NMR study of virenose and dihydrohydroxystreptose isolated from Coxiella burnetii phase I lipopolysaccharide.
A lipopolysaccharide (LPS) isolated from Coxiella burnettii in virulent phase I contains in its O-polysaccharide chain two unusual sugars, virenose (6-deoxy-3-C-methylgulose) and dihydrohydroxystreptose [3-C-(hydroxymethyl)lyxose]. The sugars were isolated from LPS I, after acid hydrolysis and removal of lipid A, by a combination of HPLC and preparative paper chromatography. Their enantiomeric forms and ring conformations were established from optical rotation and NMR data. Two-dimensional COSY, HSQC, and HMBC as well as one- and two-dimensional NOEs were used to assign all proton and carbon signals in both monosaccharides. Virenose was found to be the D-gulo enantiomer with the 4C1 ring conformation and dihydrohydroxystreptose was shown to be the L-lyxo enantiomer also with the 4C1 conformation. The latter sugar was reported [S. Schramek, J. Radziejewska-Lebrecht, and H. Mayer, Eur. J. Biochem., 148 (1985) 455-461] to be present in LPS I in a furanose form, and it appears that a furanose to pyranose tautomerization took place in the course of the isolation procedure.
Institute of Virology, Slovak Academy of Sciences, Bratislava, Slovak Republic. virutoma@savba.savba.sk
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D002236:Carbohydrate Conformation; D002851:Chromatography, High Pressure Liquid; D016997:Coxiella burnetii / Q000737:chemistry*; D003837:Deoxy Sugars / Q000737:chemistry* / Q000302:isolation & purification; D004731:Endotoxins / Q000737:chemistry*; D008401:Gas Chromatography-Mass Spectrometry; D009682:Magnetic Resonance Spectroscopy; D009904:Optical Rotation; D010429:Pentoses / Q000737:chemistry* / Q000302:isolation & purification
C114472:3-C-(hydroxymethyl)lyxose; D003837:Deoxy Sugars; D004731:Endotoxins; D010429:Pentoses; C114471:virenose