Studies on the Structures and Apoprotein Linkages of the Phycobilins

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Abstract
The structures of the phycobilins have been studied by chromic acid oxidation followed by identification of the imide products by thin layer chromatography. The results, in conjunction with spectral and other data, permit the assignment to phycoerythrobilin of a structure which may be regarded as a derivative of mesobilidiene a, b IXα, with the ethyl side‐chain and ring double‐bond of ring A replaced by an isomeric ethylidene grouping, and the ethyl side‐chain of ring D replaced by a vinyl group. Phycocyanobilin has an isomeric bilitriene structure which may be regarded as mesobilitriene IXα with the ethyl side‐chain and ring double‐bond of ring A replaced by an ethylidene grouping.Oxidation of intact algal biliproteins reveals that the covalent linkages of the above two phycobilins to their apoproteins involve both a group in ring A, probably the ring nitrogen group, and a carboxyl group of one of the propionic acid side‐chains.

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