Synthesis of Se polysaccharide catalyzed by sulfonic acid functionalized ionic liquids: Synergism effect of anion/cation

Abstract

The rational design and construction of controllable selenylation strategy are important for the study on the structure-activity relationship of Se polysaccharides. Herein, selenized Artemisia sphaerocephala polysaccharides (SePASs) were synthesized by using sulfonic acid functionalized ionic liquids (SFILs) as catalysts in order to study the regulation of the cation/anion constitute on the selenylation efficiency and Se polysaccharide structure. Impressively, SFILs could promote the efficient substitution of seleno-group on the polysaccharide backbone through the synergistic catalysis by cation/anions (Se content up to 5582.7 μg/g). Further, reaction mechanism and potential dissolution effect was supported by DFT calculation and polarized light microscopy. 13C NMR and FT-IR spectra analysis of SePASs exhibited that selenite existed in polysaccharides and the substitution position occured at C-6. SEC-MALLS, monosaccharide composition results revealed that strong acidity of SFILs lead to the driving forces toward low molecular mass polysaccharide fragments and synergistic effect of anion/cations in SFILs (-SO3H group of cations as proton donor, anions as nucleophile) showed regulation on average molecular mass. In addition, the strong attractions between the seleno-groups generated agglomeration of polysaccharide chain, which was proved by applying AFM analysis. Therefore, this work provided a new insight for manipulate Se content and MW of Se polysaccharides.