Influence of cation on the cellulose dissolution investigated by MD simulation and experiments

Cellulose is the most abundant natural polymer on the earth, and effective solvents are essential for its wide application. Among various solvents such as alkali/urea or ionic liquids, cations all play a very important role on the cellulose dissolution. In this work, the influence of cation on the cellulose dissolution in alkali/urea via a cooling process was investigated with a combination of MD simulation and experiments, including differential scanning calorimetry (DSC) and NMR diffusometry (PFG-SE NMR). The results of DSC proved that the dissolution of cellulose in both solvents was a process within a temperature range, starting at above 0 °C and completing at low temperature (−5 °C for LiOH/urea and −20 °C for NaOH/urea), indicating the necessity of low temperature for the cellulose dissolution. Molecular dynamic (MD) simulation suggested that the electrostatic force between OH− and cellulose dominated the inter-molecular interactions. In our findings, Li+ could penetrate closer to cellulose, and displayed stronger electrostatic interaction with the biomacromolecule than Na+, thus possessed a greater “stabilizing” effect on the OH−/cellulose interaction. PFG-SE NMR demonstrated a more significant binding fraction of Li+ than Na+ to cellulose, which was consistent with MD. These results indicated that the direct interactions existed between the cations and cellulose, and Li+ exhibited stronger interaction with cellulose, leading to stronger dissolving power.