Their mouths aren’t big enough, but they do have extremely strong mandibles, essentially little arms on their faces that can be used to carry things or hold food. In terms of why they hurt, first of all, ant mandibles are extremely strong for their size, ants are famous for their strength. In terms of why they hurt, it comes down to basic evolution. When an ant wants to defend itself it bites, if the bitee wasn’t aware of the bite it wouldn’t be an effective defense mechanism and those ants got killed/eaten. The ants that successfully warded off the threat survived and passed down the painful bite mechanism to their offspring.
In terms of how the bite hurts, the mandibles are designed to inflict the strongest signal for their size, rather super tiny punctures they will slice and tear the flesh to create the most pain possible, even if the damage to the tissue is insignificant. Some ant species also have venom that can chemically trigger pain signals outside of tissue damange.
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