RESUMO
This study investigates the rheological behavior of two plant-based polysaccharides, with different degrees of hydrophilicity, agar (highly hydrophilic) and guar gum (hydrophilic), in water and 1-ethyl-3-methylimidazolium acetate (EMImAc). The rheological response of these polymers is highly dependent on the solvent's ability to disrupt intermolecular associations. In water, agar forms hydrogels, while guar gum behaves as a viscoelastic liquid with slow modes. The plateau modulus (GN0) scales with polymer concentration (c) as GN0 â¼ c3, consistent with other natural polymers. In EMImAc, both polysaccharides form viscoelastic liquids, exhibiting GN0 â¼ c2.3, as expected for semiflexible polymer solutions. However, the terminal relaxation time, τD, and the specific viscosity, ηsp, scale as τD â¼ c5.3 and ηsp â¼ c7.6, indicative of intermolecular chain-chain associations. Despite the solvent or polysaccharide, the fractional viscosity overshoot and the shear strain at the maximum stress show a terminal Weissenberg number dependence similar to other synthetic polymers.
RESUMO
The addition of water to native cellulose/1-ethyl-3-methylimidazolium acetate solutions catalyzes the formation of gels, where polymer chain-chain intermolecular associations act as cross-links. However, the relationship between water content (Wc), polymer concentration (Cp), and gel strength is still missing. This study provides the fundamentals to design water-induced gels. First, the sol-gel transition occurs exclusively in entangled solutions, while in unentangled ones, intramolecular associations hamper interchain cross-linking, preventing the gel formation. In entangled systems, the addition of water has a dual impact: at low water concentrations, the gel modulus is water-independent and controlled by entanglements. As water increases, more cross-links per chain than entanglements emerge, causing the modulus of the gel to scale as Gp â¼ Cp2Wc3.0±0.2. Immersing the solutions in water yields hydrogels with noncrystalline, aggregate-rich structures. Such water-ionic liquid exchange is examined via Raman, FTIR, and WAXS. Our findings provide avenues for designing biogels with desired rheological properties.
RESUMO
Complex coacervates make up a class of versatile materials formed as a result of the electrostatic associations between oppositely charged polyelectrolytes. It is well-known that the viscoelastic properties of these materials can be easily altered with the ionic strength of the medium, resulting in a range of materials from free-flowing liquids to gel-like solids. However, in addition to electrostatics, several other noncovalent interactions could influence the formation of the coacervate phase depending on the chemical nature of the polymers involved. Here, the importance of intermolecular hydrogen bonds on the phase behavior, microstructure, and viscoelasticity of hyaluronic acid (HA)-chitosan (CHI) complex coacervates is revealed. The density of intermolecular hydrogen bonds between CHI units increases with increasing pH of coacervation, which results in dynamically arrested regions within the complex coacervate, leading to elastic gel-like behavior. This pH-dependent behavior may be very relevant for the controlled solidification of complex coacervates and thus for polyelectrolyte material design.