Ewa Stodolak-Zych

Biodegradable ceramic-polymer composites for biomedical applications: A review

The present work focuses on the state-of-the-art of biodegradable ceramic-polymer composites with particular emphasis on influence of various types of ceramic fillers on properties of the composites. First, the general needs to create composite materials for medical applications are briefly introduced. Second, various types of polymeric materials used as matrices of ceramic-containing composites and their properties are reviewed. Third, silica nanocomposites and their material as well as biological characteristics are presented. Fourth, different types of glass fillers including silicate, borate and phosphate glasses and their effect on a number of properties of the composites are described. Fifth, wollastonite as a composite modifier and its effect on composite characteristics are discussed. Sixth, composites containing calcium phosphate ceramics, namely hydroxyapatite, tricalcium phosphate and biphasic calcium phosphate are presented. Finally, general possibilities for control of properties of composite materials are highlighted.

Effect of the preparation methods on architecture, crystallinity, hydrolytic degradation, bioactivity, and biocompatibility of PCL/bioglass composite scaffolds.

In this study, two different composition gel derived silica-rich (S2) or calcium-rich (A2) bioactive glasses (SBG) from a basic CaO-P2 O5 -SiO2 system were incorporated into poly(ε-caprolactone) (PCL) matrix to obtain novel bioactive composite scaffolds for bone tissue engineering applications. The composites were fabricated in the form of highly porous 3D scaffolds using following preparation methods: solvent casting particulate leaching (SCPL), solid-liquid phase separation, phase inversion (PI). Scaffolds containing 21% vol. of each bioactive glass were characterized for architecture, crystallinity, hydrolytic degradation, surface bioactivity, and cellular response. Results indicated that the use of different preparation methods leads to obtain highly porous (60-90%) materials with differentiated morphology: pore shape, size, and distributions. Thermal analysis (DSC) showed that the preparation method of materials and addition of bioactive glass particles into polymer matrix induced the changes of PCL crystallinity. Composites obtained by SCPL and PI method containing A2 SBG rapidly formed a hydroxyapatite calcium phosphate surface layer after incubation in SBF. Bioactive glasses used as filler in composite scaffolds could neutralize the released acidic by-products of the polymer degradation. Preliminary in vitro biological studies of the composites in contact with osteoblastic cells showed good biocompatibility of the obtained materials. Addition of bioactive glass into the PCL matrix promotes mineralization estimated on the basis of the ALP activity. These results suggest that through a process of selection appropriate methods of preparation and bioglass composition it is possible to design and obtain porous materials with suitable properties for regeneration of bone tissue.

Characterisation, in vitro release study, and antibacterial activity of montmorillonite-gentamicin complex material

The present paper concerns the potential use of montmorillonite as a drug carrier and focusses on the intercalation of the studied clay with gentamicin (an aminoglycoside antibiotic) at various temperatures (20, 50 and 80°C). The experiments were performed to identify the temperature required for the optimum intercalation of gentamicin into the interlayer of montmorillonite. The structural and microstructural properties of gentamicin and the potential for introducing it between smectite clay layers were investigated by means of X-ray diffraction (XRD), Fourier transform infrared (FTIR) spectroscopic techniques, and SEM with EDS analysis. Additionally, the in vitro drug release behaviour of the montmorillonite-gentamicin complex and its antibacterial activity against Escherichia coli (E. coli) bacteria was investigated. Based on these studies, the impact of temperature on the intercalation of the drug between layers of smectite was evaluated. It was found that an intercalation temperature of 50°C resulted in the highest shift in the position of principle peak d(001) as measured by XRD, suggesting, that the greatest amount of gentamicin had been introduced into the interlayer space of montmorillonite at this temperature. Subsequently, the montmorillonite-gentamicin complex material obtained at 50°C revealed the greatest capacity for killing E. coli bacteria during an in vitro test.

Instrumental characterization of the smectite clay–gentamicin hybrids

This paper focusses on the intercalation of clay mineral with gentamicin (an aminoglycoside antibiotic). The smectite clay–gentamicin hybrids were prepared by a solution intercalation at 60∘C and the process was carried out on unmodified smectite clay and on smectite after Na+ ionic activation. The resulting structural/microstructural properties and the potential for introducing gentamicin between smectite clay layers were investigated by means of X-ray diffraction, Fourier transform infrared spectroscopic techniques and transmission electron microscopy and scanning electron microscopy with energy-dispersive spectroscopy X-ray analysis. The results confirm the successful intercalation of gentamicin into the interlayer space of smectite clay, demonstrating that the material thus obtained could potentially be used as a drug carrier.

Fibrous Polymeric Composites Based on Alginate Fibres and Fibres Made of Poly-ε-caprolactone and Dibutyryl Chitin for Use in Regenerative Medicine

This work concerns the production of fibrous composite materials based on biodegradable polymers such as alginate, dibutyryl chitin (DBC) and poly-ε-caprolactone (PCL). For the production of fibres from these polymers, various spinning methods were used in order to obtain composite materials of different composition and structure. In the case of alginate fibres containing the nanoadditive tricalcium phosphate (TCP), the traditional method of forming fibres wet from solution was used. However in the case of the other two polymers the electrospinning method was used. Two model systems were tested for biocompatibility. The physicochemical and basic biological tests carried out show that the submicron fibres produced using PCL and DBC have good biocompatibility. The proposed hybrid systems composed of micrometric fibres (zinc and calcium alginates containing TCP) and submicron fibres (DBC and PCL) meet the requirements of regenerative medicine. The biomimetic fibre system, the presence of TCP nanoadditive, and the use of polymers with different resorption times provide a framework with specific properties on which bone cells are able to settle and proliferate.

Bioactivity of a Chitosan Based Nanocomposite

In this work, experiments to produce a series of nanocomposites based on natural chitosan and nano-clay (MMT) were conducted. Commercially available montmorillonite (MMT) was used as a nanofiller. CS-MMT nanocomposites were prepared using the casting method. Thin nanocomposite foils were neutralized in NaOH solution, then the nanocomposite foils were soaked in simulated body fluid (SBF). Kinetics of crystallization of the apatite structure was observed using PIXE, FTIR-ATR and SEM/EDS techniques. It was shown that high concentrations of calcium and phosphate ions were located inside the nanocomposite structure. Bioactivity phenomena was initiated first in the nanocomposite foils (CS/MMT) and then in pure chitosan foils. These results suggest that the nano-clay particles (MMT) distributed in the biopolymer matrix acted as nucleaction centers of apatite. An apatite layer on pure chitosan crystallized much more slowly than in the case of nanocomposite materials. The CS-MMT nanocomposites therefore seem to be promising materials for bone repair implants because of their inherent bioactivity.

Bioactivity of Fibrous Polymer Based Nanocomposites for Application in Regenerative Medicine

Aim of the work was production of nanocomposite polymer fibres containing ceramic particles using the electrospinning method and characterisation of morphology and bioactivity of the produced materials. The first stage of investigations consisted in preparation of a series of poly-L-lactide (PLA) solutions in various solvents mixtures in order to reach viscosity which would allow formation of fibres by the electrospinning method. Ceramic nanoparticles such as tricalcium phosphate (TCP) and silica (SiO2) were used as nanofillers of the polymer matrix. Their particle size distribution in the solvent solution as well as in the polymer suspension was determined by dynamic light scattering method (DLS). Morphology of the nanoparticles was observed using transmission electron microscopy (TEM). Distribution of the nanofillers in the nanocomposite fibres as well as diameter and morphology of the fibres was assessed using scanning electron microscopy with energy dispersive spectroscopy method (SEM/EDS). Effect of the nanofillers addition and the shaping method on the structure of the PLA matrix was investigated on the basis of the thermal analysis methods (TG/DSC) on the nanocomposite foils prepared by casting. It was revealed that the nanocomposite fibres showed apatite nucleation in in vitro conditions i.e. after incubation in SBF (37°C/ 3 days).

Polymer Nanocomposite Scaffolds Modified with Carbon Nanotubes for Tissue Regeneration

Among the many applications of polylactide (PLA) in medicine, one of the most famous is porous scaffold for bone and cartilage regeneration. A new direction in the development of biodegradable polymer scaffolds is their modification using different types of nanoadditives. One type of these nanomaterials could be carbon nanotubes (CNT), which could influence the mechanical, electrical, physicochemical and biological properties of polymer matrices. Porous nanocomposite scaffolds were prepared using different techniques, such as salt leaching and a combination of salt leaching and gas foaming techniques. The bioactivity of MWCNTs was determined through their incubation in simulated body fluid (SBF) and verified using scanning electron microscopy (SEM). The best concentration of nanoadditives in the polymer matrices was evaluated on the basis of mechanical and in vitro tests of nanocomposite films using a universal testing machine (Zwick) and osteoblast-like human cells (MG63). The morphology, porosity and mechanical properties of the porous scaffold before and after modification with MWCNTs were evaluated using SEM, hydrostatic weighing and a universal test machine.

Potential of Superhydrophobic Layer on the Implant Surface

The aim of the work was the deposition of polymer fibres of submicrometric and nanometric diameter. A layer of the fibres was produced from biocompatible polymer, i.e. poli (ε) caprolactane (PCL). The polymer was dissolved in a mixture of DMF:DCM solvents. In order to enhance the hydrophobic effect, silica particles (5–10 nm) were introduced into the polymer solution. PCL fibres were produced using electric field of 25 kV. Wettability of the produced layer was determined using the method of sitting drop (DSA T500). Its microstructure was observed using scanning an electron microscope (Nova NanoSEM) and an atomic force microscope (MULTIMODE 8 AFM, Bruker). It was revealed that only coatings made of the pure polymer fibres showed superhydrophobicity (PCL fibres, wetting angle of 151o), while the nanocomposite fibres made of PCL and 3 wt.% SiO2 formed a layer with a wetting angle of 113o, which was more hydrophobic than a conventional polymer layer made by casting (wetting angle of PCL foil is 90o).

Search for Fibrous Aggregates Potentially Useful in Regenerative Medicine Formed under Physiological Conditions by Self-Assembling Short Peptides Containing Two Identical Aromatic Amino Acid Residues

This study investigates the propensity of short peptides to self-organize and the influence of aggregates on cell cultures. The dipeptides were derived from both enantiomers of identical aromatic amino acids and tripeptides were prepared from two identical aromatic amino acids with one cysteine or methionine residue in the C-terminal, N-terminal, or central position. The formation or absence of fibrous structures under physiological conditions was established using Congo Red and Thioflavine T assays as well as by microscopic examination using normal and polarized light. The in vitro stability of the aggregates in buffered saline solution was assessed over 30 days. Materials with potential for use in regenerative medicine were selected based on the cytotoxicity of the peptides to the endothelial cell line EA.hy 926 and the wettability of the surfaces of the films, as well as using scanning electron microscopy. The criteria were fulfilled by H-dPhedPhe-OH, H-dCysdPhedPhe-OH, H-CysTyrTyr-OH, H-dPhedPhedCys-OH, H-TyrTyrMet-OH, and H–TyrMetTyr–OH. Our preliminary results suggest that the morphology and cell viability of L919 fibroblast cells do not depend on the stereochemistry of the self-organizing peptides.