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Determination of stereochemical configuration of the glycerol moieties in glycoglycerolipids by chiral phase high‐performance liquid chromatography
Author(s) -
Takahashi Yoshinori,
Itabashi Yutaka,
Suzuki Minoru,
Kuksis Arnis
Publication year - 2001
Publication title -
lipids
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.601
H-Index - 120
eISSN - 1558-9307
pISSN - 0024-4201
DOI - 10.1007/s11745-001-0780-y
Subject(s) - chemistry , monoglyceride , enantiomer , glycerol , chromatography , glyceride , chirality (physics) , absolute configuration , high performance liquid chromatography , chiral column chromatography , derivatization , chiral derivatizing agent , organic chemistry , fatty acid , chiral symmetry breaking , physics , quantum mechanics , nambu–jona lasinio model , quark
Abstract This study reports a simple and sensitive method for determining the absolute configuration of the glycerol moieties in glycoglycerolipids. The method is based on chiral phase high‐performance liquid chromatography (HPLC) separations of enantiomeric di‐ and monoacylglycerols released from glycosyldi‐ and monoacylglycerols, respectively, by periodate oxidation followed by hydrazinolysis. The released di‐ and monoacylglycerols were chromatographed as their 3,5‐dinitrophenylurethane (3,5‐DNPU), and bis(3,5‐DNPU) derivatives, respectively. The derivatives were separated on two chiral phases of opposite configuration, ( R )‐and ( S )‐1‐(1‐naphthyl)ethylamine polymers for diacylglycerols and N‐(R) ‐1‐(1‐naphthyl)ethylaminocarbonyl‐( S )‐valine and N‐(S) ‐1‐(1‐naphyl)ethylamino‐carbonyl‐( R )‐valine for monoacylglycerols. Clear enantiomer separations, which permit the assignment of the glycerol configuration, were achieved for sn ‐1,2(2,3)‐dicyl‐ and sn ‐1(3)‐monoacylglycerols generated from linseed oil triacylglycerols by partial Grignard degradation on all the chiral stationary phases employed. Using the method, we have determined the glycerol configuration in the glycosyl‐diacylglycerols (monogalactosyl‐, digalactosyl‐, and sulfquinovo‐syldiacylglycerols) and glycosylmonoacylglycerols (monogalactosyl‐, digalactosyl‐, and sulfoquinovosylmonoacylglycerols) isolated from spinach leaves and the coralline red alga Corallina pilulifera . The results clearly showed that the glycerol moieties in all the glycoglycerolipids examined have S ‐configuration sn ‐1,2‐diacyl‐ and sn ‐1‐monoacylglycerols). The new method demonstrates that chiral phase HPLC provides unambiguous information on the configuration of the glycerol backbone in natural glycosyldi‐ and monoacylglycerols, and that the two‐step liberation of the free acylglycerols does not compromise glycerol chirality.