title: Structures and apoprotein linkages of phycoerythrobilin and phycocyanobilin.
abstract: Phycoerythrobilin and phycocyanobilin are covalently attached to the apoproteins of phycoerythrins and phycocyanins. One linkage consists of an ester bond between the hydroxy group of a serine residue and the propionate side chain on one of the inner pyrrole rings (probably ring C). The other linkage is a labile thioether bond between a cysteine residue and the two-carbon side chain on pyrrole ring A. This side chain and both of the alpha-positions of the ring A are in the reduced state. This constitutes an important structural revision, since, in the structures currently accepted for the phycobilins, the two-carbon side chain on ring A is depicted as an ethylidene grouping and this has been regarded not only as a very characteristic feature of the phycobilins, but also as a probable structural feature of the chromophore of phytochrome, largely on the basis of other analogies with the phycobilins. The ethylidene-containing structures apply instead to artefact forms of the pigments released from the apoproteins by treatment with hot methanol. Cleavage of the ring-A linkage involves an elimination reaction releasing the cysteine residue and generating a double bond in the ring-A side chain. During cleavage in methanol the direction of the elimination is towards the ring, generating the ethylidene double bond. Since this is linked to the conjugated system, the methanol-released pigments differ spectrally from the native phycobilins. During acid-catalysed release of the pigments, the elimination apparently goes in the opposite direction, generating a double bond at the outer position of the side chain. Since this double bond is not linked to the conjugated system, the acid-released pigments remain spectrally identical with their protein-bound counterparts.
mesh_terms: D000596:Amino Acids / Q000032:analysis; D001059:Apoproteins; D055598:Chemical Phenomena; D002621:Chemistry; D000432:Methanol; D010798:Phycocyanin; D010799:Phycoerythrin; D010860:Pigments, Biological; D011485:Protein Binding; D013053:Spectrophotometry
chemical_list: D000596:Amino Acids; D001059:Apoproteins; D010860:Pigments, Biological; D010798:Phycocyanin; D010799:Phycoerythrin; D000432:Methanol