A mass spectrometric study of the acid-catalysed d-fructose dehydration in the gas phase

• Gas-phase dehydration of protonated d-fructose was studied by mass spectrometry.
• The ionic gaseous intermediates and products were structurally characterized.
• A mixed population of isomeric [C6H6O3]H+ ions is formed.
• One possible gas-phase dehydration mechanism of d-fructose was hypothesized.

5-hydroxymethylfuraldehyde (5-HMF) and simpler compounds, such as levulinic acid (LA) and glyceraldehyde, are platform molecules produced by the thermal acid-catalyzed dehydration of carbohydrates coming from biomass. Understanding sugar degradation pathways on a molecular level is necessary to increase selectivity, reduce degradation by-products yields and optimize catalytic strategies, fundamental knowledge for the development of a sustainable renewable industry. In this work gaseous protonated d-fructose ions, generated in the ESI source of a triple quadrupole mass spectrometer, were allowed to undergo Collisionally Activated Decomposition (CAD) into the quadrupole collision cell. The ionic intermediates and products derived from protonated d-fructose dehydration were structurally characterized by their fragmentation patterns and the relative water-loss dehydration energies measured by energy-resolved CAD mass spectra. The data were compared with those obtained from protonated d-glucose decomposition in the same experimental conditions. In the gas phase, d-fructose dehydration leads to the formation of a mixed population of isomeric [C6H6O3]H+ ions, whose structures do not correspond exclusively to 5-hydroxymethyl-2-furaldehyde protonated at the more basic aldehydic group.

Figure optionsDownload as PowerPoint slide