The structure of phycocyanobilin, the prosthetic group of phycocyanin, has been investigated by means of mass spectral, infrared, and nuclear magnetic resonance studies. The linear tetrapyrrolic compound has a molecular weight of 588 and contains an intramolecular hydrogen bond, the rupture of which forms the basis for several of the chemical transformations. Esterification, for example, is accompanied by dehydrogenation, so the molecular weight of the dimethyl ester is 614.The structure of the phycobilin P 655 has been deduced from an analysis of the properties of phycocyanobilin; this structure is nearly identical to the one proposed by Cole, Chapman, and Siegelman. For the phycobilin P 608 only a tentative structure can be presented.
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