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Furchgott and Zawadzki showed blood vessel relaxation needs the inner endothelial cells, which release a relaxing factor.
As reported in: Furchgott, Zawadzki (1980). The obligatory role of endothelial cells in the relaxation of arterial smooth muscle by acetylcholine. Nature. doi:10.1038/288373a0
Ignarro and colleagues independently identified the relaxing factor from arteries and veins as nitric oxide.
As reported in: Ignarro, Buga, Wood et al. (1987). Endothelium-derived relaxing factor produced and released from artery and vein is nitric oxide.. Proceedings of the National Academy of Sciences. doi:10.1073/pnas.84.24.9265