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Acetylcholine is a chemical messenger, a neurotransmitter, released by nerve cells in many parts of the peripheral nervous system. It controls the contraction of all skeletal or voluntary muscles, for instance. It also affects the contraction of smooth and cardiac muscle.cetylcholineâs Effect On Smooth Muscle. Acetylcholine activates a different type of receptor present in smooth muscle: the muscarinic receptor. When this receptor binds acetylcholine, one result is the release of calcium ions from internal stores.