Designing antimicrobial biomembranes via clustering amino-modified cellulose nanocrystals on silk fibroin ß-sheets.

The continuous rising of infections caused by multidrug-resistant pathogens is becoming a global healthcare concern. Developing new bio-based materials with unique chemical and structural features that allow efficient interaction with bacteria is thus important for fighting this phenomenon. To address this issue, we report an antimicrobial biomaterial that results from clustering local facial amphiphilicity from amino-modified cellulose on silk fibroin ß-sheets, by simply blending the two components through casting technology. A simple but effective method for creating a membrane that is antibacterial and non-cytotoxic. Amino-modified cellulose nanocrystals (CNC-NH2) were mixed with proteinaceous silk fibroin (SF) which resulted in a material with improved crystallinity, higher ß-sheet content, and exposed amino-groups at its surface features, proven by Fourier transform infrared (FTIR) spectroscopy and X-ray photoelectron spectroscopy (XPS), that does not occur when the components are individually assembled. The resulting material possesses important antibacterial activity inducing >3 CFU log10 reduction of Escherichia coli and Staphylococcus epidermidis, while the pristine membranes show no antibacterial effect. The chemical interactions occurring between SF and CNC-NH2 during casting, exposing the amino moieties at the surface of the material, are proposed as the main reason for this antimicrobial activity. Importantly, the membranes are non-cytotoxic, showing their potential to be used as a new bioinspired material with intrinsic antibacterial activity for biomedical applications. Those may include coatings for medical devices for the control of healthcare-associated infections, with no need for including external antimicrobial agents in the material.

Core-Shell Fe3O4@Au Nanorod-Loaded Gels for Tunable and Anisotropic Magneto- and Photothermia.

Hyperthermia therapeutic treatments require improved multifunctional materials with tunable synergetic properties. Here, we report on the synthesis of Fe3O4@Au core-shell nanorods and their subsequent incorporation into an agarose hydrogel to obtain anisotropic magnetic and optical properties for magneto- and photothermal anisotropic transductions. Highly monodisperse ferrimagnetic Fe3O4 nanorods with tunable size were synthesized using a solvothermal method by varying the amount of hexadecylamine capping ligands. A gold shell was coated onto Fe3O4 nanorods by the intermediate formation of core-satellite structures and a subsequent controlled growth process, leading to an optical response variation from the visible to the near-infrared (NIR) region. The nanorods were oriented within an agarose hydrogel to fabricate free-standing anisotropic materials, providing a proof-of-concept for the applicability of these materials for anisotropic magneto- and photothermia applications. The strong gelling behavior upon cooling and shear-thinning behavior of agarose enable the fabrication of magnetically active continuous hydrogel filaments upon injection. These developed multifunctional nanohybrid materials represent a base for advanced sensing, biomedical, or actuator applications with an anisotropic response.

Cellulose Nanocrystal and Water-Soluble Cellulose Derivative Based Electromechanical Bending Actuators.

This study reports a versatile method for the development of cellulose nanocrystals (CNCs) and water-soluble cellulose derivatives (methyl cellulose (MC), hydroxypropyl cellulose (HPC), and sodium carboxymethyl cellulose (NaCMC)) films comprising the ionic liquid (IL) 2-hydroxy-ethyl-trimethylammonium dihydrogen phosphate ([Ch][DHP]) for actuator fabrication. The influence of the IL content on the morphology and physico-chemical properties of free-standing composite films was evaluated. Independently of the cellulose derivative, the ductility of the films increases upon [Ch][DHP] incorporation to yield elongation at break values of nearly 15%. An increase on the electrical conductivity as a result of the IL incorporation into cellulosic matrices is found. The actuator performance of composites was evaluated, NaCMC/[Ch][DHP] showing the maximum displacement along the x-axis of 9 mm at 8 Vpp. Based on the obtained high electromechanical actuation performance, together with their simple processability and renewable nature, the materials fabricated here represent a step forward in the development of sustainable soft actuators of high practical relevance.

Combining cobalt ferrite and graphite with cellulose nanocrystals for magnetically active and electrically conducting mesoporous nanohybrids.

Free-standing mesoporous membranes based on cellulose nanocrystals (CNCs) are fabricated upon the incorporation of cobalt ferrite (CoFe2O4) and graphite nanoparticles at concentrations up to 20 wt % through a soft-templating process. Scanning electron microscopy (SEM) and N2 adsorption-desorption isotherms reveal the development of highly-porous interconnected random 3D structure with surface areas up to 193.9 m2 g-1. Thermogravimetric analysis (TGA) shows an enhanced thermal stability thanks to the formation of a tortuous network limiting the hindrance of degradation by-products. Vibrating sample magnetometer (VSM) reveals a maximum magnetization saturation of 8.77 emu·g-1 with materials having either ferromagnetic or diamagnetic behaviour upon the incorporation of CoFe2O4 and graphite, respectively. Four-point-probe measurements display a maximum electrical conductivity of 9.26 ±â€¯0.04 S·m-1 when graphite is incorporated into CNCs. A proof of concept for the applicability of synthesized nanohybrids for environmental remediation is provided, presenting the advantage of their easy recovery using external magnetic fields.

Water-based 2D printing of magnetically active cellulose derivative nanocomposites.

The fabrication of magnetic materials typically involves expensive, non-scalable, time-consuming or toxic processes. Here we report a scalable, quick and environmentally-benign fabrication of magnetically active materials through screen printing using mechanically flexible paper having micron-sized pores as substrates. In comparison with traditional multicomponent inks, simple aqueous dispersions comprising solely water-soluble cellulose derivatives and cobalt ferrite nanoparticles are used. Depending on the cellulosic matrix used, inks with viscosities in the 500-2.500 mPa s range were obtained for shear rates of 20-100 s-1. Patterns with line widths from 183 to 642 µm with a maximum deviation of 9 % were fabricated. The largest magnetization saturation obtained of 0.024 emu (or 0.021 emu cm-2) for the hydroxypropyl cellulose-based ink demonstrates enough magnetization for applications in areas such as actuators and sensors. This work provides novel insights towards the processing of renewable, magnetically active and mechanically flexible materials with tailored geometries which use water as the sole solvent.

Water-Soluble Cellulose Derivatives as Suitable Matrices for Multifunctional Materials.

This work reports on a simple and environmentally benign route to prepare freestanding magnetic films based on cellulose derivatives through the combination of cobalt ferrite (CoFe2O4) nanoparticles with methyl cellulose (MC), hydroxypropyl cellulose (HPC), and sodium carboxymethyl cellulose (NaCMC). Nanoparticles are able to "shield" hydrogen bonding interactions between polysaccharide chains and lower the viscosity of water-dissolved MC, HPC, and NaCMC, allowing an easy film fabrication. Crack-free films with homogeneously dispersed nanoparticles having concentrations up to 50 wt % are fabricated by mechanical agitation followed by doctor blade casting. All of the nanocomposite films keep a substantial level of flexibility with elongation at break exceeding 5%. Halpin-Tsai equations serve to provide further insights on the character of matrix-CoFe2O4 interfaces. Magnetization saturation increases almost linearly with cobalt ferrite concentration up to a maximum value of ∼24-27 emu g-1 for nanocomposites containing 50 wt % of nanoparticles. The dielectric response of the films demonstrates a strong dependence on both the functional groups attached to the main cellulose chain and the ferrite nanoparticle content. The renewable character of the hosting matrices, together with the fabrication methods that solely uses water as a solvent, the decrease of the viscosity with the inclusion of fillers, particularly suitable for printable materials, and the resulting magnetic performance provide novel avenues for the replacement of traditional magnetoactive composites based on petroleum-derived polymers and avoiding the use of toxic solvents.