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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