Chitosan Composites with Bacterial Cellulose Nanofibers Doped with Nanosized Cerium Oxide: Characterization and Cytocompatibility Evaluation.

In this work, new composite films were prepared by incorporating the disintegrated bacterial cellulose (BCd) nanofibers and cerium oxide nanoparticles into chitosan (CS) matrices. The influence of the amount of nanofillers on the structure and properties of the polymer composites and the specific features of the intermolecular interactions in the materials were determined. An increase in film stiffness was observed as a result of reinforcing the CS matrix with BCd nanofibers: the Young's modulus increased from 4.55 to 6.3 GPa with the introduction of 5% BCd. A further increase in Young's modulus of 6.7 GPa and a significant increase in film strength (22% increase in yield stress compared to the CS film) were observed when the BCd concentration was increased to 20%. The amount of nanosized ceria affected the structure of the composite, followed by a change in the hydrophilic properties and texture of the composite films. Increasing the amount of nanoceria to 8% significantly improved the biocompatibility of the films and their adhesion to the culture of mesenchymal stem cells. The obtained nanocomposite films combine a number of favorable properties (good mechanical strength in dry and swollen states, improved biocompatibility in relation to the culture of mesenchymal stem cells), which allows us to recommend them for use as a matrix material for the culture of mesenchymal stem cells and wound dressings.

Electrospun Composites of Chitosan with Cerium Oxide Nanoparticles for Wound Healing Applications: Characterization and Biocompatibility Evaluation In Vitro and In Vivo.

Cerium oxide nanoparticles (CeONPs), as part of tissue regeneration matrices, can protect cells from reactive oxygen species and oxidative stress. In addition, they can influence the properties of the scaffold, including its electrospinnability and mechanical strength. In this work, we prepared electrospun fiber mats from a chitosan and polyethylene oxide blend (CS-PEO) with the addition of ceria nanoparticles (CS-PEO-CeONP). The addition of CeONPs resulted in a smaller fiber diameter and higher swelling compared to CS-PEO fiber mats. CeONP-modified fiber mats also had a higher Young's modulus due to the reinforcing effect of the nanoparticles. Both mats had comparable adhesion and cytocompatibility to mesenchymal stem cells, which had a more rounded morphology on CS-PEO-CeONP compared to elongated cells on the CS-PEO mats. Biocompatibility in an in vivo rat model showed no acute toxicity, no septic or allergic inflammation, and no rough scar tissue formation. The degradation of both mats passed the stage of matrix swelling. CS-PEO-CeONP showed significantly slower biodegradation, with most of the matrix remaining in the tissue after 90 days. The reactive inflammation was aseptic in nature with the involvement of multinucleated foreign-body type giant cells and was significantly reduced by day 90. CeONPs induced the formation of the implant's connective tissue capsule. Thus, the introduction of CeONPs influenced the physicochemical properties and biological activity of CS-PEO nanofiber mats.

Synergistic Effect of Metal Oxide and Carbon Nanoparticles on the Thermal and Mechanical Properties of Polyimide Composite Films.

In this paper, we report on novel polyimide (PI) nanocomposites filled with binary mixtures of metal oxide (either TiO2 or ZrO2) nanoparticles and nanocarbon (either carbon nanofibers (CNFs) or functionalized carbon nanotubes (CNTfs)). The structure and morphology of the materials obtained were comprehensively studied. An exhaustive investigation of their thermal and mechanical properties was performed. We revealed a synergistic effect of the nanoconstituents with regard to a number of functional characteristics of the PIs compared with single-filler nanocomposites, including thermal stability, stiffness (below and above glass transition temperature), yield point, and temperature of flowing. Moreover, the possibility of manipulating the properties of the materials by choosing a proper combination of the nanofillers was demonstrated. The results obtained can become a platform in the design of PI-based engineering materials with tailored characteristics capable of operating in extreme conditions.

Biocomposite films based on chitosan and cerium oxide nanoparticles with promising regenerative potential.

Polymeric nanocomposite materials have great potential in the development of tissue-engineered scaffolds because they affect the structure and properties of polymeric materials and regulate cell proliferation and differentiation. In this work, cerium oxide nanoparticles (CeONPs) were incorporated into a chitosan (CS) film to improve the proliferation of multipotent mesenchymal stem cells (MSCs). The citrate-stabilized CeONPs with a negative ζ-potential (-25.0 mV) were precoated with CS to obtain positively charged particles (+20.3 mV) and to prevent their aggregation in the composite solution. The composite CS-CeONP films were prepared in the salt and basic forms using a dry-cast process. The films obtained in both forms were characterized by a uniform distribution of CeONPs. The incorporation of CeONPs into the salt form of CS increased the stiffness of the CS-CeONP film, while the subsequent conversion of the film to the basic form resulted in a decrease in both the Young's modulus and the yield stress. The redox activity (Ce4+ ⇌ Ce3+) of cerium oxide in the CS-CeONP film was confirmed by thermal oxidative degradation. In vitro culture of MSCs showed that the CS-CeONP film has good biocompatibility, and in vivo experiments demonstrated its substantial regenerative potential.

Properties of Resorbable Conduits Based on Poly(L-Lactide) Nanofibers and Chitosan Fibers for Peripheral Nerve Regeneration.

New tubular conduits have been developed for the regeneration of peripheral nerves and the repair of defects that are larger than 3 cm. The conduits consist of a combination of poly(L-lactide) nanofibers and chitosan composite fibers with chitin nanofibrils. In vitro studies were conducted to assess the biocompatibility of the conduits using human embryonic bone marrow stromal cells (FetMSCs). The studies revealed good adhesion and differentiation of the cells on the conduits just one day after cultivation. Furthermore, an in vivo study was carried out to evaluate motor-coordination disorders using the sciatic nerve functional index (SFI) assessment. The presence of chitosan monofibers and chitosan composite fibers with chitin nanofibrils in the conduit design increased the regeneration rate of the sciatic nerve, with an SFI value ranging from 76 to 83. The degree of recovery of nerve conduction was measured by the amplitude of M-response, which showed a 46% improvement. The conduit design imitates the oriented architecture of the nerve, facilitates electrical communication between the damaged nerve's ends, and promotes the direction of nerve growth, thereby increasing the regeneration rate.

Metal Oxide Nanoparticles: An Effective Tool to Modify the Functional Properties of Thermally Stable Polyimide Films.

A series of polyimide/metal oxide (either ZrO2 or TiO2) nanocomposite films were fabricated based on two polymer matrices. The prepared films were characterized by scanning electron microscopy (SEM), atomic force microscopy (AFM), and X-ray diffraction analysis (XRD), and their thermal and mechanical properties were investigated with the use of thermogravimetric (TGA), differential thermal analysis (DTA), and thermomechanical analysis (TMA). We have found out that functional properties of the obtained materials are determined by a number of factors, not only the type, size, surface functionality, and concentration of the nanofiller, but also the chemical structure of the matrix polyimide. We have demonstrated some trends in the thermal and mechanical behavior of the materials depending on these features. The data could be of great interest in the areas where new materials with improved functional characteristics are needed.

Domain Structure, Thermal and Mechanical Properties of Polycaprolactone-Based Multiblock Polyurethane-Ureas under Control of Hard and Soft Segment Lengths.

A series of multiblock polyurethane-ureas (PUU) based on polycaprolactone diol (PCL) with a molecular mass of 530 or 2000 g/mol, as well as hard segments of different lengths and structures, were synthesized by the step-growth polymerization method. The chemical structure of the synthesized multiblock copolymers was confirmed by IR- and NMR-spectroscopy. Differential scanning calorimetry (DSC) and dynamic mechanical analysis (DMA) were used to determine the relaxation and phase transition temperatures for the entire series of the obtained PUU. The X-ray diffraction (XRD) method made it possible to identify PUU compositions in which the crystallizability of soft segments (SS) is manifested due to their sufficient length for self-organization and structuring. Visualization of the crystal structure and disordering of the stacking of SS with an increase in their molecular mobility during heating are shown using optical microscopy. The change in the size of the hard phase domains and the value of the interdomain distance depending on the PCL molecular mass, as well as the length and structure of the hard block in the synthesized PUU, were analyzed using small-angle X-ray scattering (SAXS) and small-angle neutron scattering (SANS). The evolution of the domain structure upon passing through the melting and crystallization temperatures of PUU soft blocks was studied using SANS. The studies carried out made it possible to reveal the main correlations between the chemical structure of the synthesized PUU and their supramolecular organization as well as thermal and mechanical properties.

Application of the Composite Fibers Based on Chitosan and Chitin Nanofibrils in Cosmetology.

Chitosan and composite fibers containing chitin nanofibrils have been developed for use in cosmetology. The tensile strength of the chitosan multifilaments is 160.6 ± 19.0 MPa, and of the composite multifilaments containing chitin, nanofibrils are 198.0 ± 18.4 MPa. Chitin nanofibrils introduced into the chitosan solution contribute to the creation of a new spatial arrangement of chitosan chains and their denser packing. The studies carried out by optical, scanning electron, and atomic force microscopy has shown that the serum, consisting of a mixture of lactic acid and sodium lactate, contains extended oriented structures-"liquid filaments". It has been also shown that a mixture of serum and composite fibers based on chitosan and chitin nanofibrils has mucoadhesive, film-forming properties. The introduction of composite fibers containing chitin nanofibrils into the serum promotes the reinforcing effect of liquid filaments, the lifting effect of the film. The obtained composition can be used in cosmetology as a skin care product.

Bacterial Cellulose Composites with Polysaccharides Filled with Nanosized Cerium Oxide: Characterization and Cytocompatibility Assessment.

A new biocompatible nanocomposite film material for cell engineering and other biomedical applications has been prepared. It is based on the composition of natural polysaccharides filled with cerium oxide nanoparticles (CeONPs). The preparative procedure consists of successive impregnations of pressed bacterial cellulose (BC) with a sodium alginate (ALG) solution containing nanoparticles of citrate-stabilized cerium oxide and a chitosan (CS) solution. The presence of CeONPs in the polysaccharide composite matrix and the interaction of the nanoparticles with the polymer, confirmed by IR spectroscopy, change the network architecture of the composite. This leads to noticeable changes in a number of properties of the material in comparison with those of the matrix's polysaccharide composition, viz., an increase in mechanical stiffness, a decrease in the degree of planar orientation of BC macrochains, an increase in hydrophilicity, and the shift of the processes of thermo-oxidative destruction of the material to a low-temperature region. The latter effect is considered to be caused by the redox activity of cerium oxide (reversible transitions between the states Ce4+ and Ce3+) in thermally stimulated processes in the nanocomposite films. In the equilibrium swollen state, the material retains a mechanical strength at the level of ~2 MPa. The results of in vitro tests (cultivation of multipotent mesenchymal stem cells) have demonstrated the good biocompatibility of the BC-ALG(CeONP)-CS film as cell proliferation scaffolds.

Bacterial Cellulose-Based Nanocomposites Containing Ceria and Their Use in the Process of Stem Cell Proliferation.

A technique for the fabrication of bacterial cellulose-based films with CeO2 nanofiller has been developed. The structural and morphological characteristics of the materials have been studied, their thermal and mechanical properties in dry and swollen states having been determined. The preparation methodology makes it possible to obtain composites with a uniform distribution of nanoparticles. The catalytic effect of ceria, regarding the thermal oxidative destruction of cellulose, has been confirmed by TGA and DTA methods. An increase in CeO2 content led to an increase in the elastic modulus (a 1.27-fold increase caused by the introduction of 5 wt.% of the nanofiller into the polymer) and strength of the films. This effect is explained by the formation of additional links between polymer macro-chains via the nanoparticles' surface. The materials fabricated were characterized by a limited ability to swell in water. Swelling caused a 20- to 30-fold reduction in the stiffness of the material, the mechanical properties of the films in a swollen state remaining germane to their practical use. The application of the composite films in cell engineering as substrates for the stem cells' proliferation has been studied. The increase in CeO2 content in the films enhanced the proliferative activity of embryonic mouse stem cells. The cells cultured on the scaffold containing 5 wt.% of ceria demonstrated increased cell survival and migration activity. An analysis of gene expression confirmed improved cultivation conditions on CeO2-containing scaffolds.

Structure-Property Relationship of Polyetherimide Fibers Filled with Carbon Nanoparticles.

Nanocomposite fibers based on heat-resistant amorphous polyetherimide (PEI) were prepared by twin screw melt micro-extrusion. Vapor-grown carbon nanofibers (VGCFs) and single-wall carbon nanotubes (SWCNTs) were used as fillers which helped to achieve enhanced mechanical properties. The structure and mechanical properties of such nanocomposite fibers were studied. Electron microscopy and melt rheology data revealed a uniform distribution of the nanofillers throughout the volume of the fibers. Wide-angle X-ray scattering showed that the orientational drawing of the nanocomposite fibers led to an improved orientation of the filler particles along the fiber axis. VGCFs or SWCNTs increased the tensile strength and modulus (by ∼275 MPa and ∼5 GPa, respectively) in oriented nanocomposite fibers and decreased deformation at break. SWCNTs were found to be more effective reinforcers than VGCFs.

Polystyrene-Based Nanocomposites with Different Fillers: Fabrication and Mechanical Properties.

The paper presents a comprehensive analysis of the elastic properties of polystyrene-based nanocomposites filled with different types of inclusions: small spherical particles (SiO2 and Al2O3), alumosilicates (montmorillonite, halloysite natural tubules and mica), and carbon nanofillers (carbon black and multi-walled carbon nanotubes). Block samples of composites with different filler concentrations were fabricated by melt technology, and their linear and non-linear elastic properties were studied. The introduction of more rigid particles led to a more profound increase in the elastic modulus of a composite, with the highest rise of about 80% obtained with carbon fillers. Non-linear elastic moduli of composites were shown to be more sensitive to addition of filler particles to the polymer matrix than linear ones. A non-linearity modulus ßs comprising the combination of linear and non-linear elastic moduli of a material demonstrated considerable changes correlating with those of the Young's modulus. The changes in non-linear elasticity of fabricated composites were compared with parameters of bulk non-linear strain waves propagating in them. Variations of wave velocity and decay decrement correlated with the observed enhancement of materials' non-linearity.

Polyimide-Based Nanocomposites with Binary CeO2/Nanocarbon Fillers: Conjointly Enhanced Thermal and Mechanical Properties.

To design novel polymer materials with optimal properties relevant to industrial usage, it would seem logical to modify polymers with reportedly good functionality, such as polyimides (PIs). We have created a set of PI-based nanocomposites containing binary blends of CeO2 with carbon nanoparticles (nanocones/discs or nanofibres), to improve a number of functional characteristics of the PIs. The prime novelty of this study is in a search for a synergistic effect amidst the nanofiller moieties regarding the thermal and the mechanical properties of PIs. In this paper, we report on the structure, thermal, and mechanical characteristics of the PI-based nanocomposites with binary fillers. We have found that, with a certain composition, the functional performance of a material can be substantially improved. For example, a PI containing SO2-groups in its macrochains not only had its thermal stability enhanced (by ~20 °C, 10% weight loss up to 533 °C) but also had its stiffness increased by more than 10% (Young's modulus as high as 2.9-3.0 GPa) in comparison with the matrix PI. In the case of a PI with no sulfonic groups, binary fillers increased stiffness of the polymer above its glass transition temperature, thereby widening its working temperature range. The mechanisms of these phenomena are discussed. Thus, this study could contribute to the design of new composite materials with controllable and improved functionality.

Effect of chitin nanofibrils on electrospinning of chitosan-based composite nanofibers.

Electrical conductivity, surface tension and viscosity of chitosan-based composite nanofibers are reported. 20 wt.% of chitin nanofibrils introduced into a chitosan solution leads to increase in viscosity of the mixture; the effect of shear rate becomes more pronounced. This phenomenon is caused by the formation of cluster structures involving filler particles, and by orientation of chitin nanofibrils under the action of shear stresses in electromagnetic field. Presence of chitin facilitated formation of nanofibers in electric field and led to significant decrease in the amount of defects.

Wet spinning of fibers made of chitosan and chitin nanofibrils.

Biocompatible and bioresorbable composite fibers consisting of chitosan filled with anisotropic chitin nanofibrils with the length of 600-800 nm and cross section of about 11-12 nm as revealed by SEM and XRD were prepared by coagulation. Both chitin and chitosan components of the composite fibers displayed preferred orientations. Orientation of chitosan molecules induced by chitin nanocrystallites was confirmed by molecular modeling. The incorporation of 0.1-0.3 wt.% of chitin nanofibrils into chitosan matrix led to an increase in strength and Young modulus of the composite fibers.