: Materials Letters 190 (2017) 67–70
Three-dimensional scaffolds are often used to support healing process for bone defects reconstruction.Unfortunately a common occurrence of post-implantation infections results in their high failure rate.Thus we propose new TiO2 scaffolds that combine mechanical support and controlled antibiotics release to assure bactericidal properties. Poly(L-lactide-co-glycolide) microparticles containing vancomycin were successfully immobilized on the scaffolds pore walls with the use of cross-linked sodium alginate. Prolonged drug release was achieved from such systems with initial burst release of 22% within 8 h,which falls within ‘‘decisive period” after surgical procedures of effective infection control.Antimicrobial properties of drug released from the systems against Staphylococcus spp. as well as cytocompatibility in contact with osteoblast-like cells (MG-63) were proven. Hence such scaffolds maybe promising for infection prevention and bone tissue defects treatment.
: Engineering of Biomaterials 139 (2017) 2-7
The aim of this work was to examine composite membranes obtained by means of phase inversion from a synthetic stable polymer – polyvinylidene difluoride (PVDF). The piezoelectric polymer was modified with 0.5-1wt% addition of commercial carbon fillers: graphite oxide (GO, 1wt%), multiwalled carbon nanotubes (CNT, 1wt%) and functionalized nanotu-bes (CNT-COOH, 0.5wt%). The membranes were obtained by solidification of nanocomposite solutions in coagulation bath (CH3OH). The obtained series of materials differed in surface porosity (P), electric conductivity (σ) and surface free energy (SFE). It was proved that presence of carbon nanoadditive influen-ced microstructure of the membranes: the mean size of pores in the membrane rose in the following order: GO→CNT→CNT-COOH. The very same system de-picted the influence of the filler on the membrane stru-cture: the increase in membrane crystallinity (λ) and the β phase share (FT Raman). From all the examined nanocomposite systems, the PVDF modified with 0.5wt% CNT-COOH displayed the most advantageous electric properties. These nanocomposite membrane (PVDF/CNT-COOH) could be used as a low-voltage electrodes in biomedical application. Yet, taking into account the other physicochemical, mechanical and structural properties, the membranes modified with 1wt% CNT and 1wt% GO were also interesting.
: Applied Surface Science 403 (2017) 206–217
Coating the material of choice with a layer of well-adhered carbon nanotubes is a subject of interest in many fields of materials science and industry. Electrophoretic deposition is one of the methods to handle this challenging task. In this process, careful designing of the deposition parameters is crucial in obtaining the product of strictly desired properties. This study was aimed to identify the influence of the diluent on the physicochemical ad electrochemical qualities of the final product. By analyzing the properties of the suspensions being used, we were able to hypothesize on the mechanisms of carbon nanotubes—liquid interactions and their outcome on the thickness, homogeneity, chemical and structural composition and electrical conductivity of the metal substrate covered with a layer of carbon nanotubes. We obtained a materials, composed of metal and a layer of CNTs, with conductivity that is superior to an unmodified metal. This types of materials may find numerous applications in fabrication of novel electronic devices, including the implantable electrodes for biomedicine—as reported in our previous studies, these types of coating are biocompatible.
: Applied Physics. A, Materials Science & Processing 123 (2017) 120
: Journal of Materials Science Composites (2017) 52:12221–12234
: Journal of Alloys and Compounds 709 (2017) 464-472
Titanium alloys varying in the silver content (3.5 at.%; 5 at.%; 10 at.% or 20 at.%) were produced by means of powder metallurgy. The alloys displayed different phase structure. In alloys with the silver content of 3.5 at.% and 5 at.% the solid solution α-Ti was identified. In alloys with the higher silver content, i.e. 10 and 20 at.%, both the solid solution and the equilibrium phase Ti2Ag were observed, whereas in alloys with the highest silver content of 20 at.% there were also the equilibrium phase TiAg and fine silver identified. The Ti-20%Ag alloy had 80% lower compressive stress and 30% lower hardness compared to the Ti-10%Ag alloy. The alloy with 10% silver showed the best mechanical properties as well as the best surface wettability.
: Bulletin of Materials Science 40(1) (2017) 201-212
: Materials Science and Engineering C 77 (2017) 521–533
Recent approaches in tissue regeneration focus on combining innovative achievements of stem cell biology and biomaterial sciences to develop novel therapeutic strategies for patients. Growing recent evidence indicates that mesenchymal stem cells harvested from human umbilical cord Wharton's jelly (hUC-MSCs) are a new valuable source of cells for autologous as well as allogeneic therapies in humans. hUC-MSCs are multipotent, highly pro- liferating cells with prominent immunoregulatory activity. In this study, we evaluated the impact of widely used FDA approved poly(α-esters) including polylactide (PLA) and polycaprolactone (PCL) on selected biological properties of hUC-MSCs in vitro. We found that both polymers can be used as non-toxic substrates for ex vivo propagation of hUC-MSCs as shown by no major impact on cell proliferation or viability. Moreover, PCL significantly enhanced the migratory capacity of hUC-MSCs. Importantly, genetic analysis indicated that both polymers promoted the angiogenic differentiation potential of hUC-MSCs with no additional chemical stimulation. These results indicate that PLA and PCL enhance selected biological properties of hUC-MSCs essential for their re- generative capacity including migratory and proangiogenic potential, which are required for effective vascular repair in vivo. Thus, PLA and PCL-based scaffolds combined with hUC-MSCs may be potentially employed as future novel grafts in tissue regeneration such as blood vessel reconstruction.
: Journal of Nanomaterials (2017) Article ID 6578928
Silicon carbide nanoparticles (nSiC) have been used to modify coal tar pitch (CTP) as a carbon binder. The influence of ceramic nanoparticles on the structure and microstructure was studied. The structure of CTP-based carbon residue with various nSiC contents was analyzed by using SEM with EDAX, Raman spectroscopy, and X-ray diffraction. The effect of ceramic nanofiller on the crystallite sizes (, ) and the -axis spacing () in carbonized samples after heating from 1000 to 2800°C was analyzed. Ceramic nanofillers inhibit structural changes in carbonized samples heated to 1000°C. After heating CTP with nSiC above 2000°C, the carbon samples contained two carbon components differing in structural ordering. Ceramic nanoparticles increase carbon crystallite growth, while their impact on the -axis spacing is low.
: Opakowanie 2 (2017) 61-66
: International Journal of Polymer Science (2017) article ID 9051914
The influence of nanohydroxyapatite on the glass transition region and its activation energy, as well as on the tribological and mechanical properties of polyoxymethylene nanocomposites, was investigated using DMA, TOPEM DSC, nanoindentation, and nondestructive ultrasonic methods. It was found that the glass transition for unmodified POM was in the lower temperature range than in POM/HAp nanocomposites. Moreover, and activation energy were larger for POM/HAp nanocomposites. Friction coefficient was higher for POM/HAp nanocomposites in comparison to both POM homopolymer and POM copolymer. Simultaneously, the indentation test results show that microhardness is also higher for POM/HAp nanocomposites than for POM. From ultrasonic investigations it was found that the highest values of both longitudinal and transverse propagation waves and Young’s and shear modulus for POM homopolymer (DH) and POM copolymer T2H and their nanocomposites can be attributed to their higher degree of crystallinity in comparison to UH copolymer. Moreover, for POM/HAp nanocomposites with 5% of HAp, ultrasonic longitudinal wave velocity was almost constant even after 1000000 mechanical loading cycles, evidencing an enhancement of mechanical properties by HAp nanoparticles.
: Ceramics International 43 (2017) 8109–8118
: Materials Science and Engineering. C, Biomimetic Materials, Sensors and Systems 71 (2017) 1175-1191
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.
: Journal of Polymer Science. Part A, Polymer Chemistry 55(17) (2017) 2756–2769
The main objective of the presented research was to synthesise biodegradable aliphatic polycarbonates containing reactive carboxyl pendant groups and to examine the influence of the copolymer chain microstructure and composition on the process of their hydrolytic degradation and cytocompatibility. The work describes copolymerization of cyclic trimethylene carbonate derivative containing benzyl-ester pendant group (benzyl 5-methyl-2-oxo-1,3-dioxane-5-carboxylate) with trimethylene carbonate. The copolymerization was conducted with the use of zinc (II) and lanthanum (III) acetylacetonates as ring-opening polymerization coordination initiators. Detailed NMR analysis allowed to define the microstructure of the obtained copolymers, which depended on the composition and type of used initiator. The final tapered chain microstructure of the obtained copolymers was related to huge differences in comonomers reactivity and evidenced low level of transesterification of the main copolymer backbone. Chosen copolymers, with unprotected carbonyl groups, were subjected to in vitro degradation test and cytocompatibility studies. It was found that high concentration of carboxyl groups resulted in copolymers which formed hydrogels and were very prone to hydrolytic degradation; they were also cytotoxic toward osteoblast-like MG 63 cells. Copolymers with lower content of carboxyl groups were found less susceptible to degradation and cytocompatible with studied cells.
: Materials Letters 190 (2017) 13–16
Hydrogels are popular materials for tissue regeneration. Incorporation of biologically active substances, e.g. enzymes, is straightforward. Hydrogel mineralization is desirable for bone regeneration. Here, hydrogels of Gellan Gum (GG), a biocompatible polysaccharide, were mineralized biomimetically with CaCO3 using a double enzymatic approach. The enzymes urease (U) and carbonic anhydrase (CA) were incorporated in GG hydrogels. Hydrogels were incubated in a mineralization solution containing U substrate (urea) and calcium ions. U converts urea to ammonia (which raises pH) and CO2. CA catalyses the reaction of CO2with water to form HCO3−, which undergoes deprotonation to form CO32−, which react with Ca2+ to form insoluble CaCO3.
: Biomedical Materials 12(2) (2017) Article ID 025015
: Materials Science and Engineering. C, Biomimetic Materials, Sensors and Systems 70 (2017) 471-478
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.
: Composites Structures 161 (2017) 428-434
The work presents the fatigue mechanical properties of a composite material made of polyetheretherketone (PEEK) polymer and carbon fibres (CF) designed for structural biomaterials. Composite samples with various types of carbon fibre reinforcements were studied. The mechanical durability of the composite samples in simulated body solution was analysed. The samples were loaded for a predetermined number of cycles for various applied-force levels, at a frequency of 50 Hz under a bending force, and at 1 Hz under compression force. The mechanical changes were analysed taking into consideration the anisotropic structure of the composite samples made of fibre roving 1D, 2D tissue and carbon fibres in the form of braided fibre sleeves (MD). The ultrasonic method was applied to determine the changes in velocities measured in the composites. The average variations of mechanical stability of the composite samples kept in simulated body fluid were not significant after fatigue testing up to 1 * 106 cycles.
: Bio-Algorithms and Med-Systems 13(1) (2017) 25-35
: Surface and Coatings Technology 319 (2017) 33-46
Composite bioglass/chitosan and sol-gel glass/chitosan coatings were electrophoretically deposited (EPD) on a near-β Ti-13Nb-13Zr alloy. The influence of EPD parameters, such as chemical composition and suspension pH as well as potential difference and deposition time, on the uniformity of coatings has been studied. It was found that the pH value of the suspension and chemical composition have a significant impact on the electrokinetic properties of suspended chitosan molecules and glass particles, which in turn affect the deposition rate of EPD and the uniformity of as-deposited coatings. The thicknesses of the bioglass/chitosan and sol-gel glass/chitosan coatings were up to 2μm and 860nm, respectively. The microstructure of the coatings was characterized by scanning and transmission electron microscopy as well as X-ray diffractometry. The coating microstructure was composed of sol-gel glass particles or amorphous bioglass separate particles or agglomerates, homogeneously embedded in an amorphous chitosan matrix. The sol-gel particles consisted of hydroxyapatite (hp), CaSiO3 (tp) phases. The sol-gel glass/chitosan coating exhibited better adhesion to the titanium alloy substrate than the bioglass/chitosan coating. It was found that both types of coating improve the electrochemical corrosion resistance of the Ti-13Nb-13Zr alloy in Ringer's solution and are cytocompatible with osteoblast-like cells.
: Surface and Coatings Technology 324 (2017) 64-79
In this work, nanocomposite HA/chitosan coatings were electrophoretically deposited (EPD) on a near-β Ti-13Nb-13Zr alloy. The influence of the state of the HA particles introduced to the colloidal solution of chitosan (nc-HA-p as a nanopowder and nc-HA-s as nanoparticles suspended in ethanol), as well as the chemical composition of a multi-component HA-chitosan suspension and EPD parameters, on the homogeneity of coatings has been studied. It was established that the pH value and the chemical composition of the suspension have a substantial effect on the electrokinetic properties of suspended HA and chitosan particles. These are also influenced by the deposition kinetics of EPD and the uniformity of as-deposited coatings. The thickness of the nc-HA-p/chitosan and nc-HA-s/chitosan coatings was up to 750 nm and 1.5 μm, respectively. The nc-HA-s/chitosan coating microstructure consisted of HA nanoparticles, homogeneously embedded in an amorphous chitosan matrix. The nc-HA-p/chitosan coating microstructure was non-homogeneous, composed of HA agglomerates in a chitosan matrix. The presence of thin oxide layer was observed on the coatings/titanium alloy interface. The nc-HA-s/chitosan coating exhibited better adhesion to the titanium alloy substrate than the nc-HA-p/chitosan coating. It was found that the nc-HA-s/chitosan coating improves the electrochemical corrosion resistance of the Ti-13Nb-13Zr alloy in Ringer's solution, as well as its bioactivity and other biological properties.
: International Journal of Nanomedicine 12 (2017) 464-472
The addition of an antibacterial agent to dental implants may provide the opportunity to decrease the percentage of implant failures due to peri-implantitis. For this purpose, in this study, the potential efficacy of nanosilver-doped titanium biomaterials was determined. Titanium disks were incorporated with silver nanoparticles over different time periods by Tollens reaction, which is considered to be an eco-friendly, cheap, and easy-to-perform method. The surface roughness, wettability, and silver release profile of each disc were measured. In addition, the antibacterial activity was also evaluated by using disk diffusion tests for bacteria frequently isolated from the peri-implant biofilm: Streptococcus mutans, Streptococcus mitis, Streptococcus oralis, Streptococcus sanguis, Porphyromonas gingivalis, Staphylococcus aureus, and Escherichia coli. Cytotoxicity was evaluated in vitro in a natural human osteoblasts cell culture. The addition of nanosilver significantly increased the surface roughness and decreased the wettability in a dose-dependent manner. These surfaces were significantly toxic to all the tested bacteria following a 48-hour exposure, regardless of silver doping duration. A concentration of 0.05 ppm was sufficient to inhibit Gram-positive and Gram-negative species, with the latter being significantly more susceptible to silver ions. However, after the exposure of human osteoblasts to 0.1 ppm of silver ions, a significant decrease in cell viability was observed by using ToxiLight™ BioAssay Kit after 72 hours. Data from the present study indicated that the incorporation of nanosilver may influence the surface properties that are important in the implant healing process. The presence of nanosilver on the titanium provides an antibacterial activity related to the bacteria involved in peri-implantitis. Finally, the potential toxicological considerations of nanosilver should further be investigated, as both the antibacterial and cytotoxic properties may be observed at similar concentration ranges.
: Surface and Coatings Technology 328 (2017) 1-12
During anodization, the properties of the oxide layer depend on the chemical composition of the titanium alloy and on the parameters applied during surface treatment. The properties of the anodized surfaces influence their further functionalization. In this paper, ceramic multilayer coatings were formed on the Ti-6Al-7Nb, Ti-13Nb-13Zr, and Ti-15Mo alloys. A silica layer with wollastonite particles was formed on all the previously anodized Ti alloy samples. Using scanning electron microscopy, Raman spectroscopy, and X-ray diffractometry, respectively, the surface morphology, chemical composition and phase composition of the hybrid ceramic layers were investigated. In addition, the adhesion and hardness of the coatings were determined. The contact angle of the coatings was between 90.0 ± 0.2° and 114.3 ± 5.9°, and the surface roughness was < 2 μm. The modified surfaces were immersed in solutions containing protein-like collagen type I or lactoferrin. The coated Ti-15Mo surface exhibited the highest influence on both types of protein concentration in phosphate-buffered saline solution. However, after 1 day of culture, the adsorbed lactoferrin on the entire surface enhanced the growth of osteoblast-like MG-63 cells. Significant differences in cell culture were observed after 7 days, where the number of cells was much higher on the modified surface with lactoferrin. Collagen type I did not significantly enhance the cell behaviour; moreover, a large number of dead cells were found on these samples.
: Journal of Thermal Analysis and Calorimetry 127 (2017) 871-880
: In vivo 31(5) (2017) 895-903
To evaluate the utility of a novel nanocomposite biomaterial consisting of poly-L/D-lactide, and hydroxyapatite bioceramics, enriched with sodium alginate in articular cartilage defect treatment.
The biomaterial was prepared using the method of solvent casting and particle leaching. The study was conducted on 20 New Zealand White rabbits. Experimental osteochondral defects were created in the femoral trochlear grooves and filled with biomaterials. In control groups, the defects were left to spontaneously heal. The quality of newly-formed tissue was evaluated on the basis of macroscopic and histological assessment. Additionally the level of osteogenic and cartilage degradation markers were measured.
The majority of the defects from the treatment group were covered with tissue similar in structure and colour to healthy cartilage, whereas in the control group, tissue was uneven, and not integrated into the surrounding cartilage.
The results obtained validate the choice of biomaterial used in this study as well as the method of its application.
: Journal of Dentistry 56 (2017) 84-98
This study aims at evaluating and comparing mechanical, chemical, and cytotoxicological parameters of a commercial brand name composite material against two ‘own brand label’ (OBL) composites.
Parameters included depth of cure, flexural strength, degree of conversion, polymerization shrinkage, filler particle morphology and elemental analyzes, Vickers hardness, surface roughness parameters after abrasion, monomer elution, and cytotoxicity.
The conventional composite outperformed the OBLS in terms of depth of cure (p < 0.001), degree of cure at the first and last time intervals (p < 0.001), hardness (p < 0.001), and post-abrasion roughness (p < 0.05). The polymerization volumetric shrinkage ranged from 2.86% to 4.13%, with the highest shrinkage seen among the OBLs. Both Monomer elution from the OBLs was statistically significantly higher (p < 0.001). Statistically significantly higher cytotoxicity combined with altered morphology and loss of confluence was detected in the cells exposed to extracts from the OBLs.
The OBLs were in general outdone by the conventional composite.
OBLs restorative materials have become pervasive in the dental market. Manufacturers often promise equal or better characteristics than existing brand-name composites, but at a lower price. Dentists are highly recommended to reconsider utilization of OBLs lacking sound scientific scrutiny, and our findings underscore this recommendation.
: Journal of Nanomaterials (2017) Article ID 9246802
The aim of the study was to manufacture poly(lactic acid)- (PLA-) based nanofibrous nonwovens that were modified using two types of modifiers, namely, gelatin- (GEL-) based nanofibres and carbon nanotubes (CNT). Hybrid nonwovens consisting of PLA and GEL nanofibres (PLA/GEL), as well as CNT-modified PLA nanofibres with GEL nanofibres (PLA + CNT/GEL), in the form of mats, were manufactured using concurrent-electrospinning technique (co-ES). The ability of such hybrid structures as potential scaffolds for tissue engineering was studied. Both types of hybrid samples and one-component PLA and CNTs-modified PLA mats were investigated using scanning electron microscopy (SEM), water contact angle measurements, and biological and mechanical tests. The morphology, microstructure, and selected properties of the materials were analyzed. Biocompatibility and bioactivity in contact with normal human osteoblasts (NHOst) were studied. The coelectrospun PLA and GEL nanofibres retained their structures in hybrid samples. Both types of hybrid nonwovens were not cytotoxic and showed better osteoinductivity in comparison to scaffolds made from pure PLA. These samples also showed significantly reduced hydrophobicity compared to one-component PLA nonwovens. The CNT-contained PLA nanofibres improved mechanical properties of hybrid samples and such a 3D system appears to be interesting for potential application as a tissue engineering scaffold.
: Przemysł Chemiczny 96(7) (2017) 1531–1538
: Journal of Thermal Analysis and Calorimetry 127(1) (2017) 389-398
The aim of this study was to investigate the influence of the addition of smectite clay fillers to a polylactide matrix on the physical properties of the nanocomposites thus created, studied during the degradation process. A small amount of nanofiller (3–10 mass %) was used, and the clay was additionally modified with organic ammonium salt for better compatibility with the polymer matrix. Crystallisation, glass transition and melting temperature of the nanocomposites were investigated, and the resulting thermal, structural and mechanical properties were compared to those of a neat polylactide. The degradation process of the materials was examined during immersion in distilled water at 80 °C for 60 days using differential scanning calorimetry (DSC), thermogravimetric analysis (TG), X-ray diffraction (XRD) and scanning electron microscopy (SEM). Macroscopic changes were monitored and mechanical properties tested prior to degradation to evaluate the ability of the modified clay filler to reinforce the polymer and enhance elastic modulus, mechanical strength and Brinell hardness. The influence of the modified smectite filler on the thermal, mechanical and structural properties of the nanocomposites during degradation and its dependence on filler content were discussed and confirmed in the study. It was found that the addition of 3 mass% of the clay filler provides an increase of nearly 20 % in tensile strength, with improved stiffness. It was also found that the addition of organically modified clay to the polymer matrix significantly changes the hydrolytic degradation mechanisms of the polylactide, the crystallinity of the polymer and its degradation rate, depending on the amount of the filler.