Control of the Colloidal and Adsorption Behaviors of Chitin Nanocrystals and an Oppositely Charged Surfactant at Solid, Liquid, and Gas Interfaces.

Chitin has a unique hierarchical structure, spanning the macro- and nanoscales, and presents chemical characteristics that make it a suitable component of multiphase systems. Herein, we elucidate the colloidal interactions between partially deacetylated chitin nanocrystals (cationic ChNC) and an anionic surfactant, sodium dodecyl sulfate (SDS). We investigate charge neutralization and association (electrophoretic mobility, surface tensiometry, and quartz crystal microgravimetry) and their role in the stabilization of Pickering emulsions. We find SDS adsorption and association with ChNC under distinctive regimes: At low SDS concentration, submonolayer assemblies form on ChNC, driven by the hydrophobic effect and electrostatic interactions. With the increased SDS concentration, bilayers or patchy bilayers form, followed by adsorbed hemimicelles and micelles. We further suggested the role of hydrophobic effects in the observed colloidal transitions and complex conformations. At the highest SDS concentration tested, charge neutralization and SDS/ChNC flocculation take place. Remarkably, at given concentrations, adsorbed SDS endows the chitin nanoparticles with an effective hydrophobicity that opens the opportunity to achieve tailorable Pickering stabilization. Hence, a facile route is proposed by in situ modification by SDS physisorption, which extends the potential of renewable nanoparticles in the formulation of complex fluids, for instance, those relevant to household and healthcare products.

Insulative Biobased Glaze from Wood Laminates Obtained by Self-Adhesion.

The combination of optical transparency and mechanical strength is a highly desirable attribute of wood-based glazing materials. However, such properties are typically obtained by impregnation of the highly anisotropic wood with index-matching fossil-based polymers. In addition, the presence of hydrophilic cellulose leads to a limited water resistance. Herein, this work reports on an adhesive-free lamination that uses oxidation and densification to produce transparent all-biobased glazes. The latter are produced from multilayered structures, free of adhesives or filling polymers, simultaneously displaying high optical clarity and mechanical strength, in both dry and wet conditions. Specifically, high values of optical transmittance (≈85.4%), clarity (≈20% with low haze) at a thickness of ≈0.3 mm, and highly isotropic mechanical strength and water resistance (wet strength of ≈128.25 MPa) are obtained for insulative glazes exhibiting low thermal conductivity (0.27 W m-1 K-1 , almost four times lower than glass). The proposed strategy results in materials that are systematically tested, with the leading effects of self-adhesion induced by oxidation rationalized by ab initio molecular dynamics simulation. Overall, this work demonstrates wood-derived materials as promising solutions for energy-efficient and sustainable glazing applications.

Super-Macroporous Lightweight Materials Templated from Bicontinuous Intra-Phase Jammed Emulsion Gels Based on Nanochitin.

Non-equilibrium multiphase systems are formed by mixing two immiscible nanoparticle dispersions, leading to bicontinuous emulsions that template cryogels with interconnected, tortuous channels. Herein, a renewable, rod-like biocolloid (chitin nanocrystals, ChNC) is used to kinetically arrest bicontinuous morphologies. Specifically, it is found that ChNC stabilizes intra-phase jammed bicontinuous systems at an ultra-low particle concentration (as low as 0.6 wt.%), leading to tailorable morphologies. The synergistic effects of ChNC high aspect ratio, intrinsic stiffness, and interparticle interactions produce hydrogelation and, upon drying, lead to open channels bearing dual characteristic sizes, suitably integrated into robust bicontinuous ultra-lightweight solids. Overall, it demonstrates the successful formation of ChNC-jammed bicontinuous emulsions and a facile emulsion templating route to synthesize chitin cryogels that form unique super-macroporous networks.

Toward Strong and Tough Wood-Based Hydrogels for Sensors.

The purpose of this research is to develop strong and tough wood-based hydrogels, which are reinforced by an aligned cellulosic wood skeleton. The hypothesis is that improved interfacial interaction between the wood cell wall and a polymer is of great importance for improving the mechanical performance. To this end, a facile and green approach, called ultraviolet (UV) grafting, was performed on the polyacrylamide (PAM)-infiltrated wood skeleton without using initiators. An important finding was that PAM-grafted cellulose nanofiber (CNF) architectures formed in the obtained hydrogels under UV irradiation, where CNFs themselves serve as both initiators and cross-linkers. Moreover, an alkali swelling treatment was utilized to improve the accessibility of the wood cell wall before UV irradiation and thus facilitate grafting efficiency. The resulting alkali-treated Wood-g-PAM hydrogels exhibited significantly higher tensile properties than those of the Wood/PAM hydrogel and were further assembled into conductive devices for sensor applications. We believe that this UV grafting strategy may facilitate the development of strong wood-based composites with interesting features.

Antimicrobial/Biocompatible Hydrogels Dual-Reinforced by Cellulose as Ultrastretchable and Rapid Self-Healing Wound Dressing.

Hydrogels as a wound dressing, integrated with ultrastretchability, rapid self-healing, and excellent antimicrobial activity, are in high demand, particularly for joint skin wound healing. Herein, a multifunctional and ductile composite hydrogel was developed using poly(vinyl alcohol) (PVA)-borax gel as a matrix that was synergized or dual-reinforced with dopamine-grafted oxidized carboxymethyl cellulose (OCMC-DA) and cellulose nanofibers (CNF). Moreover, neomycin (NEO), an aminoglycoside antibiotic with multifunctional groups, was incorporated into the hydrogel network as both an antibacterial agent and a cross-linker. The dynamic reversible borate ester linkages and hydrogen bonds between OCMC-DA, PVA, and CNF, along with dynamic cross-linking imine linkages between NEO and OCMC-DA, endowed the hydrogel with excellent self-healing ability and stretchability (3300%). The as-reinforced networks enhanced the mechanical properties of hydrogels significantly. More remarkably, the composite hydrogel with improved biodegradability and biocompatibility is pH-responsive and effective against a broad spectrum of bacteria, which is attributed to the controllable release of NEO for steady availability of the antibiotic on the wound location. Overall, the antimicrobial hydrogel with rapid self-healing and reliable mechanical properties holds significant promise as dressing material for wound healing.

Solid Wood Modification toward Anisotropic Elastic and Insulative Foam-Like Materials.

The methods used to date to produce compressible wood foam by top-down approaches generally involve the removal of lignin and hemicelluloses. Herein, we introduce a route to convert solid wood into a super elastic and insulative foam-like material. The process uses sequential oxidation and reduction with partial removal of lignin but high hemicellulose retention (process yield of 72.8%), revealing fibril nanostructures from the wood's cell walls. The elasticity of the material is shown to result from a lamellar structure, which provides reversible shape recovery along the transverse direction at compression strains of up to 60% with no significant axial deformation. The compressibility is readily modulated by the oxidation degree, which changes the crystallinity and mobility of the solid phase around the lumina. The performance of the highly resilient foam-like material is also ascribed to the amorphization of cellulosic fibrils, confirmed by experimental and computational (molecular dynamics) methods that highlight the role of secondary interactions. The foam-like wood is optionally hydrophobized by chemical vapor deposition of short-chained organosilanes, which also provides flame retardancy. Overall, we introduce a foam-like material derived from wood based on multifunctional nanostructures (anisotropically compressible, thermally insulative, hydrophobic, and flame retardant) that are relevant to cushioning, protection, and packaging.

Chitin Nanofibers Enable the Colloidal Dispersion of Carbon Nanomaterials in Aqueous Phase and Hybrid Material Coassembly.

Chitin nanofibrils (ChNF) sourced from discarded marine biomass are shown as effective stabilizers of carbon nanomaterials in aqueous media. Such stabilization is evaluated for carbon nanotubes (CNT) considering spatial and temporal perspectives by using experimental (small-angle X-ray scattering, among others) and theoretical (atomistic simulation) approaches. We reveal that the coassembly of ChNF and CNT is governed by hydrophobic interactions, while electrostatic repulsion drives the colloidal stabilization of the hybrid ChNF/CNT system. Related effects are found to be transferable to multiwalled carbon nanotubes and graphene nanosheets. The observations explain the functionality of hybrid membranes obtained by aqueous phase processing, which benefit from an excellent areal mass distribution (correlated to piezoresistivity), also contributing to high electromechanical performance. The water resistance and flexibility of the ChNF/CNT membranes (along with its tensile strength at break of 190 MPa, conductivity of up to 426 S/cm, and piezoresistivity and light absorption properties) are conveniently combined in a device demonstration, a sunlight water evaporator. The latter is shown to present a high evaporation rate (as high as 1.425 kg water m-2 h-1 under one sun illumination) and recyclability.

One-pot complexation of phytic acid and polyethyleneimine on cellulosic microfibers towards insulative and flame-resistant foam.

Flame resistance is required for the deployment of bio-based materials, especially those forming cellular structures that endow thermal insulation. This study proposes a one-pot strategy to prepare cellular lignocellulosic composites with excellent flame resistance. Lignocellulosic microfibers were used as the substrate onto which a flame-retardant complex consisting of P-containing phytic acid (PA) and N-containing polyethyleneimine (PEI) was formed. Following the prediction of ab initio molecular dynamics simulation, PA and PEI are integrated onto MF-CTMP following a single-step complexation assembly triggered by pH effects. The PA-PEI modified MF-CTMP can be readily transformed into a composite solid foam by dewatering a wet foam followed by oven drying. At the expense of a slightly reduced thermal insulation (thermal conductivity increase from 33.6 ± 0.6 to 40.0 ± 0.6 mW/(m·K)) the presence of PA-PEI complexes significantly improved the mechanical performance of the foam and uniquely endows it with flame resistance. Compared to unmodified MF-CTMP foams, the composite foams showed significant improvement in the Young's, specific compression, and flexural moduli (increased by 13.5, 5.5, and 7.3 folds, respectively), a high oxygen index (up to 40.8 %) and self-extinguishing effects. The results suggest the suitability of the introduced lignocellulosic foam as an alternative to traditional synthetic polymer-based counterparts as well as inorganic matter for insulation, particularly relevant to the building sector.

Efficient ultraviolet blocking film on the lignin-rich lignocellulosic nanofibril from bamboo.

The ultraviolet (UV) blocking performance of current bio-based devices is always limited by delignification and exploited chemical treatment. Lignocellulosic nanofibril (LCNF) is a promising green alternative that could efficiently impede UV radiation. Herein, we proposed a robust LCNF film that achieved 99.8 ± 0.19 % UVB blocking, 96.1 ± 0.23 % UVA blocking, and was highly transparent without complex chemical modification. Compared to conventional lignin composites, this LCNF method involves 29.5 ± 2.31 % lignin content directly extracted from bamboo as a broad-spectrum sun blocker. This bamboo-based LCNF film revealed an excellent tensile strength of 94.9 ± 3.6 MPa and outstanding stability, adapting to the natural environment's variability. The residual hemicellulose could also embed the link between lignin and cellulose, confirming high lignin content in the network. The connection between lignin and hemicelluloses in the cellulose network was explored and described for the fibrillation of lignocellulosic nanofibrils. This research highlights the promising development of LCNFs for UV protection and bio-based solar absorption materials.

Structured Emulgels by Interfacial Assembly of Terpenes and Nanochitin.

Interfacial assemblies formed by colloidal complexation are effective in multiphase stabilization, as shown in structured liquids and Pickering emulgels. Herein, we demonstrate a type of biobased colloidal system that spontaneously stabilizes an organic phase in a continuous hydrogel phase. Specifically, a triterpene extracted from bark (betulin, BE) is added to an organic phase containing a coniferous resin (rosin acid, a diterpene). BE is shown to take part in strong noncovalent interactions with the nanochitin dispersed in the aqueous (hydrogel) phase, leading to a complex of high interfacial activity. The viscoelastic response of the system is rationalized by the presence of a superstable structured dual network. When used as a templating material, the emulgel develops into structured liquids and cryogels. The herein introduced all-biobased type of nanoparticle surfactant system forms a gel ("emulsion-filled" with "aggregated droplets") that features the functional benefits of both betulin and nanochitin.