Complete Hexose Isomer Identification with Mass Spectrometry

Abstract

Abstract. The first analytical method is presented for the identification and absolute configuration determination of all 24 aldohexose and 2-ketohexose isomers, including the D and L enantiomers for allose, altrose, galactose, glucose, gulose, idose, mannose, talose, fructose, psicose, sorbose, and tagatose. Two unique fixed ligand kinetic method combinations were discovered to create significant enough energetic differences to achieve chiral discrimination among all 24 hexoses. Each of these 24 hexoses yields unique ratios of a specific pair of fragment ions that allows for simultaneous determination of identification and absolute configuration. This mass spectrometric-based methodology can be readily employed for accurate identification of any isolated monosaccharide from an unknown biological source. This work provides a key step towards the goal of complete de novo carbohydrate analysis.

Chiral detection of entecavir stereoisomeric impurities through coordination with R‐besivance and ZnII using mass spectrometry

“…More research is needed to improve the sensitivity of this method and contribute to its utility in enantioselectivity research of biological samples in vivo . In summary, this study and previous research results suggest that the KM may have great applications in the near future in the practical analysis of chiral drugs.…”

A High‐Throughput Mass‐Spectrometry‐Based Assay for Identifying the Biochemical Functions of Putative Glycosidases

“…The complex natures of carbohydrates obtained from biological sources has made their study and the development of efficient tools to probe their structures and functions particularly challenging . Conventional ways to determine carbohydrate structures often include acid hydrolysis as the first step, to break large oligosaccharides into individual monosaccharides units for further analysis by techniques such as liquid chromatography and mass spectrometry . However, the use of such a nonspecific cleavage method obliterates any stereochemical information relating to the original glycosidic linkages.…”

Analysis of stereoisomers of chiral drug by mass spectrometry

“…However, most of the work is limited to simple structure of small molecules like amino acids. [61][62][63] Amino acids; amino acids esters; 3,4-dihydroxy-L-phenylalanine; tadalafil; and isoproterenol Kinetic method: usually use metal ions and (modified) amino acids together to achieve the enantiomeric differentiation and quantitation of stereoisomers. Collision-induced dissociation of diastereomeric complex and ion mobility spectrometry are the latest methods, and there has been much work focusing on finding the suitable ligand for chiral analyte involving using computational simulation approach to explore the ligand binding mechanism for further application.…”

“…59,60 Pentose isomers, hexose isomers, and amino acid Fixed ligand kinetic method: unique fixed ligand could be created, like guanosine monophosphate. [61][62][63] Amino acids; amino acids esters; 3,4-dihydroxy-L-phenylalanine; tadalafil; and isoproterenol Kinetic method: usually use metal ions and (modified) amino acids together to achieve the enantiomeric differentiation and quantitation of stereoisomers. 38,39,[64][65][66][67] Amino acids, glucose isomer, DMEB*, polylactide, and catechin epimers Ion mobility mass spectrometry: small chiral molecules were successfully distinguished by calculating the molecular collision cross section.…”