The effect of the degree of substitution on the solubility of cellulose acetoacetates in water: A molecular dynamics simulation and density functional theory study

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The effect of the degree of substitution (DS) on the aqueous solubility of cellulose acetoacetates (CAA) was investigated by molecular dynamics simulations and density functional theory calculations. Using average non-covalent interaction and the electrostatic potential analyses done on cellobiose as the model, it was showed both polar and non-polar areas of the system increased as the more hydroxyls were replaced by acetoacetate groups. Analyses of the solvation free energies of a celludecose (glucan containing 10 monosaccharide sugar units) at constant pressure and temperature showed the polar solvation free energies and the number of decose-water hydrogen bonds increased as DS was varied from 0.3 to 0.8, which contributes to higher solubility in water. When the DS of CAA increased from 0.8 to 1.5, it became insoluble again because the plateaued increase in solvation free energy could no longer compensate for the decreasing CAA-water hydrogen bonding interactions. The growing van der Waals interactions among CAA molecules as the molecule grows bigger with each attached AA group also contributes to the decreasing water solubility.