Matching Low Viscosity with Enhanced Conductivity in Vat Photopolymerization 3D Printing: Disparity in the Electric and Rheological Percolation Thresholds of Carbon-Based Nanofillers Is Controlled by the Matrix Type and Filler Dispersion.

This study investigated the impact of carbonaceous fillers (carbon black, multiwalled carbon nanotubes, graphene, and highly defective graphene) on aromatic and nonaromatic photopolymer resins' properties, such as viscosity, long-term stability, complex permittivity, curing efficiency, final conversion, storage modulus, heat deflection and glass transition temperatures, network density, and DC resistivity. The presented results also highlight challenges that must be addressed in designing and processing carbonaceous filler-based 3D-printed photopolymer resins. The improved dielectric and electrical properties were closely tied to the dispersion quality and filler-matrix affinity. It favored the enhanced dispersion of anisotropic fillers (nanotubes) in a compatible matrix above their percolation threshold. On the other hand, the dispersed filler worsens printability due to the elevated viscosity and deteriorated penetration depth. Nonetheless, electrical and rheological percolation was found at different filler concentrations. This window of despaired percolation combines highly enhanced conductivity with only mildly increased viscosity and good printability.

Anisotropic solid-state PLA foaming templated by crystal phase pre-oriented with 3D printing: cell supporting structures with directional capillary transfer function.

Bones represent a superb biomaterial that combines high mechanical stiffness with nutrition delivery to its osteocyte cells through the microscopical Haversian canals and bone canaliculi. Such a structure is hard to reproduce artificially, though. 3D printing delivers an unprecedented shape control of the created objects. Yet the resolution limit of the most common 3D printers is insufficient, lying between tens to hundreds of microns, while more precise 3D printing techniques fail in fabricating larger objects. We present a unique, yet simple and versatile method for preparing hierarchically aligned microporous canals using a biocompatible polymer polylactic acid (PLA) with their structure controlled at the submicron to macro scale. The layout was inspired by the microscopical Haversian canals and bone canaliculi of cortical bone. This procedure takes advantage of the PLA complex crystalline behavior, which was pre-oriented by 3D printing, orientedly crystallized in CO2, foamed, and cryo-shrunk. The canal formation was assessed via WAXS, FTIR spectroscopy, and DSC and complemented by the evaluation of mechanical properties, biocompatibility, and directionally selective capillary transport in the final structure. The fine dimensions of the canals unmatched by the common 3D printing techniques capable of making macroscale objects combined with the abovementioned properties represent promising potential for various applications, such as advanced cell-supporting designs with a built-in nutrition function.

Antibacterial Electrospun Polycaprolactone Nanofibers Reinforced by Halloysite Nanotubes for Tissue Engineering.

Due to its slow degradation rate, polycaprolactone (PCL) is frequently used in biomedical applications. This study deals with the development of antibacterial nanofibers based on PCL and halloysite nanotubes (HNTs). Thanks to a combination with HNTs, the prepared nanofibers can be used as low-cost nanocontainers for the encapsulation of a wide variety of substances, including drugs, enzymes, and DNA. In our work, HNTs were used as a nanocarrier for erythromycin (ERY) as a model antibacterial active compound with a wide range of antibacterial activity. Nanofibers based on PCL and HNT/ERY were prepared by electrospinning. The antibacterial activity was evaluated as a sterile zone of inhibition around the PCL nanofibers containing 7.0 wt.% HNT/ERY. The morphology was observed with SEM and TEM. The efficiency of HNT/ERY loading was evaluated with thermogravimetric analysis. It was found that the nanofibers exhibited outstanding antibacterial properties and inhibited both Gram- (Escherichia coli) and Gram+ (Staphylococcus aureus) bacteria. Moreover, a significant enhancement of mechanical properties was achieved. The potential uses of antibacterial, environmentally friendly, nontoxic, biodegradable PCL/HNT/ERY nanofiber materials are mainly in tissue engineering, wound healing, the prevention of bacterial infections, and other biomedical applications.

Adsorption/desorption behavior of hyaluronic acid fragments at charged hydrophobic surface.

This work reveals the growing potential of novel electrochemical methods that are applicable for polysaccharides. It was shown for the first time that the molecules of hyaluronic acid (HA) exhibit electrochemical response using phase-sensitive alternating current (AC) voltammetry in phase-out mode. Adsorption and desorption processes of HA fragments at a charged interface of mercury electrode were observed in buffered HA solutions. Electrostatic and hydrophobic manners of interactions were distinguished for native hyaluronan fragments in a wide electric potential range. The AC voltammetry response depended on the temperature, concentration, and length of HA chains. Results of this work open possibilities for further structural characterization of widely used HA fragments and understanding manners of interactions with charged hydrophobic surfaces that could be useful in the future for understanding HA interactions at biological levels.

Multifunctional Electrospun Nanofibers Based on Biopolymer Blends and Magnetic Tubular Halloysite for Medical Applications.

Tubular halloysite (HNT) is a naturally occurring aluminosilicate clay with a unique combination of natural availability, good biocompatibility, high mechanical strength, and functionality. This study explored the effects of magnetically responsive halloysite (MHNT) on the structure, morphology, chemical composition, and magnetic and mechanical properties of electrospun nanofibers based on polycaprolactone (PCL) and gelatine (Gel) blends. MHNT was prepared via a simple modification of HNT with a perchloric-acid-stabilized magnetic fluid-methanol mixture. PCL/Gel nanofibers containing 6, 9, and 12 wt.% HNT and MHNT were prepared via an electrospinning process, respecting the essential rules for medical applications. The structure and properties of the prepared nanofibers were studied using infrared spectroscopy (ATR-FTIR) and electron microscopy (SEM, STEM) along with energy-dispersive X-ray spectroscopy (EDX), magnetometry, and mechanical analysis. It was found that the incorporation of the studied concentrations of MHNT into PCL/Gel nanofibers led to soft magnetic biocompatible materials with a saturation magnetization of 0.67 emu/g and coercivity of 15 Oe for nanofibers with 12 wt.% MHNT. Moreover, by applying both HNT and MHNT, an improvement of the nanofibers structure was observed, together with strong reinforcing effects. The greatest improvement was observed for nanofibers containing 9 wt.% MHNT when increases in tensile strength reached more than two-fold and the elongation at break reached a five-fold improvement.

Formulation of hyaluronan grafted with dodecanoic acid as a potential ophthalmic treatment.

This work concerns the chemical modification of medium molecular weight hyaluronan for ophthalmic applications. The synthesis of amphiphilic HA with dodecanoyl moities was carried out under mild aqueous conditions. Perfect control of the degree of substitution was obtained by varying the molar ratio of activated fatty acid used in the reaction feed. Moreover, the preparation of the derivatives was optimized to achieve the desired degree of substitution (DS = 9.0 ± 0.2 %). The prepared hyaluronan derivatives were water-soluble and exhibited self-associating properties (amphiphilicity). The structure of the prepared derivatives was elucidated by NMR spectroscopy, rheology, turbidity, SEC-MALLS, and gas chromatography (GC). The hydrophobic moieties increase the solution viscosity by physical crosslinking. Low concentration of HAC12 is needed to prepare highly viscous solutions with potential use for ophthalmic applications. Amphiphilic HA kept the biocompatibility of hyaluronan. The degree of substitution and Mw of the amphiphilic HA controls the sterilization by filtration. The protection against desiccation was tested using human keratinocytes (HaCaT) cells lines.

Synthesis and Physicochemical Characterization of Undecylenic Acid Grafted to Hyaluronan for Encapsulation of Antioxidants and Chemical Crosslinking.

In this work, a new amphiphilic derivative made of 10-undecylenic acid grafted to hyaluronan was prepared by mixed anhydrides. The reaction conditions were optimized, and the effect of the molecular weight (Mw), reaction time, and the molar ratio of reagents was explored. Using this methodology, a degree of substitution up to 50% can be obtained. The viscosity of the conjugate can be controlled by varying the substitution degree. The physicochemical characterization of the modified hyaluronan was performed by infrared spectroscopy, Nuclear Magnetic Resonance, Size-Exclusion Chromatography combined with Multiangle Laser Light Scattering (SEC-MALLS), and rheology. The low proton motility and self-aggregation of the amphiphilic conjugate produced overestimation of the degree of substitution. Thus, a novel method using proton NMR was developed. Encapsulation of model hydrophobic guest molecules, coenzyme Q10, curcumin, and α-tocopherol into the micellar core was also investigated by solvent evaporation. HA-UDA amphiphiles were also shown to self-assemble into spherical nanostructures (about 300 nm) in water as established by dynamic light scattering. Furthermore, HA-UDA was crosslinked via radical polymerization mediated by ammonium persulphate (APS/TEMED). The cross-linking was also tested by photo-polymerization catalyzed by Irgacure 2959. The presence of the hydrophobic moiety decreases the swelling degree of the prepared hydrogels compared to methacrylated-HA. Here, we report a novel hybrid hyaluronan (HA) hydrogel system of physically encapsulated active compounds and chemical crosslinking for potential applications in drug delivery.

Bulk polymer nanocomposites with preparation protocol governed nanostructure: the origin and properties of aggregates and polymer bound clusters.

Polymer nanocomposites (PNCs) hold great promise as future lightweight functional materials processable by additive manufacturing technologies. However, their rapid deployment is hindered by their performance depending strongly on the nanoparticle (NP) spatial organization. Therefore, the ability to control nanoparticle dispersion in the process of PNC preparation is a crucial prerequisite for utilizing their potential in functional composites. We report on the bulk processing technique of tailored NP spatial organization in a model glass forming polymer matrix controlled by structural and kinetic variables of the preparation protocol. Namely, we studied the impact of solvent on the NP arrangement, which was already known as a tuning parameter of the solid-state structure. We emphasized the qualitative differences between "poorly dispersed" NP arrays, which, by combination of rheological assessment and structural analysis (TEM, USAXS), we identified as chain bound clusters and aggregates of either thermodynamic or kinetical origin. They are characterized by substantially distinct formation kinetics and mismatched properties compared to each other and individually dispersed NPs. We quantitatively linked all the currently observed types of NP dispersion with their rheological properties during the solution blending step and the amount of polymer adsorption and depletion attraction. We propose the ratio of NP-polymer and NP-solvent enthalpy of adsorption as a parameter capable of the quantitative prediction of NP arrangement in systems similar to our current model PNC. Finally, we bring forth the comparison of glass transition temperatures to further demonstrate the importance of NP spatial organization in PNCs.