Solution-State One- and Two-Dimensional NMR Spectroscopy of High-Molecular-Weight Cellulose.

High-molecular-weight celluloses (which even include bacterial cellulose) can be dissolved fully in methyltrioctylphosphonium acetate/[D6 ]DMSO solutions to allow the measurement of resonance-overlap-free 1 D and 2 D NMR spectra. This is achieved by a simple and non-destructive dissolution method, without solvent suppression, pre-treatment or deuteration of the ionic component. We studied a range of cellulose samples by using various NMR experiments to make an a priori assignment of the cellulose resonances. Chain-end resonances are also visible in the (1) H NMR spectrum. This allows the rough determination of the degree of polymerisation (DP) of a sample for low-DP celluloses by the integration of non-reducing chain ends C1 versus polymeric cellobiose C1. Low-DP celluloses show a good agreement with the gel-permeation chromatography (GPC) values, but high-DP pulps show more deviation. For high-purity pulps (pre-hydrolysis kraft and sulfite), residual xyloses and mannoses can also be identified from the (1) H-(13) C heteronuclear single-quantum coherence (HSQC) spectra. Resonances are thus assigned for the common polymeric polysaccharides found in chemical pulps.