Thermoplastic Starch Biocomposite Films Reinforced with Nanocellulose from Agave tequilana Weber var. Azul Bagasse.

In this work, cellulose nanocrystals (CNCs), bleached cellulose nanofibers (bCNFs), and unbleached cellulose nanofibers (ubCNFs) isolated by acid hydrolysis from Agave tequilana Weber var. Azul bagasse, an agro-waste from the tequila industry, were used as reinforcements in a thermoplastic starch matrix to obtain environmentally friendly materials that can substitute contaminant polymers. A robust characterization of starting materials and biocomposites was carried out. Biocomposite mechanical, thermal, and antibacterial properties were evaluated, as well as color, crystallinity, morphology, rugosity, lateral texture, electrical conductivity, chemical identity, solubility, and water vapor permeability. Pulp fibers and nanocelluloses were analyzed via SEM, TEM, and AFM. The water vapor permeability (WVP) decreased by up to 20.69% with the presence of CNCs. The solubility decreases with the presence of CNFs and CNCs. The addition of CNCs and CNFs increased the tensile strength and Young's modulus and decreased the elongation at break. Biocomposites prepared with ubCNF showed the best tensile mechanical properties due to a better adhesion with the matrix. Images of bCNF-based biocomposites demonstrated that bCNFs are good reinforcing agents as the fibers were dispersed within the starch film and embedded within the matrix. Roughness increased with CNF content and decreased with CNC content. Films with CNCs did not show bacterial growth for Staphylococcus aureus and Escherichia coli. This study offers a new theoretical basis since it demonstrates that different proportions of bleached or unbleached nanofibers and nanocrystals can improve the properties of starch films.

Facile Photochemical Modification of Silk Protein-Based Biomaterials.

Silk protein-based materials show promise for application as biomaterials for tissue engineering. The simple and rapid photochemical modification of silk protein-based materials composed of either Bombyx mori silkworm silk or engineered spider silk proteins (eADF4(C16)) is reported. Radicals formed on the silk-based materials initiate the polymerization of monomers (acrylic acid, methacrylic acid, or allylamine) which functionalize the surface of the silk materials with poly(acrylic acid) (PAA), poly(methacrylic acid) (PMAA), or poly(allylamine) (PAAm). To demonstrate potential applications of this type of modification, the polymer-modified silks are mineralized. The PAA- and PMAA-functionalized silks are mineralized with calcium carbonate, whereas the PAAm-functionalized silks are mineralized with silica, both of which provide a coating on the materials that may be useful for bone tissue engineering, which will be the subject of future investigations.

Study of green nanocomposites based on corn starch and cellulose nanofibrils from Agave tequilana Weber.

Global environmental pollution issues caused by synthetic materials and the lack of practical utilization of the local industrial lignocellulosic waste, force Mexican researchers to produce new biobased sustainable materials that use industrial waste as a source of components. Herein, we show the preparation and characterization of environmentally friendly starch-based nanocomposites reinforced with cellulose nanofibrils (CNF) extracted from Agave tequilana Weber. Tensile, bending and impact mechanical properties of dried and hydrated nanocomposites were studied. Moreover, the water absorption capacity of the nanocomposites were measured and evaluated. The mechanical properties improved because of the presence of a small amount of CNF (1 wt%). This work demonstrates the importance of the addition of a natural biomodifier in a starch matrix to achieve better mechanical properties. Most importantly, this study highlights that lignocellulosic waste from the tequila industry can have a practical application, which is being a source of natural nanoreinforcements for preparation of all-biobased sustainable materials.

Cellulose Nanofibril Hydrogel Tubes as Sacrificial Templates for Freestanding Tubular Cell Constructs.

The merging of defined nanoscale building blocks with advanced additive manufacturing techniques is of eminent importance for the preparation of multiscale and highly functional materials with de novo designed hierarchical architectures. Here, we demonstrate that hydrogels of cellulose nanofibrils (CNF) can be processed into complex shapes, and used as a sacrificial template to prepare freestanding cell constructs. We showcase our approach for the fabrication of hollow fibers using a controlled extrusion through a circular die into a coagulation bath. The dimensions of the hollow fibers are tunable, and the final tubes combine the nanofibrillar porosity of the CNF hydrogel with a submillimeter wall thickness and centimeter-scale length provided by the additive manufacturing technique. We demonstrate that covalent and supramolecular cross-linking of the CNFs can be used to tailor the mechanical properties of the hydrogel tubes within 1 order of magnitude and in an attractive range for the mechanosensation of cells. The resulting tubes are highly biocompatible and allow for the growth of mouse fibroblasts into confluent cell layers in their inner lumen. A detailed screening of several cellulases enables degradation of the scaffolding, temporary CNF hydrogel tube in a quick and highly cell-friendly way, and allows the isolation of coherent cell tubes. We foresee that the growing capabilities of hydrogel printing techniques in combination with the attractive features of CNFs-sustainable, globally abundant, biocompatible and enzymatically degradable-will allow making plant-based biomaterials with hierarchical structures and on-demand degradation useful, for instance, to engineer complex tissue structures to replace animal models, and for implants.

Biomineralization of Engineered Spider Silk Protein-Based Composite Materials for Bone Tissue Engineering.

Materials based on biodegradable polyesters, such as poly(butylene terephthalate) (PBT) or poly(butylene terephthalate-co-poly(alkylene glycol) terephthalate) (PBTAT), have potential application as pro-regenerative scaffolds for bone tissue engineering. Herein, the preparation of films composed of PBT or PBTAT and an engineered spider silk protein, (eADF4(C16)), that displays multiple carboxylic acid moieties capable of binding calcium ions and facilitating their biomineralization with calcium carbonate or calcium phosphate is reported. Human mesenchymal stem cells cultured on films mineralized with calcium phosphate show enhanced levels of alkaline phosphatase activity suggesting that such composites have potential use for bone tissue engineering.

Bioactive gyroid scaffolds formed by sacrificial templating of nanocellulose and nanochitin hydrogels as instructive platforms for biomimetic tissue engineering.

A sacrificial templating process using lithographically printed minimal surface structures allows complex de novo geo-metries of delicate hydrogel materials. The hydrogel scaffolds based on cellulose and chitin nanofibrils show differences in terms of attachment of human mesenchymal stem cells, and allow their differentiation into osteogenic outcomes. The approach here serves as a first example toward designer hydrogel scaffolds viable for biomimetic tissue engineering.

Aligned bioinspired cellulose nanocrystal-based nanocomposites with synergetic mechanical properties and improved hygromechanical performance.

Natural high-performance materials inspire the pursuit of ordered hard/soft nanocomposite structures at high fractions of reinforcements and with balanced supramolecular interactions. Such biomimetic design principles remain difficult to realize for bulk nanocomposites. Herein, we establish an effective drawing procedure that induces a high orientation of crystalline cellulose nanocrystals (CNCs) in a matrix of carboxymethylcellulose (CMC) at high level of reinforcements (50 vol %). We show such alignment in rather thick bulk films and report synergetic improvement with a simultaneous increase of stiffness, strength, and work-to-fracture as a function of the degree of alignment. Scanning electron microscopy and two-dimensional X-ray diffraction quantify the alignment of the cylindrical nanoparticles and link it to the extent of drawing and improvements in mechanical properties. We further show that the decline in mechanical properties of such waterborne all biobased nanocomposites at high relative humidity can be balanced using supramolecular modulation of the ionic interactions by exchanging the monovalent Na(+) counterion, present in CMC and CNC with di- or trivalent Cu(2+) and Fe(3+). This contribution demonstrates the importance of aligning one-dimensional reinforcements to achieve synergetic improvement in mechanical properties in sustainable bioinspired nanocomposites and suggests pathways to prepare water-stable materials based on a waterborne processing route.

Mechanical performance of macrofibers of cellulose and chitin nanofibrils aligned by wet-stretching: a critical comparison.

Renewable nanofibrillated cellulose (NFC) and nanofibrillated chitin (NFCh) are attractive fibrillar bionanoparticles due to their remarkable properties such as outstanding mechanical stiffness and strength, thermostability, barrier properties, and also for their global availability from renewable resources and food waste. One major bottleneck to maximize the mechanical properties of materials based on these bionanoparticles (e.g., nanopapers and macroscale fibers) is to find pathways to control their direction of alignment and understand how preferred alignment correlates with macroscale properties. Herein, we will demonstrate how strain-rate controlled wet-stretching of rehydrated macroscale fibers composed of nanofibrillated chitin and cellulose (NFCh, NFC) induces a high degree of orientation and how the degree of alignment scales with macroscale mechanical stiffness. We find similar degrees of alignment in both types of nanofibril-based macrofibers, yet substantially different macroscale stiffness, with the NFC-based fibers (E(NFC) = 33 GPa) outperforming the NFCh-based ones (E(NFCh) = 12 GPa) considerably. These differences can be correlated to the mechanical properties of the underlying cellulose I and α-chitin crystals and the degree of crystallinity of the nanofibrils, which both govern the stiffness of an individual nanofibril. Our study likely demonstrates the maximum performance in terms of stiffness of materials prepared by NFC and NFCh and reveals a critical difference in the performance of both classes of bionanoparticles.