Gum Arabic induced assembly of cellulose nanocrystals in aqueous media

Entropy-driven assembly of nematic liquid-crystal phases of cellulose nanocrystals (SCNCs) in aqueous suspensions results in the emergence of a cholesteric liquid crystalline phase (N* phase). We report that a solvated, non-adsorbing, highly branched natural polysaccharide, Gum Arabic (GA), strongly affects the assembly of the SCNCs and modifies the phase diagram: GA leads to significant crowding of the SCNC rods and induces a new liquid-liquid phase transition, where SCNC-rich and GA-rich droplets coexist. The solvated GA does not induce coagulation or gelation of the suspended SCNCs (at low concentrations of 1-3 wt% of GA). In the SCNC-rich droplets, finite-sized nematic nano-islands assemble and further evolve into cholesteric tactoids and nucleate the formation of the N* phase at significantly lower concentration (about 1.5 wt%) than in GA-free suspensions. We observe that the inter-particle distance and the chiral pitch of the N* phase are determined by the concentration of GA (for a given SCNC concentration). The resulting mesophases are characterized via transmission electron microscopy at cryogenic temperatures (cryo-TEM), small-angle X-ray scattering (SAXS), and polarized optical microscopy (POM). Our findings indicate that GA can be used to tune the phase diagram and optical properties of SCNC suspensions, and overcome kinetic barriers that lead to gelation or kinetic arrest.