Origin of 5-hydroxymethylfurfural stability in water/dimethyl sulfoxide mixtures

George Tsilomelekis, Tyler R. Josephson, Vladimiros Nikolakis, Stavros Caratzoulas

Research output: Contribution to journalArticlepeer-review

99 Scopus citations

Abstract

In the present work, we combined vibrational spectroscopy with electronic structure calculations to understand the solvation of HMF in DMSO, water, and DMSO/water mixtures and to provide insights into the observed hindrance of HMF rehydration and aldol condensation reactions if it is dissolved in DMSO/water mixtures. To achieve this goal, the attenuated total reflection FTIR spectra of a wide composition range of binary and ternary mixtures were measured, analyzed, and compared to the findings of ab initio DFT calculations. The effect of solvent on the HMF C=O and OáH vibrational modes reveals significant differences that are ascribed to different intermolecular interactions between HMF and DMSO or water. We also found that DMSO binds to HMF more strongly than water, and interactions with the HMF hydroxyl group are stronger than those with the HMF carbonyl group. We also showed the preferential solvation of HMF C=O groups by DMSO if HMF is dissolved in DMSO/water mixed solvent. Frontier molecular orbital theory was used to examine the influence of the solvent on side reactions. The results show that HMF solvation by DMSO increases its LUMO energy, which reduces its susceptibility to nucleophilic attack and minimizes undesirable hydration and humin-formation reactions. This result, together with the preferential solvation of HMF by DMSO, provide an explanation for the enhanced HMF stability in DMSO/water mixtures observed experimentally.

Original languageEnglish (US)
Pages (from-to)117-126
Number of pages10
JournalChemSusChem
Volume7
Issue number1
DOIs
StatePublished - Jan 1 2014

Keywords

  • Ab initio calculations
  • Biomass
  • Hydroxyfurfural
  • Solvent effects
  • Vibrational spectroscopy

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