing the seeds to be spread further afield.
isothiocyanate is the chemical that makes horseradish hot. This chemical is more of an insect deterrent to protect the root bulb from being eaten by burrowing insects. Wasabi has a variant of the chemical.
They hit you differently because the spicy flavor is from different chemicals.
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