Combining Materials Obtained by 3D-Printing and Electrospinning from Commercial Polylactide Filament to Produce Biocompatible Composites.

The design of scaffolds to reach similar three-dimensional structures mimicking the natural and fibrous environment of some cells is a challenge for tissue engineering, and 3D-printing and electrospinning highlights from other techniques in the production of scaffolds. The former is a well-known additive manufacturing technique devoted to the production of custom-made structures with mechanical properties similar to tissues and bones found in the human body, but lacks the resolution to produce small and interconnected structures. The latter is a well-studied technique to produce materials possessing a fibrillar structure, having the advantage of producing materials with tuned composition compared with a 3D-print. Taking the advantage that commercial 3D-printers work with polylactide (PLA) based filaments, a biocompatible and biodegradable polymer, in this work we produce PLA-based composites by blending materials obtained by 3D-printing and electrospinning. Porous PLA fibers have been obtained by the electrospinning of recovered PLA from 3D-printer filaments, tuning the mechanical properties by blending PLA with small amounts of polyethylene glycol and hydroxyapatite. A composite has been obtained by blending two layers of 3D-printed pieces with a central mat of PLA fibers. The composite presented a reduced storage modulus as compared with a single 3D-print piece and possessing similar mechanical properties to bone tissues. Furthermore, the biocompatibility of the composites is assessed by a simulated body fluid assay and by culturing composites with 3T3 fibroblasts. We observed that all these composites induce the growing and attaching of fibroblast over the surface of a 3D-printed layer and in the fibrous layer, showing the potential of commercial 3D-printers and filaments to produce scaffolds to be used in bone tissue engineering.

Concentration Dependent Single Chain Properties of Poly(sodium 4-styrenesulfonate) Subjected to Aromatic Interactions with Chlorpheniramine Maleate Studied by Diafiltration and Synchrotron-SAXS.

The polyelectrolyte poly(sodium 4-styrenesulfonate) undergoes aromatic-aromatic interaction with the drug chlorpheniramine, which acts as an aromatic counterion. In this work, we show that an increase in the concentration in the dilute and semidilute regimes of a complex polyelectrolyte/drug 2:1 produces the increasing confinement of the drug in hydrophobic domains, with implications in single chain thermodynamic behavior. Diafiltration analysis at polymer concentrations between 0.5 and 2.5 mM show an increase in the fraction of the aromatic counterion irreversibly bound to the polyelectrolyte, as well as a decrease in the electrostatic reversible interaction forces with the remaining fraction of drug molecules as the total concentration of the system increases. Synchrotron-SAXS results performed in the semidilute regimes show a fractal chain conformation pattern with a fractal dimension of 1.7, similar to uncharged polymers. Interestingly, static and fractal correlation lengths increase with increasing complex concentration, due to the increase in the amount of the confined drug. Nanoprecipitates are found in the range of 30-40 mM, and macroprecipitates are found at a higher system concentration. A model of molecular complexation between the two species is proposed as the total concentration increases, which involves ion pair formation and aggregation, producing increasingly confined aromatic counterions in hydrophobic domains, as well as a decreasing number of charged polymer segments at the hydrophobic/hydrophilic interphase. All of these features are of pivotal importance to the general knowledge of polyelectrolytes, with implications both in fundamental knowledge and potential technological applications considering aromatic-aromatic binding between aromatic polyelectrolytes and aromatic counterions, such as in the production of pharmaceutical formulations.

Fibrous Materials Made of Poly(ε-caprolactone)/Poly(ethylene oxide)-b-Poly(ε-caprolactone) Blends Support Neural Stem Cells Differentiation.

In this work, we design and produce micron-sized fiber mats by blending poly(ε-caprolactone) (PCL) with small amounts of block copolymers poly(ethylene oxide)m-block-poly(ε-caprolactone)n (PEOm-b-PCLn) using electrospinning. Three different PEOm-b-PCLn block copolymers, with different molecular weights of PEO and PCL, were synthesized by ring opening polymerization of ε-caprolactone using PEO as initiator and stannous octoate as catalyst. The polymer blends were prepared by homogenous solvent mixing using dichloromethane for further electrospinning procedures. After electrospinning, it was found that the addition to PCL of the different block copolymers produced micron-fibers with smaller width, equal or higher hydrophilicity, lower Young modulus, and rougher surfaces, as compared with micron-fibers obtained only with PCL. Neural stem progenitor cells (NSPC), isolated from rat brains and grown as neurospheres, were cultured on the fibrous materials. Immunofluorescence assays showed that the NSPC are able to survive and even differentiate into astrocytes and neurons on the synthetic fibrous materials without any growth factor and using the fibers as guidance. Disassembling of the cells from the NSPC and acquisition of cell specific molecular markers and morphology progressed faster in the presence of the block copolymers, which suggests the role of the hydrophilic character and porous topology of the fiber mats.

Ionic Nanocomplexes of Hyaluronic Acid and Polyarginine to Form Solid Materials: A Green Methodology to Obtain Sponges with Biomedical Potential.

We report on the design, development, characterization, and a preliminary cellular evaluation of a novel solid material. This material is composed of low-molecular-weight hyaluronic acid (LMWHA) and polyarginine (PArg), which generate aqueous ionic nanocomplexes (INC) that are then freeze-dried to create the final product. Different ratios of LMWHA/PArg were selected to elaborate INC, the size and zeta potential of which ranged from 100 to 200 nm and +25 to -43 mV, respectively. Turbidimetry and nanoparticle concentration analyses demonstrated the high capacity of the INC to interact with increasing concentrations of LMWHA, improving the yield of production of the nanostructures. Interestingly, once the selected formulations of INC were freeze-dried, only those comprising a larger excess of LMWHA could form reproducible sponge formulations, as seen with the naked eye. This optical behavior was consistent with the scanning transmission electron microscopy (STEM) images, which showed a tendency of the particles to agglomerate when an excess of LMWHA was present. Mechanical characterization evidenced low stiffness in the materials, attributed to the low density and high porosity. A preliminary cellular evaluation in a fibroblast cell line (RMF-EG) evidenced the concentration range where swollen formulations did not affect cell proliferation (93-464 µM) at 24, 48, or 72 h. Considering that the reproducible sponge formulations were elaborated following inexpensive and non-contaminant methods and comprised bioactive components, we postulate them with potential for biomedical purposes. Additionally, this systematic study provides important information to design reproducible porous solid materials using ionic nanocomplexes.

Intrinsic electron trapping in amorphous oxide.

We demonstrate that electron trapping at intrinsic precursor sites is endemic in non-glass-forming amorphous oxide films. The energy distributions of trapped electron states in ultra-pure prototype amorphous (a)-HfO2 insulator obtained from exhaustive photo-depopulation experiments demonstrate electron states in the energy range of 2-3 eV below the oxide conduction band. These energy distributions are compared to the results of density functional calculations of a-HfO2 models of realistic density. The experimental results can be explained by the presence of intrinsic charge trapping sites formed by under-coordinated Hf cations and elongated Hf-O bonds in a-HfO2. These charge trapping states can capture up to two electrons, forming polarons and bi-polarons. The corresponding trapping sites are different from the dangling-bond type defects responsible for trapping in glass-forming oxides, such as SiO2, in that the traps are formed without bonds being broken. Furthermore, introduction of hydrogen causes formation of somewhat energetically deeper electron traps when a proton is immobilized next to the trapped electron bi-polaron. The proposed novel mechanism of intrinsic charge trapping in a-HfO2 represents a new paradigm for charge trapping in a broad class of non-glass-forming amorphous insulators.