Guanidinylated nanochitins: guanidinylated chitin nanocrystals are dispersible at neutral pH

Abstract

Despite nanochitins showing favorable biological effects, the colloid stability of positively charged nanochitins by virtue of the amino group is limited to acidic pH, which is different from biological conditions. Here, we show that guanidinylated chitin nanocrystals (GChNCs) are dispersible at neutral pH. The GChNCs are prepared by guanidinylation of partially deacetylated chitin nanocrystals (ChNCs) with 1-amidinopyrazole hydrochloride. The degrees of guanidinylation and acetylation of the GChNCs are 4.6% and 75.7%, respectively. A 1.0 wt% GChNC dispersion is prepared with 0.5 wt% acetic acid solution by sonication treatment. Although slight white turbidity is observed due to scattering, no visible macroscopic precipitates are observed. The average diameter of the GChNCs estimated by DLS analysis is 327.2 nm. When the GChNC dispersion is neutralized by adding 0.1 M NaOH solution, the transmittance of the GChNC dispersion is decreased by aggregation. However, the transmittance of the GChNC dispersion is higher than that of the ChNC dispersion, suggesting that the GChNC particles are less aggregated than the ChNC particles due to the positive charge by virtue of the high basicity of the guanidino group. Interestingly, we find that the GChNCs homogeneously disperse in 0.1 M HEPES buffer (pH 7.4) up to 0.5 wt% by sonication treatment, even though the average diameter of the GChNCs in the solution is 3.4-fold higher (1115.1 nm) than that prepared at pH 3.0. We additionally find no observation of this improved dispersibility of guanidinylated chitin nanofibers due to the guanidino group. This result indicates that the guanidinylation is effective in improving the dispersion of nanochitins with smaller aspect ratios, like ChNCs. Furthermore, we demonstrate that the dispersibility of GChNCs at neutral pH can be utilized for material development, where a gelatin–GChNF composite hydrogel displaying enhanced mechanical properties is successfully prepared by adding 10% (w/w) GChNCs.