title: Hydroxymethylated phyllobilins: a puzzling new feature of the dioxobilin branch of chlorophyll breakdown.
abstract: Colorless nonfluorescent chlorophyll (Chl) catabolites (NCCs) are formyloxobilin-type phyllobilins, which are considered the typical products of Chl breakdown in senescent leaves. However, in degreened leaves of some plants, dioxobilin-type Chl catabolites (DCCs) predominate, which lack the formyl group of the NCCs, and which arise from Chl catabolites by oxidative removal of the formyl group by a P450 enzyme. Here a structural investigation of the DCCs in the methylesterase16 mutant of Arabidopsis thaliana is reported. Eight new DCCs were identified and characterized structurally. Strikingly, three of these DCCs carry stereospecifically added hydroxymethyl groups, and represent bilin-type linear tetrapyrroles with an unprecedented modification. Indeed, DCCs show a remarkable structural parallel, otherwise, to the bilins from heme breakdown.
authors.affiliation: Institute of Organic Chemistry and Center for Molecular Biosciences, University of Innsbruck, Innrain 80/82, 6020 Innsbruck (Austria).
authors.forename: Iris
authors.initials: I
authors.lastname: Süssenbacher
authors.forename: Bastien
authors.initials: B
authors.lastname: Christ
authors.forename: Stefan
authors.initials: S
authors.lastname: Hörtensteiner
authors.forename: Bernhard
authors.initials: B
authors.lastname: Kräutler
mesh_terms: D017360:Arabidopsis / Q000201:enzymology / Q000378:metabolism; D029681:Arabidopsis Proteins / Q000235:genetics / Q000378:metabolism; D002734:Chlorophyll / Q000031:analogs & derivatives / Q000378:metabolism*; D003577:Cytochrome P-450 Enzyme System / Q000378:metabolism; D004950:Esterases / Q000235:genetics / Q000378:metabolism; D005456:Fluorescent Dyes / Q000737:chemistry; D018515:Plant Leaves / Q000201:enzymology / Q000378:metabolism; D045725:Tetrapyrroles / Q000737:chemistry*
chemical_list: D029681:Arabidopsis Proteins; C585921:CYP89A9 protein, Arabidopsis; D005456:Fluorescent Dyes; D045725:Tetrapyrroles; C000590876:dioxobilin; D002734:Chlorophyll; D003577:Cytochrome P-450 Enzyme System; D004950:Esterases
keywords: Arabidopsis thaliana; bilin; chlorophyll; cytochrome P450; phyllobilin