Synthesis of 5-hydroxymethylfurfural using sulfonated calix[4]arene in brine and rapid reaction monitoring with micellar capillary electrokinetic chromatography
- 1Department of Chemistry, Nanoscience Center, P.O. Box 35, Finland, 40014
- 2Department of Chemistry, University of Helsinki, A.I. Virtasen aukio, Finland, 00014
Abstract
The acid-catalyzed dehydration of D-(−)-fructose into 5-hydroxymethylfurfural (HMF) and side product levulinic acid (LA) in saturated aqueous sodium chloride was investigated with 1 H quantitative nuclear magnetic resonance spectroscopy (qNMR) and micellar capillary electrokinetic chromatography (MEKC). The highest isolated HMF yield of 32.7 ± 5.4 % was obtained with 2 mol% sulfonated calix[4]arene (sC4A) from 0.3 M fructose over 4 hours at 140 °C showing modestly improved performance over p -toluenesulfonic acid, methanesulfonic acid, p-hydroxybenzenesulfonic acid, sulfuric acid and hydrochloric acid. Host-guest interactions between sC4A and HMF were investigated with 1 H NMR titrations at different temperatures revealing supramolecular complexation at 30 °C, whereas p -hydroxybenzenesulfonic acid bearing same functional groups but lacking the macrocyclic cavity of sC4A did not show interactions with HMF. A MECK method for the HMF analysis from acidic reaction mixtures was developed reaching limit of detection and limit of quantification values of 0.003 mM and 0.009 mM, respectively. Here we demonstrate that MEKC can be used to track the production of HMF at the concentration range 0.1–10 mM within a total analysis time of 2 minutes.
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BibTeX
@misc{naulapaa2026synthesis,
title = {{Synthesis of 5-hydroxymethylfurfural using sulfonated calix[4]arene in brine and rapid reaction monitoring with micellar capillary electrokinetic chromatography}},
author = {Julia Naulapää and Luukas Määttänen and Sara Korkeakunnas and Susanne K. Wiedmer and Kaisa Helttunen},
howpublished = {ChemRxiv},
year = {2026},
month = oct,
doi = {10.26434/chemrxiv.15010875/v1},
url = {https://chemrxiv.org/doi/full/10.26434/chemrxiv.15010875/v1},
note = {CC BY-NC-ND},
}
RIS
TY - UNPB
TI - Synthesis of 5-hydroxymethylfurfural using sulfonated calix[4]arene in brine and rapid reaction monitoring with micellar capillary electrokinetic chromatography
AU - Julia Naulapää
AU - Luukas Määttänen
AU - Sara Korkeakunnas
AU - Susanne K. Wiedmer
AU - Kaisa Helttunen
PY - 2026
DA - 2026/10/22
PB - ChemRxiv
DO - 10.26434/chemrxiv.15010875/v1
UR - https://chemrxiv.org/doi/full/10.26434/chemrxiv.15010875/v1
AB - The acid-catalyzed dehydration of D-(−)-fructose into 5-hydroxymethylfurfural (HMF) and side product levulinic acid (LA) in saturated aqueous sodium chloride was investigated with 1 H quantitative nuclear magnetic resonance spectroscopy (qNMR) and micellar capillary electrokinetic chromatography (MEKC). The highest isolated HMF yield of 32.7 ± 5.4 % was obtained with 2 mol% sulfonated calix[4]arene (sC4A) from 0.3 M fructose over 4 hours at 140 °C showing modestly improved performance over p -toluenesulfonic acid, methanesulfonic acid, p-hydroxybenzenesulfonic acid, sulfuric acid and hydrochloric acid. Host-guest interactions between sC4A and HMF were investigated with 1 H NMR titrations at different temperatures revealing supramolecular complexation at 30 °C, whereas p -hydroxybenzenesulfonic acid bearing same functional groups but lacking the macrocyclic cavity of sC4A did not show interactions with HMF. A MECK method for the HMF analysis from acidic reaction mixtures was developed reaching limit of detection and limit of quantification values of 0.003 mM and 0.009 mM, respectively. Here we demonstrate that MEKC can be used to track the production of HMF at the concentration range 0.1–10 mM within a total analysis time of 2 minutes.
ER -