Crystalline polysaccharides are useful for important and rapidly growing applications ranging from advanced energy storage, green electronics, and catalyst or enzyme supports to tissue engineering and biological devices. However, the potential value of chitin in such applications is currently neglected because of its poor swellability, reactivity, and solubility in most commonly used solvents. Here, a high-efficiency, energy-saving, and “green” route for the fabrication of extremely strong and transparent chitin films is described in which chitin is dissolved in an aqueous KOH/urea solution and neutralized in aqueous ethanol solution. The neutralization temperature, ethanol concentration, and chitin solution deacetylation time are critical parameters for the self-assembly of chitin chains and for tuning the morphology and aggregate structures of the resulting chitin hydrogels and films. Moreover, the drawing orientation can produce extremely strong and tough chitin films with a tensile strength, Young's modulus, and work of fracture of 226 MPa, 7.2 GPa, and 20.3 MJ m−3, respectively. The method developed here should contribute to the utilization of seafood waste and, thereby, to the sustainable use of marine resources.

TiO2/cellulose composite aerogels were easily fabricated by the in situ synthesis of TiO2 nanoparticles in a cellulose matrix at a mild temperature (≤80 °C). The TiO2/cellulose aerogel structure and morphology were analyzed with scanning electron microscopy, transmission electron microscopy, X-ray diffraction, thermal gravimetric analysis, and nitrogen adsorption–desorption tests as well as tensile testing. The results revealed that the TiO2 content in the composite aerogels increased dramatically with an increase of the treating times in tetrabutyl titanate to achieve a value of 65 wt%, which was much higher than that in literatures. Depending on the number of hydrolysis cycles, the mean diameter of the TiO2 nanoparticles was controlled to be approximately from 1.5 ± 1.0 to 3.5 ± 2.0 nm. The TiO2/cellulose nanocomposite aerogel exhibited excellent mechanical strength, good UV screening ability as well as highly efficient photo-catalytic activity under weak UV light irradiation. This work opens a new avenue to construct TiO2/cellulose aerogels with a high content and small size of TiO2 nanoparticles, thus demonstrating potential applications in the fields of UV screening and catalyst.

Most hydrogels involve synthetic polymers and organic cross-linkers that cannot simultaneously fulfill the mechanical and cell-compatibility requirements of biomedical applications. We prepared a new type of chitosan physical hydrogel with various degrees of deacetylation (DDs) via the heterogeneous deacetylation of nanoporous chitin hydrogels under mild conditions. The DD of the chitosan physical hydrogels ranged from 56 to 99%, and the hydrogels were transparent and mechanically strong because of the extra intra- and intermolecular hydrogen bonding interactions between the amino and hydroxyl groups on the nearby chitosan nanofibrils. The tensile strength and Young’s modulus of the chitosan physical hydrogels were 3.6 and 7.9 MPa, respectively, for a DD of 56% and increased to 12.1 and 92.0 MPa for a DD of 99% in a swelling equilibrium state. In vitro studies demonstrated that mouse bone mesenchymal stem cells (mBMSCs) cultured on chitosan physical hydrogels had better adhesion and proliferation than those cultured on chitin hydrogels. In particular, the chitosan physical hydrogels promoted the differentiation of the mBMSCs into epidermal cells in vitro. These materials are promising candidates for applications such as stem cell research, cell therapy, and tissue engineering.

Incorporation of nanofillers into aliphatic polyesters is a convenient approach to create new nanomaterials with significantly reinforced mechanical properties compared to the neat polymers or conventional composites. Nanoporous cellulose gels (NCG) prepared from aqueous alkali hydroxide/urea solutions can act as alternative reinforcement nanomaterials for polymers with improved mechanical properties. We report a simple and versatile process for the fabrication of NCG/poly(l-lactide-co-caprolactone) (NCG/P(LLA-co-CL) nanocomposites through in situ ring-opening polymerization of l-lactide (LLA) and ε-caprolactone (ε-CL) monomers in the NCG. The volume fraction of the NCG in the nanocomposites was tunable and ranged from 4.5% to 37%. Fourier transform infrared (FT-IR), X-ray diffraction (XRD), and differential scanning calorimetry (DSC) results indicated that P(LLA-co-CL) were synthesized within the NCG and partially grafted onto the surface of the cellulose nanofibrils. The glass-transition temperature (Tg) of the NCG/P(LLA-co-CL) nanocomposites could be altered by varying the molar ratio of LLA/ε-CL and was affected by the volume fraction of NCG. Atomic force microscopy (AFM) and scanning electron microscopy (SEM) images confirmed that the interconnected nanofibrillar cellulose network structure of the NCG was finely distributed and preserved in the P(LLA-co-CL) matrix after polymerization. The dynamic mechanical analysis (DMA) results showed remarkable reinforcement of the tensile storage modulus (E′) of the P(LLA-co-CL) nanocomposites in the presence of NCG, especially above the Tg of the P(LLA-co-CL). The modified percolation model agreed well with the mechanical properties of the NCG/P(LLA-co-CL) nanocomposites. The introduction of NCG into the P(LLA-co-CL) matrix improved the mechanical properties and thermal stability of the NCG/P(LLA-co-CL) nanocomposites. Moreover, the NCG/P(LLA-co-CL) nanocomposites have tunable biodegradability and biocompatibility and potential applications in tissue engineering repair, biomedical implants, and packing.

Light weight and mechanically strong α-chitin aerogels were fabricated using the sol-gel/self-assembly method from α-chitin in different aqueous alkali hydroxide (KOH, NaOH and LiOH)/urea solutions. All of the α-chitin solutions exhibited temperature-induced rapid gelation behavior. 13C nuclear magnetic resonance (NMR) spectra revealed that the aqueous alkali hydroxide/ urea solutions are non-derivatizing solvents for α-chitin. Fourier transform infrared (FT-IR), X-ray diffraction (XRD) and cross-polarization magic angle spinning (CP/MAS) 13C NMR confirmed that α-chitin has a stable aggregate structure after undergoing dissolution and regeneration. Subsequently, nanostructured α-chitin aerogels were fabricated by regeneration from the chitin solutions in ethanol and then freeze-drying from t-BuOH. These α-chitin aerogels exhibited high porosity (87% to 94%), low density (0.09 to 0.19 g/cm3), high specific surface area (419 to 535 m2/g) and large pore volume (2.7 to 3.8 cm3/g). Moreover, the α-chitin aerogels exhibited good mechanical properties under compression and tension models. In vitro studies showed that mBMSCs cultured on chitin hydrogels have good biocompatibility. These nanostructured α-chitin aerogels may be useful for various applications, such as catalyst supports, carbon aerogel precursors and biomedical materials.

High strength cellulose composite films with antibacterial activities were prepared by dispersing montmorillonites (MMT) into cellulose solution in LiOH/urea aqueous solvent followed by regeneration in ethanol coagulation bath, and then by soaking in 5 wt% hexadecylpyridine bromide ethanol solutions to induce the antibacterial action. The cellulose/MMT composite films were characterized by field emission scanning electron microscopy, transmission electron microscopy, thermogravimetric analysis, FTIR, UV-spectra, wide angle X-ray diffraction and mechanical test. The results revealed that MMT was dispersed well in the cellulose matrix to form layer structure with a thickness of approximately 3 nm. The mechanical properties of the cellulose/MMT composite films were significantly improved to achieve 132 MP for tensile strength as a result of the MMT delamination. The hexadecylpyridine bromide was fixed well in the cellulose/MMT matrix through cation exchange, leading to the excellent antibacterial activities against Staphylococcus aureus and Escherichia coli, which is important in their practical applications.

With the world’s focus on utilization of sustainable natural resources, the conversion of wood and plant fibers into cellulose nanowhiskers/nanofibers is essential for application of cellulose in polymer nanocomposites. Here, we present a novel fabrication method of polymer nanocomposites by in-situ polymerization of monomers in three-dimensionally nanoporous cellulose gels (NCG) prepared from aqueous alkali hydroxide/urea solution. The NCG have interconnected nanofibrillar cellulose network structure, resulting in high mechanical strength and size stability. Polymerization of the monomer gave P(MMA/BMA)/NCG, P(MMA/BA)/NCG nanocomposites with a volume fraction of NCG ranging from 15% to 78%. SEM, TEM, and XRD analyses show that the NCG are finely distributed and preserved well in the nanocomposites after polymerization. DMA analysis demonstrates a significant improvement in tensile storage modulus E′ above the glass transition temperature; for instance, at 95 °C, E′ is increased by over 4 orders of magnitude from 0.03 MPa of the P(MMA/BMA) up to 350 MPa of nanocomposites containing 15% v/v NCG. This reinforcement effect can be explained by the percolation model. The nanocomposites also show remarkable improvement in solvent resistance (swelling ratio of 1.3–2.2 in chloroform, acetone, and toluene), thermal stability (do not melt or decompose up to 300 °C), and low coefficients of thermal expansion (in-plane CTE of 15 ppm·K–1). These nanocomposites will have great promising applications in flexible display, packing, biomedical implants, and many others.Keywords: mechanical properties; nanoporous cellulose gels; polymer nanocomposites; solvent resistance; thermal expansion

Three-dimensionally nanoporous cellulose gels (NCG) were prepared by dissolution and coagulation of cellulose from aqueous alkali hydroxide-urea solution, and used to fabricate NCG/poly(ε-caprolactone) (PCL) nanocomposites by in situ ring-opening polymerization of ε-CL monomer in the NCG. The NCG content of the NCG/PCL nanocomposite could be controlled between 7 and 38% v/v by changing water content of starting hydrogel by compression dewatering. FT-IR and solid-state 13C NMR showed that the grafting of PCL onto cellulose are most likely occurred at the C6-OH groups and the grafting percentage of PCL is 25 wt % for the nanocomposite with 7% v/v NCG. 1H NMR, XRD, and DSC results indicate that the number-average molecular weight and crystal formation of PCL in the nanocomposites are remarkably restricted by the presence of NCG. AFM images confirm that the interconnected nanofibrillar cellulose network structure of NCG are finely distributed and preserved well in the PCL matrix after polymerization. DMA results show remarkable increase in tensile storage modulus of the nanocomposites above glass transition and melting temperatures of the PCL matrix. The percolation model was used to evaluate the mechanical properties of the nanocomposites, in which stress transfer among the interconnected nanofibrillar network is facilitated through strong intermolecular hydrogen bonding and entanglement of cellulose nanofibers.Keywords: bionanocomposites; mechanical properties; nanoporous cellulose gel; percolation model; poly(ε-caprolactone);

•Regulated-photoluminescence cellulose gels are prepared with lanthanide elements.•The color of the luminescence can be modulated.•It has potential applications in the fields of bioimaging and fluoroimmunoassay.In this study cellulose hydrogels with lanthanide ions nanoparticles embedded in were prepared via in situ doping using a low-temperature alkali hydroxide/urea aqueous solution as a cellulose solvent. Depending on the type and relative concentrations of the constituent lanthanide ions, the color of light emission were modulated to generate the three primary colors and other adjusted colors by blending red, green and blue at certain ratios. This work has opened new and convenient pathway to create regulated fluorescent cellulose hydrogels for potential applications in the fields of bioimaging and fluoroimmunoassay.