Hemicellulosic Polysaccharides Mimics: Synthesis of Tailored Bottlebrush-Like Xyloglucan Oligosaccharide Glycopolymers as Binders of Nanocrystalline Cellulose.

We report in this contribution that while low molecular weight hemicellulosic building blocks are known not to interact with cellulosic materials, their multivalent presentation on a polymeric scaffold significantly enhanced the binding interactions that are remarkably in the same range as those usually observed for lectin-carbohydrate interactions. We developed a poly(propargyl methacrylate) scaffold on which we conjugated, by "post-click" reaction, a variety of azide reducing-end functionalized xyloglucan oligosaccharides with controlled enzymatic-mediated rate of degalactosylation. Bottlebrush-like xyloglucan oligosaccharide glycopolymers (poly(XGOn)) were obtained and their self-assemblies in aqueous solution were investigated using dynamic light scattering (DLS). We demonstrated that increasing the extent of degalactosylation promoted self-association of poly(XGOn), which we attribute to the appearance of hydrophobic domains. A sharp thermoresponsiveness, which corresponds to a decrease in aggregate size with increasing temperature, was observed when the extent of degalactosylation was 30% or greater. Importantly, isothermal titration calorimetry (ITC) and polarized/depolarized DLS revealed that poly(XGOn) exhibit a significant capacity to interact with nanocrystalline cellulose (NCC) surfaces particularly for the nondegalactosylated form, emphasizing the important role of galactosyl residues in the binding mechanism and in the 3-dimensional structures of glycopolymers.