Download PDF
Planta Med 2012; 78(08): 834-837
DOI: 10.1055/s-0031-1298432
Analytical Studies
Original Papers
Georg Thieme Verlag KG Stuttgart · New York

Simultaneous Determination of the Absolute Configuration of Twelve Monosaccharide Enantiomers from Natural Products in a Single Injection by a UPLC-UV/MS Method

Yan-Hong Wang
1   National Center for Natural Products Research, Research Institute of Pharmaceutical Sciences, School of Pharmacy, University of Mississippi, University, MS 38677, USA
,
Bharathi Avula
1   National Center for Natural Products Research, Research Institute of Pharmaceutical Sciences, School of Pharmacy, University of Mississippi, University, MS 38677, USA
,
Xiang Fu
2   Department of Pharmacognosy, School of Pharmacy, University of Mississippi, University, MS 38677, USA
,
Mei Wang
1   National Center for Natural Products Research, Research Institute of Pharmaceutical Sciences, School of Pharmacy, University of Mississippi, University, MS 38677, USA
,
Ikhlas A. Khan
1   National Center for Natural Products Research, Research Institute of Pharmaceutical Sciences, School of Pharmacy, University of Mississippi, University, MS 38677, USA
2   Department of Pharmacognosy, School of Pharmacy, University of Mississippi, University, MS 38677, USA
3   Department of Pharmacognosy, College of Pharmacy, King Saud University, Riyadh, Saudi Arabia
› Author Affiliations
Further Information

Publication History

received 15 December 2011
revised 27 February 2012

accepted 12 March 2012

Publication Date:
24 April 2012 (online)

    Permissions and Reprints

Abstract

In natural product chemistry, it is often crucial to determine sugar composition as well as the absolute configuration of each monosaccharide in glycosides. An ultra-performance liquid chromatography method using both photodiode array (PDA) and mass spectrometry detectors (UPLC-UV/MS) was developed for qualitative analysis of the absolute configuration of monosaccharide enantiomers. Within a single injection, 16 monosaccharide derivatives including 6 pairs of aldose enantiomers (D/L-glucose, D/L-galactose, D/L-allose, D/L-arabinose, D/L-xylose, and D/L-fucose) and 4 other monosaccharides (L-rhamnose, 2-deoxy-D-glucose, 6-deoxy-D-glucose, and 2-deoxy-D-glalactose) were identified in less than 25 minutes. It was found that the structures of derivatives of sugar enantiomers correlated with retention time. Among derivatives of sugar enantiomers in the current study, the stereoisomer of R-configuration at C-3′ retained longer than the corresponding S-configuration isomer. The UPLC-MS method can increase sensitivity of detection of the saccharides by more than 10 times compared to previously reported methods. The one-pot reaction of monosaccharide with L-cysteine methyl ester and phenyl isothiocyanate is easily reproduced, clean, and relatively simple in a screw-capped reaction vial. The developed method was successfully applied for the analysis of different types of glycosides, viz., glycosides of triterpenes, steroids, and flavonoids, that commonly exist in nature. The absolute configurations of composed monosaccharides are clearly characterized from tested samples.

Key words

monosaccharide - enantiomer - arylthiocarbamate derivatives - absolute configuration - glycosides - UPLC-UV/MS
 

  • References

  • 1 Gerwig GJ, Kamerling JP, Vliegenthart JFG. Determination of the D and L configuration of neutral monosaccharides by high-resolution capillary GLC. Carbohydr Res 1978; 62: 349-357
    CrossrefPubMedGoogle Scholar
  • 2 Little MR. Separation, by GLC, of enantiomeric sugars as diastereoisomeric dithioacetals. Carbohydr Res 1982; 105: 1-8
    CrossrefPubMedGoogle Scholar
  • 3 Hara S, Okabe H, Mihashi K. Gas-liquid chromatographic separation of aldose enantiomers as trimethylsilyl ethers of methyl 2-(polyhydroxyalkyl)thiazolidine-4(R)-carboxylates. Chem Pharm Bull 1987; 35: 501-506
    CrossrefPubMedGoogle Scholar
  • 4 Honda S, Iwase S, Makino A, Fujiwara S. Simultaneous determination of reducing monosaccharides by capillary zone electrophoresis as the borate complexes of N-2-pyridylglycamines. Anal Biochem 1989; 176: 72-77
    CrossrefPubMedGoogle Scholar
  • 5 Honda S, Akao E, Suzuki S, Okuda M, Kakehi K, Nakamura J. High-performance liquid chromatography of reducing carbohydrates as strongly ultraviolet-absorbing and electrochemically sensitive 1-phenyl-3-methyl-5-pyrazolone derivatives. Anal Biochem 1989; 180: 351-357
    CrossrefPubMedGoogle Scholar
  • 6 Liu JP, Shirota O, Wiesler D, Novotny M. Ultrasensitive fluorometric detection of carbohydrates as derivatives in mixtures separated by capillary electrophoresis. Proc Natl Acad Sci USA 1991; 88: 2302-2306
    CrossrefPubMedGoogle Scholar
  • 7 Noe CR, Freissmuth J. Capillary zone electrophoresis of aldose enantiomers : separation after derivatization with S-(−)-1-phenylethylamine. J Chromatogr A 1995; 704: 503-512
    CrossrefPubMedGoogle Scholar
  • 8 Honda S, Taga A, Kotani M, Grover ER. Separation of aldose enantiomers by capillary electrophoresis in the presence of optically active N-dodecoxycarbonylvaline. J Chromatogr A 1997; 791: 385-391
    PubMedGoogle Scholar
  • 9 Tanaka T, Nakashima T, Ueda T, Tomii K, Kouno I. Facile discrimination of aldose enantiomers by reversed-phase HPLC. Chem Pharm Bull 2007; 55: 899-901
    CrossrefPubMedGoogle Scholar
  • 10 Lopes JF, Gaspar EMSM. Simultaneous chromatographic separation of enantiomers, anomers, and structural isomers of some biologically relevant monosaccharides. J Chromatogr A 2008; 1188: 34-42
    CrossrefPubMedGoogle Scholar
  • 11 Ali Z, Khan IA. Alkaloids and saponins from blue cohosh. Phytochemistry 2008; 69: 1037-1042
    CrossrefPubMedGoogle Scholar
  • 12 Jadhav AN, Pawar RS, Avula B, Khan IA. Ecdysteroid glycosides from Sida rhombifolia L. Chem Biodivers 2007; 4: 2225-2230
    CrossrefPubMedGoogle Scholar