title: Development of a carbohydrate silylation method in ionic liquids for their gas chromatographic analysis.
abstract: This paper reports on the feasibility of silylation of low molecular weight carbohydrates dissolved in different ionic liquids (ILs) for their further analysis by gas chromatography (GC). Derivatization reagents (nature and amounts), temperature and time of reaction and stirring conditions were evaluated for different carbohydrates (i.e., glucose, mannose, fructose and lactose) dissolved in 1-ethyl-3-methylimidazolium dicyanamide [EMIM][DCA]. Evaluation of conformational isomerism of glucose dissolved in [EMIM][DCA] revealed the effect of the time of dissolution in the equilibration of α- and β-furanoses (up to 3% and 6%, respectively, after 70 h of incubation) and that 21 h sufficed to obtain results similar to those provided by the reference method involving pyridine. Once optimized, the proposed derivatization procedure provided satisfactory yields (i.e., close to 100%) using 100 μL of trimethylsilylimidazole (TMSI) at mild conditions (25°C) for a relatively short time (1h) for most of the investigated carbohydrates. Under these experimental conditions, linear responses (i.e., R(2) better than 0.974) were obtained in the tested range of 0.25-1mg of the derivatized target compounds. Other reagents, such as N,O-bis(trimethylsilyl)trifluoroacetamide (BSTFA)+1% trimethylchlorosilane (TMCS), were successfully used under ultrasonic conditions for aldose monosaccharides and disaccharides derivatization, while BSTFA was useful for ketose monosaccharides. The possibility of using the proposed method for the derivatization of selected carbohydrates dissolved in different ILs and the efficiency of the method applied to the analysis of carbohydrates present in real samples (fruit juices) have also been investigated.
authors.affiliation: Instituto de Química Orgánica General (CSIC), Madrid, Spain.
authors.forename: L
authors.initials: L
authors.lastname: Ruiz-Aceituno
authors.forename: C
authors.initials: C
authors.lastname: Carrero-Carralero
authors.forename: L
authors.initials: L
authors.lastname: Ramos
authors.forename: I
authors.initials: I
authors.lastname: Martinez-Castro
authors.forename: M L
authors.initials: ML
authors.lastname: Sanz
mesh_terms: D002241:Carbohydrates / Q000032:analysis*; D002623:Chemistry Techniques, Analytical / Q000379:methods*; D002849:Chromatography, Gas / Q000379:methods; D052578:Ionic Liquids / Q000032:analysis*; D012821:Silanes / Q000032:analysis*
chemical_list: D002241:Carbohydrates; D052578:Ionic Liquids; D012821:Silanes
keywords: Carbohydrate derivatization; Conformational isomerism; Gas chromatography; Ionic liquids; Silylation