Enhanced dissolution of galactomannan and highly efficient selenium functionalization using ionic liquids with dual roles as solvents and catalysts

Abstract

Galactomannan stands as a promising heteropolysaccharide, yet its randomly distributed non-linear structures and high molecular mass remain a huge challenge in solubilization and wide range of chemical modifications. This work develops a task specific approach for efficient dissolve of galactomannan in ionic liquids (ILs) by destructing and reconstructing intermolecular/intramolecular hydrogen bonds of galactomannan. Combining density functional theory calculations and experimental results, a reasonable mechanism of polysaccharide dissolution is proposed that the hydrogen bond networks of polysaccharide are broken, thus the hydroxyl groups are fully exposed and activated to facilitate functionalization. In view of the enhanced solubilization, an excellent effect in selenylation of galactomannan is notably improved by employing ILs with dual roles as solvents and catalysts. Typically, the introduction of -SO3H in ILs (SFILs) effectively enhances the protonation ability of selenium donor and thus further improves the functionalization efficiency. Furthermore, a surprising finding is observed that selenium content and average molecular mass of functionalized polysaccharide can be manipulated by the anions-cations synergistic effect which is highly dependent on SFILs acidity strength. This work proposed an integrated and promising strategy for improving the solubilization and functionalization manipulating by ILs, showing a great referential value for the widespread application in polysaccharide-rich resources.