Chitosan nanocoatings N-acylated with decanoic anhydride: Hydrophobic, hygroscopic and structural properties.

Thin (ca. 340 nm) chitosan coatings were deposited onto glass substrates via dip-coating, then modified with the methanol solution of decanoic anhydride (0.17-56 mM). NMR, FTIR and XPS measurements confirmed that the acylation degree increased from 18 % to 45 %, and at the highest degree, the whole layer was acylated homogeneously by the reagent molecules. The coating thickness increased (up to 60 %), and the refractive index decreased (from 1.541 to 1.532) due to the acylation, that was determined by UV-visible spectroscopy. The AFM did not reveal morphological changes, but wetting tests showed that the acylation rendered the coating hydrophobic (water contact angle increased from ca. 75° to 100°). The contact angle, however, decreased to 85° due to the development of a second molecular layer of the decanoic acid by-product at the highest (over 25 mM) reagent concentrations. XRD studies showed a self-assembling structuring of the alkyl-chains in the bulk phase, which occurred in the case of the highest degree of acylation. This also manifested itself in a significant decrease of the layer hygroscopicity: the swelling degree decreased from 40 % to 8 % in a saturated water atmosphere monitored by spectroscopic ellipsometry.