Glycoinositolphosphosphingolipids (basidiolipids) of higher mushrooms.
The basidiolipids of six mushroom species, i.e. the basidiomycetes Amanita virosa (engl., death cup), Calvatia exipuliformis (engl., puffball), Cantharellus cibarius (engl., chanterelle), Leccinum scabrum (engl., red birch boletus), Lentinus edodes (jap., Shiitake), and Pleurotus ostreatus (engl., oystermushroom), were isolated, and their chemical structures investigated. All glycolipids are structurally related to those of the Agaricales (engl., field mushroom). They are glycoinositolphosphosphingolipids, their ceramide moiety consisting of t18:0-trihydroxysphinganine and an alpha-hydroxy long-chain fatty acid. In contrast to a previous study [Jennemann, R., Bauer, B.L., Bertalanffy, H., Geyer, R., Gschwind, R.M., Selmer, T. & Wiegandt, H. (1999) Eur. J. Biochem. 259, 331--338], the glycoside anomery of the hexose (mannose) connected to the inositol of all investigated basidiomycete glycolipids, including the basidiolipids of Agaricus bisporus, was determined unequivocally to be alpha. Therefore, the root structure of all basidiolipids consists of alpha-DManp-2Ins1-[PO(4)]-Cer. In addition, for some mushroom species, the occurrence of an inositol substitution position variant, alpha-Manp-4Ins1-[PO(40]-Cer, is shown. The carbohydrate of chanterelle basidiolipids consists solely of mannose, i.e. Cc1, Man alpha-3 or -6Man alpha; Cc2, Man alpha-3(Man alpha-6)Man alpha-. All other species investigated show extension of the alpha-mannoside in the 6-position by beta-galactoside, which, in some instances, is alpha-fucosylated in 2-position (Fuc alpha-2)Gal beta-6Man alpha-. Further sugar chain elongation at the beta-galactoside may be in 3- and/or 6-position by alpha-galactoside, e.g. Ce4, Po2, Gal alpha-3-(Gal alpha-6)(Fuc alpha-2)Gal beta-6Man alpha-, whereas A. virosa, Av-3, has a more complex, highly alpha-fucosylated terminus, Gal alpha-3 (Fuc alpha-2)(Fuc alpha-6)Gal alpha-2(Gal alpha-3)Gal beta-6Man alpha-. L. edodes basidiolipids show further elongation by alpha-mannoside, e.g. Le3, Man alpha-2Man alpha-6Gal alpha-3(Fuc alpha-2)Gal beta-6Man alpha-, C. exipuliformis glycolipid by alpha-glucoside, i.e. Ce3, Glc alpha-6Gal beta-6Man alpha-. Basidiolipid Ls1 from L. scabrum, notably, has a 3-alpha-mannosylated alpha-fucose, i.e. Gal alpha-6(Man alpha-3Fuc alpha-2)Gal alpha-6Gal beta-6Man alpha-. In conclusion, basidiolipids, though identical in their ceramide constitution, display wide and systematic mushroom species dependent variabilities of their chemical structures.
Jennemann
R
R
Abteilung für Zelluläre und Molekulare Pathologie, Deutsches Krebsforschungszentrum, Heidelberg, Germany. r.jennemann@dkfz.de
Geyer
R
R
Sandhoff
R
R
Gschwind
R M
RM
Levery
S B
SB
Gröne
H J
HJ
Wiegandt
H
H
D000363:Agaricales / Q000737:chemistry*; D002236:Carbohydrate Conformation; D002240:Carbohydrate Sequence; D002518:Ceramides / Q000737:chemistry / Q000378:metabolism; D002855:Chromatography, Thin Layer; D005227:Fatty Acids / Q000032:analysis / Q000737:chemistry; D006017:Glycolipids / Q000737:chemistry* / Q000378:metabolism; D006026:Glycoside Hydrolases / Q000378:metabolism; D006868:Hydrolysis; D007294:Inositol / Q000032:analysis / Q000737:chemistry; D009682:Magnetic Resonance Spectroscopy; D008358:Mannose / Q000032:analysis / Q000737:chemistry; D008745:Methylation; D008970:Molecular Weight; D010504:Periodic Acid / Q000378:metabolism; D010758:Phosphorus / Q000032:analysis; D021241:Spectrometry, Mass, Electrospray Ionization; D013110:Sphingosine / Q000032:analysis / Q000737:chemistry
D002518:Ceramides; D005227:Fatty Acids; D006017:Glycolipids; D010504:Periodic Acid; D010758:Phosphorus; D007294:Inositol; C009288:metaperiodate; D006026:Glycoside Hydrolases; D013110:Sphingosine; D008358:Mannose