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Title: Tandem mass spectrometric characterization of the conversion of xylose to furfural

Abstract

We report thermal decomposition of xylose into furfural under acidic conditions has been studied using tandem mass spectrometry. Two different Brønsted acids, maleic and sulfuric acids, were used to demonstrate that varying the Brønsted acid does not affect the mechanism of the reaction. Two selectively labeled xylose molecules, 1-13C and 5-13C-xyloses, were examined to determine which carbon atom is converted to the aldehyde carbon in furfural. This can be done by using tandem mass spectrometry since collision-activated dissociation (CAD) of protonated unlabeled furfural results in the loss of CO from the aldehyde moiety. The loss of a neutral molecule with MW of 29 Da (13CO) was observed for protonated furfural derived from 1-13C-labeled xylose while the loss of a neutral molecule with MW of 28 Da (CO) was observed for protonated furfural derived from 5-13C labeled xylose. These results support the hypothesis that the mechanism of formation of furfural under mildly hot acidic conditions involves an intramolecular rearrangement of protonated xylose into the pyranose form rather than into an open-chain form.

Authors:
 [1];  [1];  [1];  [1];  [1];  [1];  [1]
  1. Purdue Univ., West Lafayette, IN (United States)
Publication Date:
Research Org.:
Energy Frontier Research Centers (EFRC) (United States). Center for Direct Catalytic Conversion of Biomass to Biofuels (C3Bio) (C3Bio)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES)
OSTI Identifier:
1384962
Alternate Identifier(s):
OSTI ID: 1250593
Grant/Contract Number:  
SC000997; SC0000997
Resource Type:
Accepted Manuscript
Journal Name:
Biomass and Bioenergy
Additional Journal Information:
Journal Volume: 74; Journal Issue: C; Related Information: C3Bio partners with Purdue University (lead); Argonne National Laboratory; National Renewable Energy Laboratory; Northeastern University; University of Tennessee; Journal ID: ISSN 0961-9534
Publisher:
Elsevier
Country of Publication:
United States
Language:
English
Subject:
59 BASIC BIOLOGICAL SCIENCES; Xylose; Furfural; Tandem mass spectrometry; Catalytic conversion; Maleic acid; 13C labeling; Catalysis (homogeneous); Catalysis (heterogeneous); Biofuels (including algae and biomass); Bio-inspired; Materials and chemistry by design; Synthesis (self-assembly); Synthesis (scalable processing)

Citation Formats

Vinueza, Nelson R., Kim, Eurick S., Gallardo, Vanessa A., Mosier, Nathan S., Abu-Omar, Mahdi M., Carpita, Nicholas C., and Kenttämaa, Hilkka I. Tandem mass spectrometric characterization of the conversion of xylose to furfural. United States: N. p., 2015. Web. doi:10.1016/j.biombioe.2014.10.012.
Vinueza, Nelson R., Kim, Eurick S., Gallardo, Vanessa A., Mosier, Nathan S., Abu-Omar, Mahdi M., Carpita, Nicholas C., & Kenttämaa, Hilkka I. Tandem mass spectrometric characterization of the conversion of xylose to furfural. United States. https://doi.org/10.1016/j.biombioe.2014.10.012
Vinueza, Nelson R., Kim, Eurick S., Gallardo, Vanessa A., Mosier, Nathan S., Abu-Omar, Mahdi M., Carpita, Nicholas C., and Kenttämaa, Hilkka I. Fri . "Tandem mass spectrometric characterization of the conversion of xylose to furfural". United States. https://doi.org/10.1016/j.biombioe.2014.10.012. https://www.osti.gov/servlets/purl/1384962.
@article{osti_1384962,
title = {Tandem mass spectrometric characterization of the conversion of xylose to furfural},
author = {Vinueza, Nelson R. and Kim, Eurick S. and Gallardo, Vanessa A. and Mosier, Nathan S. and Abu-Omar, Mahdi M. and Carpita, Nicholas C. and Kenttämaa, Hilkka I.},
abstractNote = {We report thermal decomposition of xylose into furfural under acidic conditions has been studied using tandem mass spectrometry. Two different Brønsted acids, maleic and sulfuric acids, were used to demonstrate that varying the Brønsted acid does not affect the mechanism of the reaction. Two selectively labeled xylose molecules, 1-13C and 5-13C-xyloses, were examined to determine which carbon atom is converted to the aldehyde carbon in furfural. This can be done by using tandem mass spectrometry since collision-activated dissociation (CAD) of protonated unlabeled furfural results in the loss of CO from the aldehyde moiety. The loss of a neutral molecule with MW of 29 Da (13CO) was observed for protonated furfural derived from 1-13C-labeled xylose while the loss of a neutral molecule with MW of 28 Da (CO) was observed for protonated furfural derived from 5-13C labeled xylose. These results support the hypothesis that the mechanism of formation of furfural under mildly hot acidic conditions involves an intramolecular rearrangement of protonated xylose into the pyranose form rather than into an open-chain form.},
doi = {10.1016/j.biombioe.2014.10.012},
journal = {Biomass and Bioenergy},
number = C,
volume = 74,
place = {United States},
year = {Fri Jan 16 00:00:00 EST 2015},
month = {Fri Jan 16 00:00:00 EST 2015}
}

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Works referenced in this record:

Ethanol Can Contribute to Energy and Environmental Goals
journal, January 2006


Chemicals from Biomass
journal, November 2007


Cell-wall carbohydrates and their modification as a resource for biofuels
journal, May 2008


Maize and sorghum: genetic resources for bioenergy grasses
journal, August 2008


Biomimetic Catalysis for Hemicellulose Hydrolysis in Corn Stover
journal, February 2007

  • Lu, Y.; Mosier, N. S.
  • Biotechnology Progress, Vol. 23, Issue 1
  • DOI: 10.1021/bp060223e

Liquid-Phase Catalytic Processing of Biomass-Derived Oxygenated Hydrocarbons to Fuels and Chemicals
journal, September 2007

  • Chheda, Juben N.; Huber, George W.; Dumesic, James A.
  • Angewandte Chemie International Edition, Vol. 46, Issue 38, p. 7164-7183
  • DOI: 10.1002/anie.200604274

Synergies between Bio- and Oil Refineries for the Production of Fuels from Biomass
journal, September 2007

  • Huber, George W.; Corma, Avelino
  • Angewandte Chemie International Edition, Vol. 46, Issue 38, p. 7184-7201
  • DOI: 10.1002/anie.200604504

Phase Modifiers Promote Efficient Production of Hydroxymethylfurfural from Fructose
journal, June 2006

  • Roman-Leshkov, Yuriy; Chheda, Juben N.; Dumesic, James A.
  • Science, Vol. 312, Issue 5782, p. 1933-1937
  • DOI: 10.1126/science.1126337

Metal Chlorides in Ionic Liquid Solvents Convert Sugars to 5-Hydroxymethylfurfural
journal, June 2007


Synthesis of Furfural from Xylose and Xylan
journal, September 2010

  • Binder, Joseph B.; Blank, Jacqueline J.; Cefali, Anthony V.
  • ChemSusChem, Vol. 3, Issue 11
  • DOI: 10.1002/cssc.201000181

The conversion of -xylose and -glucuronic acid to 2-furaldehyde
journal, January 1970


Routes of conversion of D-xylose, hexuronic acids, and L-ascorbic acid to 2-furaldehyde
journal, May 1972

  • Feather, Milton S.; Harris, Donald W.; Nichols, Susan B.
  • The Journal of Organic Chemistry, Vol. 37, Issue 10
  • DOI: 10.1021/jo00975a032

Evidence for a C-2→C-1 intramolecular hydrogen-transfer during the acid-catalyzed isomerization of D-glucose to D-fructose ag]
journal, October 1973


Pentose Reactions. i. Furfural Formation
journal, January 1932

  • Hurd, Charles D.; Isenhour, Lloyd L.
  • Journal of the American Chemical Society, Vol. 54, Issue 1
  • DOI: 10.1021/ja01340a048

Mechanism of formation of 2-furaldehyde from d-xylose
journal, September 1991


13C-labeled aldopentoses: detection and quantitation of cyclic and acyclic forms by heteronuclear 1D and 2D NMR spectroscopy
journal, February 1998


Energetics of Xylose Decomposition as Determined Using Quantum Mechanics Modeling
journal, October 2006

  • Nimlos, Mark R.; Qian, Xianghong; Davis, Mark
  • The Journal of Physical Chemistry A, Vol. 110, Issue 42
  • DOI: 10.1021/jp0626770

Selective Conversion of Biomass Hemicellulose to Furfural Using Maleic Acid with Microwave Heating
journal, January 2012

  • Kim, Eurick S.; Liu, Shuo; Abu-Omar, Mahdi M.
  • Energy & Fuels, Vol. 26, Issue 2
  • DOI: 10.1021/ef2014106

Phase-modulated stored waveform inverse Fourier transform excitation for trapped ion mass spectrometry
journal, February 1987

  • Chen, Ling.; Wang, Tao Chin Lin.; Ricca, Tom L.
  • Analytical Chemistry, Vol. 59, Issue 3
  • DOI: 10.1021/ac00130a016

Tailored excitation for Fourier transform ion cyclotron mass spectrometry
journal, December 1985

  • Marshall, Alan G.; Wang, Tao Chin Lin; Ricca, Tom L.
  • Journal of the American Chemical Society, Vol. 107, Issue 26
  • DOI: 10.1021/ja00312a015

Works referencing / citing this record:

Biobased Furanics: Kinetic Studies on the Acid Catalyzed Decomposition of 2-Hydroxyacetyl Furan in Water Using Brönsted Acid Catalysts
journal, April 2017

  • Soetedjo, J. N. M.; van de Bovenkamp, H. H.; Deuss, P. J.
  • ACS Sustainable Chemistry & Engineering, Vol. 5, Issue 5
  • DOI: 10.1021/acssuschemeng.6b03198