title: A mass spectrometric study of the acid-catalysed d-fructose dehydration in the gas phase.
abstract: 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.
authors.affiliation: Department of Chemistry and Drugs Technologies, 'Sapienza' University of Rome, P.le A. Moro, 5-00185 Rome, Italy. Electronic address: federico.pepi@uniroma1.it.
authors.forename: Federico
authors.initials: F
authors.lastname: Pepi
authors.affiliation: Department of Mathematics and Physics, Second University of Naples, Via Vivaldi, 43-81100 Caserta, Italy.
authors.forename: Andreina
authors.initials: A
authors.lastname: Ricci
authors.affiliation: Department of Chemistry and Drugs Technologies, 'Sapienza' University of Rome, P.le A. Moro, 5-00185 Rome, Italy.
authors.forename: Stefania
authors.initials: S
authors.lastname: Garzoli
authors.affiliation: Department of Chemistry and Drugs Technologies, 'Sapienza' University of Rome, P.le A. Moro, 5-00185 Rome, Italy.
authors.forename: Anna
authors.initials: A
authors.lastname: Troiani
authors.affiliation: Department of Chemistry and Drugs Technologies, 'Sapienza' University of Rome, P.le A. Moro, 5-00185 Rome, Italy.
authors.forename: Chiara
authors.initials: C
authors.lastname: Salvitti
authors.affiliation: Department of Mathematics and Physics, Second University of Naples, Via Vivaldi, 43-81100 Caserta, Italy.
authors.forename: Brunella
authors.initials: B
authors.lastname: Di Rienzo
authors.affiliation: Department of Chemistry and Drugs Technologies, 'Sapienza' University of Rome, P.le A. Moro, 5-00185 Rome, Italy.
authors.forename: Pierluigi
authors.initials: P
authors.lastname: Giacomello
mesh_terms: D002384:Catalysis; D005632:Fructose / Q000737:chemistry*; D005662:Furaldehyde / Q000031:analogs & derivatives / Q000737:chemistry; D005740:Gases / Q000737:chemistry*; D007982:Levulinic Acids / Q000737:chemistry; D021241:Spectrometry, Mass, Electrospray Ionization; D014867:Water / Q000737:chemistry*
chemical_list: D005740:Gases; D007982:Levulinic Acids; D014867:Water; D005632:Fructose; C008046:5-hydroxymethylfurfural; D005662:Furaldehyde; C032246:levulinic acid
keywords: 5-Hydroxymethylfuraldehyde; Biomass; Fructose dehydration; Gas phase; Mass spectrometry