Anything that allows for better nerval communications would probably do this.
Capsaicin is a pretty good example, too. It mimics the sensation of heat, rather than exclusively pain, but it does work on the basis of acting on an ion-channel-type receptor, directly fooling the nervous system into reporting false stimuli.
You can block the signals of the nerves that morphine and other opiates act on using a drug like naloxone.
Your body produces chemicals like opiates to lessen pain after there is an initial signal that something hurts. It's used when people are overdosing on opiates.
Giving it to someone who is already in pain, addicted to opiates or before hitting someone with a hammer will cause everything to hurt a lot more
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