Publikacje

The main purpose of the work was to develop a drug releasing coatings on the surface of medical devices exposed to blood flow, what should enable effective inhibition of blood coagulation process. As a part of the work, the process of encapsulating the anticoagulant drug eptifibatide (EPT) in poly(DL-lactic-co-glycolic acid) (PLGA) nanoparticles was developed. EPT encapsulation efficiency was 29.1 ± 2.1%, while the EPT loading percentage in the nanoparticles was 4.2 ± 0.3%. The PLGA nanoparticles were suspended in a polyanion solution (hyaluronic acid (HA)) and deposited on the surface-treated thermoplastic polyurethane (TPU) by a layer-by-layer method. As a polycation poly-L-lysine (PLL) was used. The influence of released EPT on the activation of the coagulation system was analyzed using dynamic blood tester. Performed experiments show an effective delivery of the drug to the bloodstream and low risk of platelets (membrane receptor) activation. The dynamic blood test process, including its physical phenomenon, was described using numerical methods, i.e. a finite volume cone-and-plate test model as well as non-Newtonian blood models. The values of shear stress and blood flow velocity under the fast-rotating cone were computed applying boundary conditions of cylinder wall imitating blood-nanomaterial interaction. Implementing boundary conditions as initial shear stress values of bottom cylinder wall resulted in the increase of shear stress in blood under rotating cone. The developed system combining drug eluting polymeric nanoparticles with the polyelectrolyte “layer-by-layer” coating can be easily introduced to medical implants of various shape, with the advantages of resorbable drug carriers allowing for local and controllable delivery of anti-thrombogenic drugs.

Cancer is one of the biggest healthcare concerns in our century, a disease whose treatment has become even more difficult following reports of drug-resistant tumors. When this happens, chemotherapy treatments fail or decrease in efficiency, leading to catastrophic consequences to the patient. This discovery, along with the fact that drug resistance limits the efficacy of current treatments, has led to a new wave of discovery for new methods of treatment. The use of nanomedicine has been widely studied in current years as a way to effectively fight drug resistance in cancer. Research in the area of cancer nanotechnology over the past decades has led to tremendous advancement in the synthesis of tailored nanoparticles with targeting ligands that can successfully attach to chemotherapy-resistant cancer by preferentially accumulating within the tumor region through means of active and passive targeting. Consequently, these approaches can reduce the off-target accumulation of their payload and lead to reduced cytotoxicity and better targeting. This review explores some categories of nanocarriers that have been used in the treatment of drug-resistant cancers, including polymeric, viral, lipid-based, metal-based, carbon-based, and magnetic nanocarriers, opening the door for an exciting field of discovery that holds tremendous promise in the treatment of these tumors.

Physicochemical, electrochemical and biological performance of 4 types of all-carbon nanotube layers was studied. Higher oxidation state of carbon was responsible for micro-scaled uniformity of the layers and excellent electrical conductivity, while nitrogen containing functional groups yielded materials with anisotropy similar to natural tissues and reduced work function. All materials were cytocompatible with mammalian fibroblasts (viability >80%, cytotoxicity <3% at day 7) and human dermal fibroblast (viability of cells >70% at day 1), while reducing bacterial and cancer cells proliferation without adding any drug. After 8 h culture, a ~50% depletion in the number of Gram-positive bacteria was observed on materials with lower work function, while Gram-negative bacteria were more sensitive towards carbon coordination number and presence of nitrogen atoms (cell depletion of up to 48% on amidized carbon nanotubes). After 1-day culture, >80% reduction in the melanoma cells number, connected with enhanced production of reactive oxygen species (ROS) was observed. All-carbon nanotube layers decreased bacteria and cancer cell functions without negatively influencing mammalian cells nor using drugs and we believe that this can be explained by various sensitivity of the tested cells towards exogenous ROS overproduction. As the concerns over implant-related infections as well as rates of antibiotic-resistant bacteria and chemotherapeutic-resistant cancer cells are growing, such materials should pave the way for a wide range of biomedical applications.

Acoustic emission (AE) was applied for detection of microcrack initiation in carbon fiber reinforced polymer composites subjected to shear stresses. Experimental materials were prepared from polyester bonded unidirectional (1D) non-crimp fabric and 2D plain-weave carbon fiber fabrics, using the resin transfer moulding technology. Control of epoxy resin/carbon textile proportions enabled variation of fiber volume content from small (34/35% for 2D/1D), through medium (51%) to high (68%). Rectangular samples (45×4×2 mm) were cut from 1D plates along [0] and across [90] fibers. Similar size samples from 2D plates were cut along warp/weft axes as well as in two orthogonal bias directions. Selected side surfaces were polished for microscopic (SEM) observations. Short-beam-strength tests were performed in 3-point bending (l/h=4), with two AE sensors attached for damage monitoring, which allowed to interrupt loading sequence before final failure. The acoustic emission historic index was the most effective AE parameter in damage initiation control. Microcracks developing on polished composite side-surfaces were observed under the SEM and direct microscopic evidence confirmed fiber debonding to be the principal mechanism of crack initiation in these materials and testing conditions before any further damage.

The goal of this study was to investigate the influence of multi-walled carbon nanotubes (MWCNTs) before and after chemical functionalisation, graphene oxide (GO), and hybrid coating deposited on a titanium (Ti) surface on the nerve cell response in vitro. The physicochemical properties of the surface of the carbon nanomaterial coatings deposited on the Ti substrate using electrophoretic deposition were investigated, followed by biological tests. Scanning and transmission electron microscopy and X-ray photoelectron spectroscopy were used to evaluate the microstructure and chemistry of the carbon nanomaterial coatings. Electrochemical characterisation of the carbon nanomaterial coatings on metal substrates was investigated using cyclic voltammetry and cathodic charge storage capacity. During in vitro analysis, all samples were placed in direct contact with human neuroblastoma SH-SY5Y cells. The viability were analysed after 48 and 72 h of culture. Moreover, the cell morphology in contact with the carbon nanomaterial coatings was observed using fluorescence microscopy. Additionally, the neurite outgrowth and number of pyknotic nuclei were examined using cell microphotographs. GO exhibited the best biological results among all analysed samples, with a positive effect on cell viability, neural cell morphology, and especially neurite outgrowth, and significantly improved the biological properties of the other hybrid (nanocomposite) coatings. GO coating is not an electrochemically active material, thus its applicability for the production of electrodes for nerve stimulation is limited. However, it may be useful as a scaffold for nerve cell stimulation and regeneration. The advantageous electrochemical activity of MWCNT coatings and a satisfactory cell response greater than the Ti surface alone will pave the way for further research on electrodes for nerve cell stimulation

In this paper we have presented results of our studies on chitosan/graphene oxide (CS/GO) and chitosan/re-duced graphene oxide (CS/rGO) hybrid nanocomposites. First, L-ascorbic acid (L-AA), grape extract (GE), and green tea extract (GT) were tested as green reducing agents for reduced graphene oxide synthesis. Structural and chemical properties of the obtained rGOs were examined by X-ray diffraction (XRD), attenuated total re flection Fourier-transform infrared spectroscopy (ATR-FTIR), and X-ray photoelectron spectroscopy (XPS). Next, GO and rGOs were introduced into the chitosan matrix to prepare a series of hybrid nanocomposites. Their physico-chemical properties were evaluated by XRD, ATR-FTIR, DSC (differential scanning calorimetry), SEM (scanning electron microscopy), wettability and mechanical testing. It was found that all of the introduced nanofillers affected the structural, thermal, microstructural, mechanical, and surface properties of the nanocomposites. Addition of GO resulted in the increase of Young's modulus by 35%, while the composites reinforced with rGO_L-AA were soft and easy to bend in hand without cracking. We showed that simultaneous synthesis of rGO-L-AA and fabrication of the CS/rGO_L-AA hybrid nanocomposite allowed to fully exploit the potential of the chitosan/rGO system. The developed materials, after detailed biological characterization, may be potentially applicable in bone and cartilage tissue engineering.

Increased application of organic compounds, mainly in form of synthetic resins, used as binders for moulding and core sands in metal casting, may have an adverse effect on the environment and work conditions in foundry plants. In this article we focused on the identification of the degradation products formed during laboratory scale simulation of complex thermal degradation of commercial binder. For our investigation we have chosen the phenol-formaldehyde based resin hardened by a mixture of organic esters (PFRE) as it is widely used in the core and mould sand technology. The identified degradation products obtained during the experiments varied depending on mechanism used for pyrolysis. In the “slow” evaluation, simple compounds such as: CO, CO2,NH3,H2O, phenol and CH4 were generated. Meanwhile, during the “fl” pyrolysis (500, 700, 900 and 1100 °C), mainly phenol and its methyl and ethyl derivatives as well as benzene were released. It was determined that the pyrolysis products and their ratio depended on the temperature during the degradation process.

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.

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.

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.

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.

Phase change materials (PCMs) are currently an important class of modern materials used for storage of thermal energy coming from renewable energy sources such as solar energy or geothermal energy. PCMs are used in modern applications such as smart textiles, biomedical devices, and electronics and automotive industry. These materials accumulate thermal energy in the form of latent heat of phase transition that provides a greater energy storage density with a smaller temperature difference between storing and releasing heat, compared to the sensible heat storage method. Since the 1980s, different groups of materials have been investigated as potential phase change materials, including salts and salt hydrates, paraffins, saturated fatty acids, and polymeric materials, for example, poly(ethylene glycol). Recently, a growing interest in application of nanotechnology and nanomaterials to improve properties, usability, and processability of PCMs has been observed. This chapter reviews the current state of the art in nanotechnology and nanomaterials application for phase change materials to develop composites with improved product performance and safety.

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.

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.

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.

Coal tar pitch (CTP) modified with silicon carbide nanoparticles (nSiC) was used as a carbon binder precursor for the manufacture of carbon materials. Carbon samples were prepared in the form of a composition consisting of synthetic coke, graphite and nSiC- modified CTP prior to heat treatment at temperatures from 800 °C to 2800 °C. The effect of ceramic nanofiller in CTP on oxidation resistance of carbon samples obtained at various temperatures was studied. Physical and mechanical properties of carbon samples obtained at 2000 °C and 2800 °C were analysed. nSiC presence in CTP was found to change the elevated temperature properties of carbon samples. The oxidation tests conducted at 600 °C in air showed a significant improvement of the resistance of carbon samples modified with small amount of nSiC and annealed at 2000 °C. Properties investigated included characteristics important for application of carbon materials for carbon electrode manufacturing, i.e., electrical and thermal conductivities as well as mechanical properties. Due to micro-structural changes of carbon samples in the presence of nSiC filler physical and mechanical properties improved after annealing the samples at high temperature in comparison to unmodified carbon samples.

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.

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.

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.

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.

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.

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.

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.

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.

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.

AIM:

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.

MATERIALS AND METHODS:

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.

RESULTS:

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.

CONCLUSION:

The results obtained validate the choice of biomaterial used in this study as well as the method of its application.

Objectives

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.

Methods

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.

Results

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.

Conclusions

The OBLs were in general outdone by the conventional composite.

Clinical significance

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.

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.

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.

The aim of the study was the evaluation of gamma irradiation and electron beams for sterilization of porous scaffolds with shape memory behavior obtained from biodegradable terpolymers: poly(L-lactide-co-glycolide-co-trimethylene carbonate) and poly(L-lactide-co-glycolide-co-"-caprolactone). The impact of mentioned sterilization techniques on the structure of the scaffolds before and after the sterilization process using irradiation doses ranged from 10 to 25 kGy has been investigated. Treatment of the samples with gamma irradiation at 15 kGy dose resulted in considerable drop in glass transition temperature (Tg) and number average molecular weight (Mn). For comparison, after irradiation of the samples using an electron beam with the same dose, no significant changes in structure or properties of examined scaffolds have been noticed. Higher doses of irradiation via electron beam caused essential changes of the scaffolds’ pores resulting in partial melting of their surface. Nevertheless, obtained results have revealed that sterilization with electron beam, when compared to gamma irradiation, is a better method because it does not affect significantly the physicochemical properties of the scaffolds. Both used methods of sterilization did not influence the shape memory behavior of the examined materials.

Hydrogels offer several advantages as biomaterials for bone regeneration, including ease of incorporation of soluble substances such as mineralization-promoting enzymes and antibacterial agents. Mineralization with calcium phosphate (CaP) increases bioactivity, while antibacterial activity reduces the risk of infection. Here, gellan gum (GG) hydrogels were enriched with alkaline phosphatase (ALP) and/or Seanol®,a seaweed extract rich in phlorotannins (brown algae-derived polyphenols), to induce mineralization with CaP and increase antibacterial activity, respectively. The sample groups were unmineralized hydrogels, denoted as GG, GG/ALP, GG/Seanol and GG/Seanol/ALP, and hydrogels incubated in mineralization medium (0.1 M calcium glycerophosphate), denoted as GG/ALP_min, GG/Seanol_min and GG/Seanol/ALP_min. Seanol® enhanced mineralization with CaP and also increased compressive modulus. Seanol® and ALP interacted in a non-covalent manner. Release of Seanol® occurred in a burst phase and was impeded by ALP-mediated mineralization. Groups GG/Seanol and GG/ALP/Seanol exhibited antibacterial activity against methicillin-resistant Staphylococcus aureus. GG/Seanol/ALP_min, but not GG/Seanol_min, retained some antibacterial activity. Eluates taken from groups GG/ALP_min, GG/Seanol_min and GG/ALP/Seanol_min displayed comparable cytotoxicity towards MG-63 osteoblast-like cells. These results suggest that enrichment of hydrogel biomaterials with phlorotannin-rich extracts is a promising strategy to increase mineralizability and antibacterial activity.

Bone scaffolds are susceptible for bacterial infection when implanted, particularly in compromised bone. Therefore anti-bacterial bone scaffolds are desirable. Here a novel approach to provide bactericidal properties for titanium dioxide scaffolds is proposed. Gentamicin loaded poly(L-lactide-co-glycolide) microparticles were immobilized on the scaffold pore walls by sodium alginate hydrogel. The results show that the microparticles were effectively immobilized on the scaffolds. Desired burst release was observed within the first 8 h and gentamicin dose reached 125 μg from single scaffold that corresponded to ~ 25% of total drug introduced in the system. Following the initial burst, the dose was gradually decreasing up to day 10 and afterwards a sustained release of 3 μg/day was measured. Cumulatively ~ 90% of the drug was delivered up to day 50. Above pattern, i.e. burst release with following sustained release, is desired for prevention of perioperative bone infections: burst release stops local infections during post-implantation “decisive period” while further sustained drug release prevents bacterial recolonization. In vitro studies confirmed antimicrobial activity of released gentamicin against Staphylococcus spp. and cytocompatibility of the system with osteoblast-like cells (MG-63). Thus the system is a viable option for the treatment of bone tissue defects.

In addition to the many benefits of coal tar pitch, these materials are known to contain polycyclic aromatic hydrocarbons. For this reason, studies are being developed to elaborate new, ecologically friendly, alternative binders for carbon–graphite technology. This article presents the results of wood tar recovered during thermal degradation of selected types of woods as alternative binders in the manufacture of carbon materials. Two kinds of wood tars obtained from different raw materials were analyzed. Sawdust thermal conversion makes it possible to obtain carbon binders with a lower coking value and quinoline-insoluble matters in comparison to coal tar pitch. These binders produce significantly reduced emissions of polycyclic aromatic hydrocarbons in carbon–graphite technology. Carbon samples manufactured using wood-derived binders with carbon fillers showed similar density and mechanical compression strength values compared to those based on conventional coal tar pitch binders.

Przedmiotem wynalazku jest sposób otrzymywania bioaktywnych, resorbowalnych implantów do leczenia ubytków kostnych, w postaci modyfikowanych, resorbowalnych gąbek polimerowych. Porowate struktury wytwarzane z polimerów resorbowalnych są coraz powszechniej stosowane do leczenia i rekonstrukcji tkanki kostnej człowieka. Ubytki kostne, szczególnie o większych rozmiarach, powstające w wyniku urazu, infekcji, zmian degeneracyjnych itp. nie ulegają samoistnemu wygojeniu i stanowią nadal nierozwiązany problem w chirurgii kostnej. Jedyną alternatywą dla auto lub alloprzeszczepów stają się metody z wykorzystaniem kościozastępczych materiałów syntetycznych. Jednym z polimerów, coraz powszechniej stosowanym w medycynie, jest resorbowalny polilaktyd (PLA), należący do grupy poliestrów alifatycznych. Pomimo jego zalet w z astosowaniu w leczeniu tkanki kostnej, nie jest on jednak bioaktywnym materiałem zwiększającym potencjał regeneracyjny tkanki kostnej. Z tego względu, jako fazę modyfikującą matrycę polimerową, często wprowadza się bioaktywne nanododatki, takie jak hydroksyapatyt lub bioszkło.Przedmiotem wynalazku jest sposób otrzymywania bioaktywnych, resorbowalnych implantów.

The work presents results on the manufacture and comparative assessment of the structure and microstructure parameters of polyacrylonitrile polymer (PAN)-based carbon nano- and micro-fibers. Using the same polymer solution, PAN nano- and microfibers were obtained. The PAN nanofibers were obtained by electrospinning, and microfibers were spun using the conventional solution-spinning method. The PAN-based fiber precursors were annealed to 1000 °C, 2000 °C and to 2800 °C. Using X-ray diffraction and Raman spectroscopy, the structural and microstructural parameters of both types of carbon fibers were examined. The morphology of PAN nanofibers and carbon nanofibers (CNF) were studied by SEM. Both types of ex-PAN carbon fibers (nano and micro) have similar the c-axis spacing (d002) values and crystallite sizes after heat treatment to 2000 °C presenting turbostratic structure. HR-TEM images of low temperature CNF show uniform microstructure with the misoriented small carbon crystallites along the fiber axis. The ratio of the integrated intensities of the D and G peaks for carbon nanofibers after heat treatment at 2000 °C was distinctly higher in comparison to carbon microfibers (CF). After additional annealing the fibers to 2800 °C a better structural ordering show CNF. The crystallite sizes (Lc, La) in CNF were distinctly higher in comparison to the crystallites in CF. CF consist of two carbon components, whereas CNF contain three carbon components varying in structural and microstructural parameters. One of carbon phases in CNF was found to have the interlayer spacing close to graphite, i.e. d002=0.335 nm.

The aims in treating patients diagnosed with The aims in treating patients diagnosed with critical-sized bone defects resulting from bone cysts are to replace the lost bone mass after its removal and to restore function. The standard treatment is autologous or allogeneic bone transplantation, notwithstanding the known consequences and risks due to possible bone infection, donor site morbidity, bleeding and nerve injury and possible undesirable immune reactions. Additionally, allogeneic grafts are inhomogeneous, with a mosaic of components with difficult-to-predict regenerative potential, because they consist of cancellous bone obtained from different bones from various cadavers. In the present study, a 22-year-old patient with a history of right humerus fracture due to bone cysts was diagnosed with recurrent cystic lesions based on X-ray results. The patient qualified for an experimental program, in which he was treated with the application of a bioresorbable polylactide hybrid sponge filled with autologous platelet-rich plasma. Computed tomography and magnetic resonance imaging performed 3, 6, and 36 months after surgery showed progressive ossification and bone formation inside the defect cavity in the humerus. Three years after treatment with the bone substitute, the patient is pain free, and the cystic lesions have not reoccurred.

Akrylanowy cement kostny według niniejszego wynalazku eliminuje szkodliwy dla otoczenia efekt cieplny występujący w trakcie jego wiązania, poprzez łatwą modyfikację dostępnych na rynku medycznym cementów kostnych, bez zmiany stosowanych dotychczas procedur chirurgicznych. Zastosowanie do akumulacji energii cieplnej materiału fazowo – zmiennego ze składnikiem aktywnym w postaci PEG, dzięki zachodzącym w nim przemianom fazowym, w czasie których pochłaniane są duże ilości ciepła, umożliwia obniżenie temperatury wiązania materiału do około 45°C. Jednocześnie, zgodnie z normą ISO 5833:2002 pt.: „Implants for surgery - Acrylic resin cements” zostaje zachowany odpowiedni czas wiązania materiału.

Multi-walled carbon nanotubes (MWCNTs) as a modifying phase on the titanium support can be potentially used for medical purposes as a material for the production of implants or implantable electrodes or for applications for cardiac surgery. Developing better blood compatible biomaterials must be connected with the condition of their anti-thrombogenic characteristic. A carbon nanotube layer was formed on a titanium plate coated in half with MWCNTs to have admission to: MWCNTs coating, to the Ti/MWCNTs interface region at the MWCNTs coating edge and finally to the Ti support. The Raman measurements were performed in two different locations: in the interface/edge region of the titanium and MWCNTs coating and in the center of the MWCNTs layer. For each of these positions, measurements in two different depths were performed: on the sample top surface of the MWCNT layer and near the bottom of the MWCNTs layer, i.e. at the titanium support interface. The studied sample regions differ in G-, D- and D′-mode structural characteristics as dispersion, crystallinity, the size of the arranged domains, and the distance between the point defects. The phase boundary region is more disordered and exposed to a greater surface tension. These features influence the interactions with albumin which represented the material behavior in contact with the tissue. The MWCNTs coating is hydrophilic (contact angle ∼55°), in the border area this value increases to ∼60°, then Ti support is hydrophobic (∼98°). Two dimensional correlation analysis allows us to unravel albumin-MWCNTs' interaction. The cross-peaks show a contribution from G+ and G− carbon nanotubes bands and protein secondary structure demonstrating the formation of a film on the surface of the test sample and indicate the change of the albumin conformation during adhesion.

Since there are more and more cases of multiresistance among microorgani sms, rational use of antibiotics (especially their systemic vs. local application)is of great importance. Here we propose polymeric nanoparticles as locally applied gentamicin delivery system useful in osteomyelitis therapy. Gentamicin sulphate (GS) was encapsulated in the poly(lactide-co-glycolide)(PLGA 85:15)nanoparticles by double emulsification (water/oil/water, W1/O/W2). The nanoparticles were characterized by dynamic light scattering, laser electrophoresis and atomic force microscopy. UV-vis spectroscopy (O-phthaldialdehyde assay, OPA) and Kirby-Bauer tests were used to evaluate drug release and antimicrobial activity, respectively. Physicochemical characterization showed that size, shape and drug solubilization of the nanoparticles mainly depended on GS content and concentration of surface stabilizer (polyvinyl alcohol, PVA). Laser electrophoresis demonstrated negative value of zeta potential of the nanoparticles attributed to PLGA carboxyl end group presence. Drug release studies showed initial burst release followed by prolonged 35-day sustained gentamicin delivery.Agar-diffusion tests performed with pathogens causing osteomyelitis (Staphylococcus aureus and Staphylococcus epidermidis, both reference strains and clinical isolates) showed antibacterial activity of GS loaded nanoparticles (GS-NPs). It can be concluded that GS-NPs are a promising form of biomaterials useful in osteomyelitis therapy.

The surface of Ti–13Nb–13Zr alloy was modified in 0.1 M calcium hypophosphite (Ca(H2PO2)2) solutions via the addition of tricalcium phosphate, wollastonite or silica powders using a plasma electrolytic oxidation process. Depending on the anodizing bath chemical composition and applied voltage, various oxide layers were formed on the substrate. The water contact angle of the oxide layer was measured. The biological investigations using osteoblast-like cells MG-63 showed that the suspensions utilized during anodization strongly influenced the oxide layer bioactivity. Only the traces of the alloy elements were involved in Ringer solution after 5 months of immersion.

In the current study, the effect of post-plasma grafting of 2-aminoethyl methacrylate (AEMA) and the subsequent covalent immobilization of gelatin (GelB) on poly(-lactide-co-glycolide) (PLGA) thin films were investigated. The applied modification resulted in surface chemistry changes of PLGA. More specifically, an increase of nitrogen from 0 at% to 14 at% with a concomitant decrease in carbon and oxygen concentration was observed. The samples were more hydrophilic after the treatment as reflected by a decrease of the water contact angle from 72° to 33° and more rough at the nanoscale as shown by atomic force microscopy (increase of Ra roughness from 0.7 nm to 10 nm). The growth of osteoblast-like MG-63 cells was enhanced on biofunctionalised PLGA-AEMA-GelB surfaces and the cells were more homogenously distributed than on non-modified PLGA. Our findings are especially important for tissue engineering applications, where substrates supporting homogenous cell cultures are particularly promising.

One of the major problems in orthopedic surgery is infection associated with implantation. The treatment is a very difficult and long-term process. A solution to this issue can be the use of implants which additionally constitute an antibiotic carrier preventing the development of an infection. Prototypes of biodegradable intramedullary nails made of three different composites with a poly(L-lactide) matrix were designed. The nails served as gentamicin sulfate (GS) carrier — an antibiotic commonly used in the treatment of osteomyelitis. The matrix was reinforced with carbon fibers (CF), alginate fibers (Alg) and magnesium alloy wires (Mg), as well as modified with bioactive particles of tricalcium phosphate (TCP) in various systems. In this way, novel, multi-phase and multifunctional degradable intramedullary nails were obtained. The tests demonstrated strong dependence between the type of the modifying phase introduced into the composite, and the rate of drug release. Introduction of gentamicin into the nail structure strengthened and prolonged antibacterial activity of the nails.

In the present article, new polylactide/alginate fibers composites were investigated. Composite pre-pregs were made by solution casting method. The aim of the study was to define physico-mechanical properties of developed materials. The scope of the studies included: examining the static mechanical properties, properties of the surface and their changes during degradation. Moreover, intensity of the release of degradation products to the environment and a change of the mass of examined samples were analyzed. Obtained results were evaluated taking into account possibility to use prepared composited as materials for vascular implants.