Precisely Printable Silk Fibroin/Carboxymethyl Cellulose/Alginate Bioink for 3D Printing.

Three-dimensional (3D) bioprinting opens up many possibilities for tissue engineering, thanks to its ability to create a three-dimensional environment for cells like an extracellular matrix. However, the use of natural polymers such as silk fibroin in 3D bioprinting faces obstacles such as having a limited printability due to the low viscosity of such solutions. This study addresses these gaps by developing highly viscous, stable, and biocompatible silk fibroin-based inks. The addition of 2% carboxymethyl cellulose sodium and 1% sodium alginate to an aqueous solution containing 2.5 to 5% silk fibroin significantly improves the printability, stability, and mechanical properties of the printed scaffolds. It has been demonstrated that the more silk fibroin there is in bioinks, the higher their printability. To stabilize silk fibroin scaffolds in an aqueous environment, the printed structures must be treated with methanol or ethanol, ensuring the transition from the silk fibroin's amorphous phase to beta sheets. The developed bioinks that are based on silk fibroin, alginate, and carboxymethyl cellulose demonstrate an ease of printing and a high printing quality, and have a sufficiently good biocompatibility with respect to mesenchymal stromal cells. The printed scaffolds have satisfactory mechanical characteristics. The resulting 3D-printing bioink composition can be used to create tissue-like structures.

Influence of Molecular Weight on Thermal and Mechanical Properties of Carbon-Fiber-Reinforced Plastics Based on Thermoplastic Partially Crystalline Polyimide.

For the first time, a study of the influence of the molecular weight of the thermoplastic partially crystalline polyimide R-BAPB on the thermophysical and mechanical properties of carbon plastics was presented. The molecular weight of polyimide was determined using the method of light scattering and the study of the intrinsic viscosity of polyamic acid solutions. To obtain CFRPs, the uniform distribution of polyimide powder on continuous carbon fibers via electrostatic spraying and further hot calendering and pressing were applied. The study of the structure of the obtained carbon plastics via scanning electron microscopy has shown that the growth of the molecular weight of polyimide prevents the impregnation of carbon fiber with the introduced polyimide. Moreover, an increase in the molecular weight of polyimide leads to a rise in glass transition and thermal decomposition temperatures up to 590 °C, while the degree of crystallinity of CFRP falls. Nonetheless, raising the molecular weight from 22,000 to 70,000 g/mol of a binder polymer improves the interlayer fracture toughness G1C by more than five times.

Carrageenan/Chitin Nanowhiskers Cryogels for Vaginal Delivery of Metronidazole.

The development of polymeric carriers based on partially deacetylated chitin nanowhiskers (CNWs) and anionic sulfated polysaccharides is an attractive strategy for improved vaginal delivery with modified drug release profiles. This study focuses on the development of metronidazole (MET)-containing cryogels based on carrageenan (CRG) and CNWs. The desired cryogels were obtained by electrostatic interactions between the amino groups of CNWs and the sulfate groups of CRG and by the formation of additional hydrogen bonds, as well as by entanglement of carrageenan macrochains. It was shown that the introduction of 5% CNWs significantly increased the strength of the initial hydrogel and ensured the formation of a homogeneous cryogel structure, resulting in sustained MET release within 24 h. At the same time, when the CNW content was increased to 10%, the system collapsed with the formation of discrete cryogels, demonstrating MET release within 12 h. The mechanism of prolonged drug release was mediated by polymer swelling and chain relaxation in the polymer matrix and correlated well with the Korsmeyer-Peppas and Peppas-Sahlin models. In vitro tests showed that the developed cryogels had a prolonged (24 h) antiprotozoal effect against Trichomonas, including MET-resistant strains. Thus, the new cryogels with MET may be promising dosage forms for the treatment of vaginal infections.

Development and Processing of New Composite Materials Based on High-Performance Semicrystalline Polyimide for Fused Filament Fabrication (FFF) and Their Biocompatibility.

Samples of composite materials based on high-performance semicrystalline polyimide R-BAPB (based on the dianhydride R: 1,3-bis-(3',4,-dicarboxyphenoxy)benzene and diamine BAPB: 4,4'-bis-(4″-aminophenoxy)diphenyl)) filled with carbon nanofibers and micron-sized discrete carbon fibers were obtained by FFF printing for the first time. The viscosity of melts of the composites based on R-BAPB, thermal, mechanical characteristics of the obtained composite samples, their internal structure, and biocompatibility were studied. Simultaneously with FFF printing, samples were obtained by injection molding. The optimal concentrations of carbon fillers in polyimide R-BAPB for their further use in FFF printing were determined. The effect of the incorporation of carbon fillers on the porosity of the printed samples was investigated. It was shown that the incorporation of carbon nanofibers reduces the porosity of the printed samples, which leads to an increase in deformation at break. Modification of polyimide with discrete carbon fibers increases the strength and Young's modulus sufficiently but decreases the deformation at break. The cytotoxicity analysis showed that the obtained composite materials are bioinert.

Rheological and Mechanical Properties of Thermoplastic Crystallizable Polyimide-Based Nanocomposites Filled with Carbon Nanotubes: Computer Simulations and Experiments.

Recently, a strong structural ordering of thermoplastic semi-crystalline polyimides near single-walled carbon nanotubes (SWCNTs) was found that can enhance their mechanical properties. In this study, a comparative analysis of the results of microsecond-scale all-atom computer simulations and experimental measurements of thermoplastic semi-crystalline polyimide R-BAPB synthesized on the basis of dianhydride R (1,3-bis-(3',4-dicarboxyphenoxy) benzene) and diamine BAPB (4,4'-bis-(4″-aminophenoxy) biphenyl) near the SWCNTs on the rheological properties of nanocomposites was performed. We observe the viscosity increase in the SWCNT-filled R-BAPB in the melt state both in computer simulations and experiments. For the first time, it is proven by computer simulation that this viscosity change is related to the structural ordering of the R-BAPB in the vicinity of SWCNT but not to the formation of interchain linkage. Additionally, strong anisotropy of the rheological properties of the R-BAPB near the SWCNT surface was detected due to the polyimide chain orientation. The increase in the viscosity of the polymer in the viscous-flow state and an increase in the values of the mechanical characteristics (Young's modulus and yield peak) of the SWCNT-R-BAPB nanocomposites in the glassy state are stronger in the directions along the ordering of polymer chains close to the carbon nanofiller surface. Thus, the new experimental data obtained on the R-BAPB-based nanocomposites filled with SWCNT, being extensively compared with simulation results, confirm the idea of the influence of macromolecular ordering near the carbon nanotube on the mechanical characteristics of the composite material.

Morphological Transformation in Polymer Composite Materials Filled with Carbon Nanoparticles: Part 1-SEM and XRD Investigations.

HDPE-based nanocomposite fibers have been extruded from a melt and drawn up to draw ratio DR = 8. Two kinds of carbon nanodiscs (original ones and those exposed to additional annealing) have been used as fillers. Obtained nanocomposite fibers have been investigated with the help of different experimental methods: rheology, SEM and WAXS. It has been demonstrated that the annealed carbon nanodiscs possess a nucleation ability that finally leads to strong transformation of the material morphology.

Investigation of Polyetherimide Melt-Extruded Fibers Modified by Carbon Nanoparticles.

The fibers based on thermoplastic partially crystalline polyetherimide R-BAPB modified by vapor grown carbon nanofibers (VGCF) were prepared by melt extrusion, exposed to orientational drawing, and crystallized. All of the samples were examined by scanning electron microscopy, X-ray scattering, and differential scanning calorimetry to study how the carbon nanofiller influences on the internal structure and crystallization behavior of the obtained R-BAPB fibers. The mechanical properties of the composite R-BAPB fibers were also determined. It was found that VGCF nanoparticles introduced into R-BAPB polyimide can act as a nucleating agent that leads, in turn, to significant changes in the composite fibers morphology as well as thermal and mechanical characteristics. VGCF are able to improve an orientation degree of the R-BAPB macromolecules along the fiber direction, accelerate crystallization rate of the polymer, and enhance the fiber stability during crystallization process.

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.

Alginate Gel Reinforcement with Chitin Nanowhiskers Modulates Rheological Properties and Drug Release Profile.

Hydrogels are promising materials for various applications, including drug delivery, tissue engineering, and wastewater treatment. In this work, we designed an alginate (ALG) hydrogel containing partially deacetylated chitin nanowhiskers (CNW) as a filler. Gelation in the system occurred by both the protonation of alginic acid and the formation of a polyelectrolyte complex with deacetylated CNW surface chains. Morphological changes in the gel manifested as a honeycomb structure in the freeze-dried gel, unlike the layered structure of an ALG gel. Disturbance of the structural orientation of the gels by the introduction of CNW was also expressed as a decrease in the intensity of X-ray diffraction reflexes. All studied systems were non-Newtonian liquids that violated the Cox-Merz rule. An increase in the content of CNW in the ALG-CNW hydrogel resulted in increases in the yield stress, maximum Newtonian viscosity, and relaxation time. Inclusion of CNW prolonged the release of tetracycline due to changes in diffusion. The first phases (0-5 h) of the release profiles were well described by the Higuchi model. ALG-CNW hydrogels may be of interest as soft gels for controlled topical or intestinal drug delivery.