Enantiomeric Excess Determination for Monosaccharides Using Chiral Transmission to Cold Gas-Phase Tryptophan in...

Chiral transmission between monosaccharides and amino acids via photodissociation in the gas phase was examined using a tandem mass spectrometer fitted with an electrospray ionization source and a cold ion trap in order to investigate the origin of the homochirality of biomolecules in molecular clouds. Ultraviolet photodissociation mass spectra of cold gas-phase noncovalent complexes of the monosaccharide enantiomers glucose (Glc) and galactose (Gal) with protonated L-tryptophan H⁺(L-Trp) were obtained by photoexcitation of the indole ring of L-Trp. L-Trp dissociated via C_α-C_β bond cleavage when noncovalently complexed with D-Glc; however, no dissociation of L-Trp occurred in the homochiral H⁺(L-Trp)(L-Glc) noncovalent complex, where the energy absorbed by L-Trp was released through the evaporation of L-Glc. This enantioselective photodissociation of Trp was due to the transmission of chirality from Glc to Trp via photodissociation in the gas-phase noncovalent complexes, and was applied to the quantitative chiral analysis of monosaccharides. The enantiomeric excess of monosaccharides in solution could be determined by measuring the relative abundance of the two product ions in a single photodissociation mass spectrum of the cold gas-phase noncovalent complex with H⁺(L-Trp), and by referring to the linear relationships derived in this work. Graphical Abstract ᅟ.