Differentiation of Underivatized Diastereomeric Hexosamine Monosaccharides and Their Quantification in a Mixture Using the Kinetic Method under Electrospray Ionization Conditions

Abstract

A simple method to differentiate underivatized diastereomeric hexosamine monosaccharides, glucosamine, galactosamine, and mannosamine is reported by applying the kinetic method using N-acetylhexosamines or naturally occurring amino acids as reference bases under electrospray ionization conditions. The observed differences to distinguish the diastereomeric hexosamines are found mainly due to the proton affinity (PA) differences between the analyte and the reference base. The PA values of the hexosamines are not available in the literature, and hence, we estimated them by the kinetic method using N-acetylhexosamines as reference bases. The determined PA values are 223.97 kcal/mol for glucosamine, 224.99 kcal/mol for mannosamine, and 224.71 kcal/mol for galactosamine. The similar PA values were also obtained by using amino acids as reference bases. We have applied the same methodology to quantify these hexosamines in a mixture following the three-point calibration method suggested in the literature.

Chiral discrimination of D- and L-amino acids using iodinated tyrosines as chiral references: Effect of iodine substituent

“…The kinetic method has been used for the estimation of thermodynamic properties as well as for chiral discrimination [21][22][23][24][25][26][27][28][29][30][31][32][33][34]. In this method, mostly the cluster ion [M II (ref) 2 A Ϫ H] ϩ consisting of an analyte molecule of interest (A), two molecules of chiral reference ligand (ref), and a metal ion arranged in either octahedral or tetrahedral fashion around the metal ion are generated in the source of a mass spectrometer and their dissociation studied (Scheme 1).…”

“…The mass spectrometry based chiral recognition (gas phase) methods fall into the following categories: (1) measurement of relative abundance of diastereomeric adducts ions formed between analyte of interest and a chiral reference [6 -9]; (2) Host-guest ion/molecule (equilibrium) reactions; diastereomeric complex ion allowed to react with a neutral reagent (guest) either chiral or non chiral. Chiral discrimination is achieved by investigating the differences in exchange rate with time due to chirality of the analyte [10 -16]; (3) Collision induced dissociation mass spectra of proton or metal bound diastereomeric adduct ion formed between an analyte and a chiral reference shows the difference in fragmentation pattern [17][18][19][20][21][22].The kinetic method has been used for the estimation of thermodynamic properties as well as for chiral discrimination [21][22][23][24][25][26][27][28][29][30][31][32][33][34]. In this method, mostly the cluster ion [M II (ref) 2 A Ϫ H] ϩ consisting of an analyte molecule of interest (A), two molecules of chiral reference ligand (ref), and a metal ion arranged in either octahedral or tetrahedral fashion around the metal ion are generated in the source of a mass spectrometer and their dissociation studied (Scheme 1).…”

“…The mass spectrometry based chiral recognition (gas phase) methods fall into the following categories: (1) measurement of relative abundance of diastereomeric adducts ions formed between analyte of interest and a chiral reference [6 -9]; (2) Host-guest ion/molecule (equilibrium) reactions; diastereomeric complex ion allowed to react with a neutral reagent (guest) either chiral or non chiral. Chiral discrimination is achieved by investigating the differences in exchange rate with time due to chirality of the analyte [10 -16]; (3) Collision induced dissociation mass spectra of proton or metal bound diastereomeric adduct ion formed between an analyte and a chiral reference shows the difference in fragmentation pattern [17][18][19][20][21][22].…”

The distinction of underivatized monosaccharides using electrospray ionization ion trap mass spectrometry

“…22 Collisioninduced dissociation of ammonium-cationized a-and b-hexose peracetates has been studied for anomeric distinction. 23 A kinetic method based on proton affinity differences has been employed to differentiate diastereomeric hexosamines 12 and N-acetylhexosamines 14 with a triple quadrupole mass spectrometer. In this study, we aimed to distinguish monosaccharide stereoisomers without derivatization using ion trap mass spectrometry (ITMS .…”

Capillary electrophoretic determination of glucosamine in osteoarthritis tablets via microwave-accelerated dansylation

“…Kanurnyy [4] carboxyphenyl anthranilic acid could alleviate emotional hypertension caused by high stress. Separation and analysis of aminosaccharides have since become an interesting research topic for many years, and some powerful methods [5][6][7] have been inspected or explored such as mass spectrometry (MS), gas chromatography (GC), high performance liquid chromatography (HPLC) and spectrophotometry. HPLC analysis of aminosaccharides using silica-based packing materials with refractive index (RI) detection offers a general way for intact solutes but possesses only moderate sensibility.…”