Derivatization of small oligosaccharides prior to analysis by matrix-assisted laser desorption/ionization using glycidyltrimethylammonium chloride and Girard's reagent T.
In matrix-assisted laser desorption/ionization (MALDI) analyses of small oligosaccharides a very large increase in sensitivity (by a factor of 1000) may be obtained by introducing a quaternary ammonium center ('quaternization'). Such a quaternary ammonium center may be introduced into the saccharide by reaction with commercially available glycidyltrimethylammonium chloride (GTMA), or by using Girard's reagent T (Naven and Harvey, Rapid Commun. Mass Spectrom. 1996; 10: 829). GTMA reacts with alcohol functionalities, whereas Girard's reagent T is specific for aldehyde and keto groups. Thus reducing saccharides can be derivatized by both GTMA and Girard's reagent T. For example, glucose or cellobiose having a stock concentration of 3 x 10(-5) M (5 microg/mL) produces no sugar-derived signals in conventional MALDI, but their quaternized derivatives, also at 3 x 10(-5) M, yield intense signals, with the matrix-derived signals only being weak. Similar results were obtained for glucosamine. Non-reducing saccharides as well as sugar alcohols can be derivatized using GTMA; thus, although sucrose, raffinose and sorbitol do not react with Girard's reagent T, they all produce intense signals after derivatization with GTMA. An example of the application of these derivatization reactions is provided by the analysis of oligosaccharides in beer.
Gouw
Joost W
JW
Hercules European Research Center, Hercules B.V., P.O. Box 252, 3770 AG, Barneveld, The Netherlands.
Burgers
Peter C
PC
Trikoupis
Moschoula A
MA
Terlouw
Johan K
JK
D001515:Beer / Q000032:analysis; D001622:Betaine / Q000031:analogs & derivatives* / Q000737:chemistry*; D002241:Carbohydrates / Q000032:analysis; D004852:Epoxy Compounds / Q000737:chemistry*; D005947:Glucose / Q000737:chemistry; D007202:Indicators and Reagents; D009844:Oligosaccharides / Q000737:chemistry*; D000644:Quaternary Ammonium Compounds / Q000737:chemistry*; D012996:Solutions; D012997:Solvents; D019032:Spectrometry, Mass, Matrix-Assisted Laser Desorption-Ionization
D002241:Carbohydrates; D004852:Epoxy Compounds; D007202:Indicators and Reagents; D009844:Oligosaccharides; D000644:Quaternary Ammonium Compounds; D012996:Solutions; D012997:Solvents; C045006:glycidyl trimethylammonium; D001622:Betaine; D005947:Glucose; C012332:Girard's reagent T