Carbohydrate stabilization extends the kinetic limits of chemical polysaccharide depolymerization


Polysaccharide depolymerization is an essential step for valorizing lignocellulosic biomass. In inexpensive systems such as pure water or dilute acid mixtures, carbohydrate monomer degradation rates exceed hemicellulose—and especially cellulose—depolymerization rates at most easily accessible temperatures, limiting sugar yields. Here, we use a reversible stabilization of xylose and glucose by acetal formation with formaldehyde to alter this kinetic paradigm, preventing sugar dehydration to furans and their subsequent degradation. During a harsh organosolv pretreatment in the presence of formaldehyde, over 90% of xylan in beech wood was recovered as diformylxylose (compared to 16% xylose recovery without formaldehyde). The subsequent depolymerization of cellulose led to carbohydrate yields over 70% and a final concentration of ~5 wt%, whereas the same conditions without formaldehyde gave a yield of 28%. This stabilization strategy pushes back the longstanding kinetic limits of polysaccharide depolymerization and enables the recovery of biomass-derived carbohydrates in high yields and concentrations.

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Fig. 1: Carbohydrate stabilization using formaldehyde (FA).
Fig. 2: Hemicellulose stabilization and lignin extraction during biomass pretreatment.
Fig. 3: Soluble carbohydrates produced from cellulose-rich pretreated solids using a flow-through reactor.
Fig. 4: Pentose dehydration to furfural in biphasic water–alkylphenol reaction systems.

Data availability

The data that support the findings of this study are available from the corresponding author upon reasonable request.


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This work was supported by the Swiss National Science Foundation through grant PYAPP2_154281, by the Swiss Competence Center for Energy Research: Biomass for a Swiss Energy Future through the Swiss Commission for Technology and Innovation grant KTI.2014.0116, and by EPFL. The authors thank M. Studer from Bern University of Applied Sciences (Switzerland) for providing beech wood.

Author information




Y.M.Q.S. and J.S.L. conceived of the idea, designed the study and wrote the manuscript. Y.M.Q.S performed all experiments unless noted otherwise, and analysed the data. R.Z.V. performed xylose and diformylxylose dehydration reactions, and assisted in purifying diformylxylose and diformylglucose. M.T.A produced some of the pretreated solids and performed the preliminary techno-economic calculations. All authors edited the manuscript.

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Correspondence to Jeremy S. Luterbacher.

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Supplementary information

Supplementary materials and methods, supplementary text, supplementary figures 1–22 and tables 1–10

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Questell-Santiago, Y.M., Zambrano-Varela, R., Talebi Amiri, M. et al. Carbohydrate stabilization extends the kinetic limits of chemical polysaccharide depolymerization. Nature Chem 10, 1222–1228 (2018).

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