Energetics of xylose decomposition as determined using quantum mechanics modeling

The decomposition of xylose has been studied using quantum mechanical calculations supported by NMR data. Proposed mechanisms for the decomposition of xylose have been investigated by obtaining the structures and energies of transition states and products. The intent of this study was to understand the experimentally observed formation of furfural and formic acid that occurs during the decomposition of xylose in mildly hot acidic solutions. A mechanism of furfural formation involving the opening of the pyranose ring and subsequent dehydration of the aldose was compared to a direct intramolecular rearrangement of the protonated pyranose. Energies were determined using CBS-QB3, and it was shown that the barriers for dehydration of the aldose were high compared to intramolecular rearrangement. This result suggests that the latter mechanism is a more likely mechanism for furfural formation. The intramolecular rearrangement step results from protonation of xylose at the O2 hydroxyl group. In addition, it has been shown that formic acid formation is a likely result of the protonation of xylose at the O3 hydroxyl group. Finally, solvation of xylose decomposition was studied by calculating energy barriers for xylose in selected water clusters. The mechanisms proposed here were supported in part by C-13-labeling studies using NMR.