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How do shrooms work (very simplified)?
There is space between the neurons. When you take a drug, the drug gets into the spaces between the neurons and alters how/when the neuron fires. (Very simplified)
The neurons have receptors, which are a lot like a keyhole. Think of a drug as a key. The drug usually only effects a neuron if it fits into one of the neurons receptors.
A tryptamine has a shape very similar to serotonin. Because of this, it will fit into the same 'keyhole' that serotonin fits into... but because the tryptamine shape is a bit different, the effects are different.
For a more scientific explanation see How do shrooms work?.