Grafting of calcium chelating functionalities onto PLA monofilament fiber surfaces.

Polymer surface grafting is widely used in the field of bone regeneration to increase calcium phosphate (CaP) adhesion, with the intent of improving mechanical properties of CaP-polymer composite cements. Reinforcement can be achieved using multiple combined functional groups and/or complex surface geometries that, however, concurrently influence multiple effects such as wetting, roughness, and interfacial strengthening. This study focused on the influence of a chelating group, namely aspartic acid, on the adsorption of divalent ions such as Ba2+ or Ca2+ onto poly-l-lactic acid (PLA) films. The films were analyzed using contact angle measurements and X-ray photoelectron spectroscopy. The adsorption of CaP and its interfacial mechanical properties were investigated using functionalized PLA monofilaments whose surface roughness was analyzed using white light interferometry. Mechanical analysis was conducted by performing pull-out tests. The surfaces were analyzed using scanning electron microscopy and energy dispersive X-ray spectroscopy. Using aspartic acid as a chelating group resulted in a 50 % increased adsorption of barium, an almost threefold increase in calcium coverage of the fiber compared to the control group and a twofold increase in interfacial stiffness. No significant increase in interfacial strength was determined, most likely due to the weakness of the CaP matrix, which was partially visible as residues on the monofilaments in the postfracture imaging. This study shows the potential of surfaces functionalized with aspartic acid as a simple alternative to complex polypeptide based functional groups for the adsorption of divalent ions such as calcium on poly-lactic acid in bone regenerating applications.

Absorbable mineral nanocomposite for biomedical applications: Influence of homogenous fiber dispersity on mechanical properties.

Electrospun micro- and nanosized fibers are frequently used as reinforcing elements in low temperature ceramic composites for biomedical applications. Electrospinning of fibers yield, however, not individual fibers, but rather fiber-mats that are difficult to separate. Most investigations have been performed on diced mats and highly nonhomogenous composites. We examined the influence of dispersed electrospun single micro- and nanometer fibers on the mechanical properties of calcium phosphate cement composites. Absorbable poly-l-lactic-acid was electrospun yielding fibers with diameters of 244 ± 78 nm, named nanofibers (NF), and 1.0 ± 0.3 µm, named microfibers (MF). These fibers were cut using a particle assisted ultrasonication process and dispersed with hydroxyapatite nanoparticles and composites of low (5%) and high (30%) NF/MF content were engineered. The homogeneity of the fiber distribution was investigated by analyzing fracture areas regarding the number of fibers and Voronoi area size distribution. Variation of fiber distribution was significantly lower in the NF group as compared to the MF group. For composites containing 5% NF (V/V), an eightfold increase in the compressive fracture strength, and for the 30% NF (V/V) a threefold increase compared was measured. The composite containing 5% NF was identified as optimal regarding fiber distribution and strength. Our new method of engineering these composites allows for high volume fractions of NF with low variation in fiber distribution to be incorporated into composites, and shows the importance of using single filaments as reinforcing agents. © 2017 Wiley Periodicals, Inc. J Biomed Mater Res Part A: 106A: 850-857, 2018.

Fabrication of biopolymer-based staple electrospun fibres for nanocomposite applications by particle-assisted low temperature ultrasonication.

We demonstrate the fabrication of staple polymer-based fibres by the ultrasound-assisted processing of electrospun meshes. Bioabsorbable Poly-L-Lactic Acid (PLLA) was electrospun from organic solvent mixtures, yielding continuous fibres with diameters in the range of 244±78 nm. Subsequently, the obtained fibres were sonicated at low temperatures in the presence of nanoparticles in order to obtain fibres with small aspect ratios. The influence of the dispersion medium, the sonication process parameters (temperature and time) and the dimensions of the particles used on the respective length distribution of the obtained nanofibres was investigated. Hexane was identified as an optimal dispersion medium for the system studied in this work. When a cooling bath temperature of 0°C was used, a slight increase in the obtained fibres' average length and distribution was observed as compared to cooling at -80°C (54±43 µm vs 44±31 µm). Moreover, in the presence of hydroxyapatite and hydrophilic and hydrophobic TiO2 nanoparticles in the dispersion medium longer fibres were obtained (44±31 µm, 63±47 µm, and 51±52 µm). Finally, the application of the obtained PLLA-fibre-hydroxyapatite (HA) nanoparticle precursors for the fabrication of a fibre-reinforced Brushite-based cement with high compressive strength is shown. This method of obtaining nanoscaled fibre-reinforced materials opens up a wide range of perspectives for the fabrication of composites for tissue engineering applications.