Xyloglucan-cellulose nanocrystal-chitosan double network hydrogels for soft actuators.

Hydrogels are materials consisting in a three-dimensional hydrophilic polymer network swollen by a large amount of water. An efficient strategy to elaborate hydrogels consists in establishing double polymer networks in order to achieve high strengthening effect associated with other properties such as transparency or tailored swelling capacities. In this work, we prepared cellulose nanocrystals (CNC)-based hydrogels with double network architecture. The first network, formed by CNC and xyloglucan (XG), takes advantage of entropic adsorption of XG on the CNC surface while the second network relies on electrostatic interactions between cationic Chitosan (Chi) and anionic CNC. Hydrogels with different compositions were successfully prepared. Their rheological properties, stability and swelling capacities in acidic and alkaline solutions were evaluated. Internal organizations of hydrogels were investigated by fluorescence microscopy after polymer labelling and polarized optical microscopy (POM). Finally, hydrogels demonstrated excellent mechanical properties and tuneable swelling capacities that can be leveraged for the implementation of bilayer actuators. Therefore, we further prepared films composed of two hydrogels layers, each one containing a different XG/CNC ratio. Bilayered films bended in water due to the asymmetric swelling of layers and the extent of bending can be modulated by the XG/CNC ratio.

Cellulose Nanofibrils/Xyloglucan Bio-Based Aerogels with Shape Recovery.

Bio-based aerogels containing cellulose nanofibrils (CNFs) are promising materials due to the inherent physical properties of CNF. The high affinity of cellulose to plant hemicelluloses (xyloglucan, xylan, pectin) is also an opportunity to develop biomaterials with new properties. Here, we prepared aerogels from gelled dispersions of CNFs and xyloglucan (XG) at different ratios by using a freeze-casting procedure in unidirectional (UD) and non-directional (ND) manners. As showed by rheology analysis, CNF and CNF/XG dispersions behave as true gels. We investigated the impact of the freezing procedure and the gel's composition on the microstructure and the water absorption properties. The introduction of XG greatly affects the microstructure of the aerogel from lamellar to cellular morphology. Bio-based aerogels showed high water absorption capacity with shape recovery after compression. The relation between morphology and aerogel compositions is discussed.

Bioinspired Thermoresponsive Xyloglucan-Cellulose Nanocrystal Hydrogels.

Thermoresponsive hydrogels present unique properties, such as tunable mechanical performance or changes in volume, which make them attractive for applications including wound healing dressings, drug delivery vehicles, and implants, among others. This work reports the implementation of bioinspired thermoresponsive hydrogels composed of xyloglucan (XG) and cellulose nanocrystals (CNCs). Starting from tamarind seed XG (XGt), thermoresponsive XG was obtained by enzymatic degalactosylation (DG-XG), which reduced the galactose residue content by ∼50% and imparted a reversible thermal transition. XG with native composition and comparable molar mass to DG-XG was produced by an ultrasonication treatment (XGu) for a direct comparison of behavior. The hydrogels were prepared by simple mixing of DG-XG or XGu with CNCs in water. Phase diagrams were established to identify the ratios of DG-XG or XGu to CNCs that yielded a viscous liquid, a phase-separated mixture, a simple gel, or a thermoresponsive gel. Gelation occurred at a DG-XG or XGu to CNC ratio higher than that needed for the full surface coverage of CNCs and required relatively high overall concentrations of both components (tested concentrations up to 20 g/L XG and 30 g/L CNCs). This is likely a result of the increase in effective hydrodynamic volume of CNCs due to the formation of XG-CNC complexes. Investigation of the adsorption behavior indicated that DG-XG formed a more rigid layer on CNCs compared to XGu. Rheological properties of the hydrogels were characterized, and a reversible thermal transition was found for DG-XG/CNC gels at 35 °C. This thermoresponsive behavior provides opportunities to apply this system widely, especially in the biomedical field, where the mechanical properties could be further tuned by adjusting the CNC content.

Influence of arabinoxylan on the drying of cellulose nanocrystals suspension: From coffee ring to Maltese cross pattern and application to enzymatic detection.

Evaporation of sessile droplet containing suspension of cellulose nanocrystals (CNC) results on birefringent coffee ring pattern (CR), due to the concentration increase and self-assembly of CNC carried by the flow at the edge of evaporating droplet. In this work, we studied the apparition of Maltese cross pattern, (MC) after addition of an hydrosoluble biopolymer belonging to the hemicellulose family, i.e. arabinoxylan (AX). To investigate the mechanisms that control MC pattern apparition, distribution of the two components inside the dried droplet was investigated using FTIR. CNC and AX were found to be homogenously deposited and CNC self-assembly induces nanoparticles orientation in the CR deposit. We demonstrate that the increase of concentration during drying induces gelation of CNC/AX mixture leading to MC pattern apparition. We take advantage of the apparition of MC pattern to develop a novel catalytic activity detection assay based on the variation of viscosity. Indeed, addition of Endo-1,4-ß-Xylanase (Xyl) addition to a suspension containing CNC/AX complex leads to hydrolysis of AX that decrease in droplet viscosity leading to MC disappearance. The enzymatic detection assay is thus simple, easy to handle, fast, sensitive and do not require complex analytical devices.

Arabinoxylan/Cellulose Nanocrystal Hydrogels with Tunable Mechanical Properties.

Hydrogels are three-dimensional networks of hydro-soluble polymers containing a large amount of water that have found a wide panel of applications in many sectors. The need for eco-friendly and nontoxic materials for the elaboration of sustainable hydrogels is obvious, and materials derived from biomass can easily meet these requirements. Cellulose nanocrystals (CNC) and arabinoxylans (AX) are abundant, biobased, hydrophilic, and renewable nanoparticles and polymers that interact together. In this study, we have built fully biobased hydrogels using CNC and AX. First, as revealed by Quartz Crystal Microbalance with Dissipation (QCM-D) experiments, AX adsorbs almost instantly on cellulosic surfaces in an irreversible manner. Nevertheless, gelation kinetics is not instantaneous and shows temperature dependence. The determination of phase diagrams using the inverted tube method leads to the conclusion that high AX/CNC ratios are needed for gel formation. The mechanical properties of CNC-AX hydrogels were investigated by measuring storage and loss moduli (G', G'') as a function of concentrations and hydrogel reformation after submission to high shear rates. Hydrogel properties were also tuned by increasing the ionic strength and the enzymatic removal of arabinose moieties from AX. In light of the obtained results, we hypothesize that gel formation occurs in two steps, i.e., AX adsorption followed by gelation of the complexes, and is due to the formation of reversible and tunable interactions between CNC/AX complexes interacting with each other, offering a wide panel of physicochemical tools to tune and trigger the final properties of hydrogels.

Structural, Viscoelastic, and Electrochemical Characteristics of Self-Assembled Amphiphilic Comblike Copolymers in Aqueous Solutions.

Self-assembly in aqueous solutions of an amphiphilic comblike polyelectrolyte (80C12) that consists of a polystyrene (PS) backbone onto which quaternary ammonium pendant moieties have been grafted has been investigated by light scattering and cryo-transmission electron microscopy measurements in the presence of KCl and methylviologen dication (MV2+) under conditions mimicking those for electrochemical measurements. Polymer chains self-assemble within branched cylindrical micelles that display viscoelastic properties, characterized by a relaxation time of 4 s. To tune this time, 80C12 was mixed with a polyoxyethylene nonionic surfactant (Brij C12E10). Relatively increasing the amount of the latter leads to a decrease in the relaxation time of the 80C12 solution. Correlatively, electrochemical experiments with a rotating disk electrode show a transition of the mass transport rate, which deviates from the classical Newtonian behavior in the same velocity domain. This result generalizes what has been already observed with solutions of linear polymers of high molecular weight and wormlike micelles based on surfactants subjected to elongational deformations. Moreover, the critical times derived from rheological and electrochemical experiments display the same trend.