Anion-Specific Water Interactions with Nanochitin: Donnan and Osmotic Pressure Effects as Revealed by Quartz...

The development of new materials emphasizes greater use of sustainable and eco-friendly resources, including those that take advantage of the unique properties of nanopolysaccharides. Advances in this area, however, necessarily require a thorough understanding of interactions with water. Our contribution to this important topic pertains to the swelling behavior of partially deacetylated nanochitin (NCh), which has been studied here by quartz crystal microgravimetry. Ultrathin films of NCh supported on gold-coated resonators have been equilibrated in aqueous electrolyte solutions (containing NaF, NaCl, NaBr, NaNO₃, Na₂SO₄, Na₂SO₃, or Na₃PO₄) at different ionic strengths. As anticipated, NCh displays contrasting swelling/deswelling responses, depending on the ionic affinities and valences of the counterions. The extent of water uptake induced by halide anions, for instance, follows a modified Hofmeister series with F^- producing the highest swelling. In marked contrast, Cl^- induces film dehydration. We conclude that larger anions promote deswelling such that water losses increase with increasing anion valence. Results such as the ones reported here are critical to ongoing efforts designed to dry chitin nanomaterials and develop bio-based and sustainable materials, including particles, films, coatings, and other nanostructured assemblies, for various devices and applications.