Chemical Modification of Dental Dimethacrylate Copolymer with Tetramethylxylylene Diisocyanate-Based Quaternary Ammonium Urethane-Dimethacrylates-Physicochemical, Mechanical, and Antibacterial Properties.

In this study, two novel quaternary ammonium urethane-dimethacrylates (QAUDMAs) were designed for potential use as comonomers in antibacterial dental composite restorative materials. QAUDMAs were synthesized via the reaction of 1,3-bis(1-isocyanato-1-methylethyl)benzene with 2-(methacryloyloxy)ethyl-2-decylhydroxyethylmethylammonium bromide (QA10+TMXDI) and 2-(methacryloyloxy)ethyl-2-dodecylhydroxyethylmethylammonium bromide (QA12+TMXDI). Their compositions with common dental dimethacrylates comprising QAUDMA 20 wt.%, urethane-dimethacrylate monomer (UDMA) 20 wt.%, bisphenol A glycerolate dimethacrylate (Bis-GMA) 40 wt.%, and triethylene glycol dimethacrylate (TEGDMA) 20 wt.%, were photocured. The achieved copolymers were characterized for their physicochemical and mechanical properties, including their degree of conversion (DC), glass transition temperature (Tg), polymerization shrinkage (S), water contact angle (WCA), flexural modulus (E), flexural strength (FS), hardness (HB), water sorption (WS), and water leachability (WL). The antibacterial activity of the copolymers was characterized by the minimum bactericidal concentration (MBC) and minimum inhibitory concentration (MIC) against Staphylococcus aureus and Escherichia coli. The achieved results were compared to the properties of a typical dental copolymer comprising UDMA 40 wt.%, Bis-GMA 40 wt.%, and TEGDMA 20 wt.%. The introduction of QAUDMAs did not deteriorate physicochemical and mechanical properties. The WS and WL increased; however, they were still satisfactory. The copolymer comprising QA10+TMXDI showed a higher antibacterial effect than that comprising QA12+TMXDI and that of the reference copolymer.

Shaping the Structure and Properties of TiO2-ZnO Oxide Coatings Produced by Plasma Electrolytic Oxidation on Titanium Substrate.

The paper presents the results of preliminary research on the possibility of synthesizing ZnO-TiO2 mixed coatings by plasma electrochemical oxidation (PEO). The aim of the work was to synthesize TiO2-ZnO mixed coatings on a titanium substrate from an electrolyte containing ZnO nanoparticles (NPs) and to assess the parameters of PEO on the structure, chemical composition, and properties of the obtained oxide coatings. The PEO process was carried out under various current-voltage conditions using different signals: DC, DC pulse, and AC. In this work, optimal conditions for the PEO process were determined to obtain well-adhering oxide coatings with the highest possible content of ZnO. The structure and morphology of the resulting oxide coatings were investigated, and their chemical and phase composition was comprehensively examined (EDX, XRD, XPS, and GD-OES). In addition, their basic optical properties were assessed. It has been shown that in the PEO DC pulse process, it is possible to obtain oxide coatings characterized by a high degree of structure order, high ZnO content in the oxide coating (3.6 at.%, XPS), and prospective applications for photocatalytic purposes (3.12 eV).

Cerium(IV) chitosan-based hydrogel composite for efficient adsorptive removal of phosphates(V) from aqueous solutions.

The excess presence of phosphate(V) ions in the biosphere is one of the most serious problems that negatively affect aqueous biocenosis. Thus, phosphates(V) separation is considered to be important for sustainable development. In the presented study, an original cerium(IV)-modified chitosan-based hydrogel (Ce-CTS) was developed using the chemical co-precipitation method and then used as an adsorbent for efficient removal of phosphate(V) ions from their aqueous solutions. From the scientific point of view, it represents a completely new physicochemical system. It was found that the adsorptive removal of phosphate(V) anions by the Ce-CTS adsorbent exceeded 98% efficiency which is ca. 4-times higher compared with the chitosan-based hydrogel without any modification (non-cross-linked CTS). The best result of the adsorption capacity of phosphates(V) on the Ce-CTS adsorbent, equal to 71.6 mg/g, was a result of adsorption from a solution with an initial phosphate(V) concentration 9.76 mg/dm3 and pH 7, an adsorbent dose of 1 g/dm3, temperature 20 °C. The equilibrium interphase distribution data for the Ce-CTS adsorbent and aqueous solution of phosphates(V) agreed with the theoretical Redlich-Peterson and Hill adsorption isotherm models. From the kinetic point of view, the pseudo-second-order model explained the phosphates(V) adsorption rate for Ce-CTS adsorbent the best. The specific effect of porous structure of adsorbent influencing the diffusional mass transfer resistances was identified using Weber-Morris kinetic model. The thermodynamic study showed that the process was exothermic and the adsorption ran spontaneously. Modification of CTS with cerium(IV) resulted in the significant enhancement of the chitosan properties towards both physical adsorption (an increase of the point of zero charge of adsorbent), and chemical adsorption (through the presence of Ce(IV) that demonstrates a chemical affinity for phosphate(V) anions). The elaborated and experimentally verified highly effective adsorbent can be successfully applied to uptake phosphates(V) from aqueous systems. The Ce-CTS adsorbent is stable in the conditions of the adsorption process, no changes in the adsorbent structure or leaching of the inorganic filling were observed.

Poly(sebacic acid) microparticles loaded with azithromycin as potential pulmonary drug delivery system: Physicochemical properties, antibacterial behavior, and cytocompatibility studies.

Recurrent bacterial infections are a common cause of death for patients with cystic fibrosis and chronic obstructive pulmonary disease. Herein, we present the development of the degradable poly(sebacic acid) (PSA) microparticles loaded with different concentrations of azithromycin (AZ) as a potential powder formulation to deliver AZ locally to the lungs. We characterized microparticle size, morphology, zeta potential, encapsulation efficiency, interaction PSA with AZ and degradation profile in phosphate buffered saline (PBS). The antibacterial properties were evaluated using the Kirby-Bauer method against Staphylococcus aureus. Potential cytotoxicity was evaluated in BEAS-2B and A549 lung epithelial cells by the resazurin reduction assay and live/dead staining. The results show that microparticles are spherical and their size, being in the range of 1-5 µm, should be optimal for pulmonary delivery. The AZ encapsulation efficiency is nearly 100 % for all types of microparticles. The microparticles degradation rate is relatively fast - after 24 h their mass decreased by around 50 %. The antibacterial test showed that released AZ was able to successfully inhibit bacteria growth. The cytotoxicity test showed that the safe concentration of both unloaded and AZ-loaded microparticles was equal to 50 µg/ml. Thus, appropriate physicochemical properties, controlled degradation and drug release, cytocompatibility, and antibacterial behavior showed that our microparticles may be promising for the local treatment of lung infections.

Novel mechanically strong and antibacterial dimethacrylate copolymers based on quaternary ammonium urethane-dimethacrylate analogues.

OBJECTIVES: This study assumed that the quaternary ammonium urethane-dimethacrylate derivative (QAUDMA-m, where m was 8, 10, 12, 14, 16, 18, and corresponded to the number of carbon atoms in the N-alkyl substituent) can be used to achieve copolymers with high mechanical performance and antibacterial activity. METHODS: Photocured copolymers of bisphenol A glycerolate dimethacrylate (Bis-GMA) 40 wt%, QAUDMA-m 40 wt%, and triethylene glycol dimethacrylate (TEGDMA) 20 wt% (BG:QAm:TEG) were characterized by the degree of conversion (DC), flexural strength (FS), flexural modulus (E), hardness (HB), and antibacterial properties (the number of bacteria colonies adhered to copolymer surfaces and inhibition zone diameter (IZD)) against Staphylococcus aureus and Escherichia coli. Reference copolymers of Bis-GMA, urethane-dimethacrylate monomer (UDMA), and TEGDMA (BG:TEG and BG:UD:TEG) were also characterized. RESULTS: The DC of BG:QAm:TEGs ranged from 0.59 to 0.68, HB from 83.84 to 153.91 MPa, FS from 50.81 to 74.47 MPa, and E from 1986.74 to 3716.68 MPa. The number of S. aureus and E. coli bacteria adhered to BG:QAm:TEG surfaces was from 0 (no bacteria observed) to 6.47 and 4.99 log(CFU/mL), respectively. IZD was from 10 and 5 mm (no inhibition zone) to 23 and 21 mm, respectively. Three copolymers: BG:QA8:TEG, BG:QA10:TEG, and BG:QA12:TEG had similar or better mechanical properties than the reference copolymers, but unlike them, they showed high antibacterial activity against both bacteria strains. SIGNIFICANCE: The obtained copolymers can offer a good, mechanically efficient, bioactive alternative to BG:TEG and BG:UD:TEG copolymers. The use of such materials can help to make progress in dental health care.

Cytotoxicity and Microbiological Properties of Copolymers Comprising Quaternary Ammonium Urethane-Dimethacrylates with Bisphenol A Glycerolate Dimethacrylate and Triethylene Glycol Dimethacrylate.

Using dental composite restorative materials with a copolymeric matrix chemically modified towards bioactive properties can help fight secondary caries. In this study, copolymers of 40 wt.% bisphenol A glycerolate dimethacrylate, 40 wt.% quaternary ammonium urethane-dimethacrylates (QAUDMA-m, where m represents 8, 10, 12, 14, 16 and 18 carbon atoms in the N-alkyl substituent), and 20 wt.% triethylene glycol dimethacrylate (BG:QAm:TEGs) were tested for (i) cytotoxicity on the L929 mouse fibroblast cell line; (ii) fungal adhesion, fungal growth inhibition zone, and fungicidal activity against C. albicans; and (iii) bactericidal activity against S. aureus and E. coli. BG:QAm:TEGs had no cytotoxic effects on L929 mouse fibroblasts because the reduction of cell viability was less than 30% compared to the control. BG:QAm:TEGs also showed antifungal activity. The number of fungal colonies on their surfaces depended on the water contact angle (WCA). The higher the WCA, the greater the scale of fungal adhesion. The fungal growth inhibition zone depended on the concentration of QA groups (xQA). The lower the xQA, the lower the inhibition zone. In addition, 25 mg/mL BG:QAm:TEGs suspensions in culture media showed fungicidal and bactericidal effects. In conclusion, BG:QAm:TEGs can be recognized as antimicrobial biomaterials with negligible biological patient risk.

Nitrilotriacetic Acid Improves Plasma Electrolytic Oxidation of Titanium for Biomedical Applications.

Dental implants have become a routine, affordable, and highly reliable technology to replace tooth loss. In this regard, titanium and its alloys are the metals of choice for the manufacture of dental implants because they are chemically inert and biocompatible. However, for special cohorts of patients, there is still a need for improvements, specifically to increase the ability of implants to integrate into the bone and gum tissues and to prevent bacterial infections that can subsequently lead to peri-implantitis and implant failures. Therefore, titanium implants require sophisticated approaches to improve their postoperative healing and long-term stability. Such treatments range from sandblasting to calcium phosphate coating, fluoride application, ultraviolet irradiation, and anodization to increase the bioactivity of the surface. Plasma electrolytic oxidation (PEO) has gained popularity as a method for modifying metal surfaces and delivering the desired mechanical and chemical properties. The outcome of PEO treatment depends on the electrochemical parameters and composition of the bath electrolyte. In this study, we investigated how complexing agents affect the PEO surfaces and found that nitrilotriacetic acid (NTA) can be used to develop efficient PEO protocols. The PEO surfaces generated with NTA in combination with sources of calcium and phosphorus were shown to increase the corrosion resistance of the titanium substrate. They also support cell proliferation and reduce bacterial colonization and, hence, lead to a reduction in failed implants and repeated surgeries. Moreover, NTA is an ecologically favorable chelating agent. These features are necessary for the biomedical industry to be able to contribute to the sustainability of the public healthcare system. Therefore, NTA is proposed to be used as a component of the PEO bath electrolyte to obtain bioactive surface layers with properties desired for next-generation dental implants.

Surface Multifunctionalization of Inert Ceramic Implants by Calcium Phosphate Biomimetic Coating Doped with Nanoparticles Encapsulating Antibiotics.

Aseptic loosening and periprosthetic infections are complications that can occur at the interface between inert ceramic implants and natural body tissues. Therefore, the need for novel materials with antibacterial properties to prevent implant-related infection is evident. This study proposes multifunctionalizing the inert ceramic implant surface by biomimetic calcium phosphate (CaP) coating decorated with antibiotic-loaded nanoparticles for bioactivity enhancement and antibacterial effect. This study aimed to coat zirconium dioxide (ZrO2) substrates with a bioactive CaP-layer containing drug-loaded degradable polymer nanoparticles (NPs). The NPs were loaded with two antibiotics, gentamicin or bacitracin. The immobilization of NPs happened by two deposition methods: coprecipitation and drop-casting. X-ray diffraction (XRD), scanning electron microscopy (SEM), and cross-section analyses were used to characterize the coatings. MG-63 osteoblast-like cells and human mesenchymal stem cells (hMSC) were chosen for in vitro tests. Antibacterial activity was assessed with S. aureus and E. coli. The coprecipitation method allowed for a favorable homogeneous distribution of the NPs within the CaP coating. The CaP coating was constituted of hydroxyapatite and octacalcium phosphate; its thickness was 3.8 ± 1 µm with cavities of around 1 µm suitable for hosting NPs with a size of 200 nm. Antibiotics were released from the coatings in a controlled manner for 1 month. The cell culture study has confirmed the excellent behavior of the coprecipitated coating, showing cytocompatibility and a homogeneous distribution of the cells on the coated surfaces. The increase in alkaline phosphatase activity showed osteogenic differentiation. The materials were found to inhibit the growth of bacteria. Newly developed coatings with antibacterial and bioactive properties are promising candidates to prevent peri-implant infectious bone diseases.

Recent Advances in the Control of Clinically Important Biofilms.

Biofilms are complex structures formed by bacteria, fungi, or even viruses on biotic and abiotic surfaces, and they can be found in almost any part of the human body. The prevalence of biofilm-associated diseases has increased in recent years, mainly because of the frequent use of indwelling medical devices that create opportunities for clinically important bacteria and fungi to form biofilms either on the device or on the neighboring tissues. As a result of their resistance to antibiotics and host immunity factors, biofilms have been associated with the development or persistence of several clinically important diseases. The inability to completely eradicate biofilms drastically increases the burden of disease on both the patient and the healthcare system. Therefore, it is crucial to develop innovative ways to tackle the growth and development of biofilms. This review focuses on dental- and implant-associated biofilm infections, their prevalence in humans, and potential therapeutic intervention strategies, including the recent advances in pharmacology and biomedical engineering. It lists current strategies used to control the formation of clinically important biofilms, including novel antibiotics and their carriers, antiseptics and disinfectants, small molecule anti-biofilm agents, surface treatment strategies, and nanostructure functionalization, as well as multifunctional coatings particularly suitable for providing antibacterial effects to the surface of implants, to treat either dental- or implant-related bacterial infections.

Design, Synthesis and Preliminary Evaluation of the Cytotoxicity and Antibacterial Activity of Novel Triphenylphosphonium Derivatives of Betulin.

For several decades, natural products have been widely researched and their native scaffolds are the basis for the design and synthesis of new potential therapeutic agents. Betulin is an interesting biologically attractive natural parent molecule with a high safety profile and can easily undergo a variety of structural modifications. Herein, we describe the synthesis of new molecular hybrids of betulin via covalent linkage with an alkyltriphenylphosphonium moiety. The proposed strategy enables the preparation of semi-synthetic derivatives (28-TPP⊕ BN and 3,28-bisTPP⊕ BN) from betulin through simple transformations in high yields. The obtained results showed that the presence of a lipophilic cation improved the solubility of the tested analogs compared to betulin, and increased their cytotoxicity. Among the triphenylphosphonium derivatives tested, analogs 7a (IC50 of 5.56 µM) and 7b (IC50 of 5.77 µM) demonstrated the highest cytotoxicity against the colorectal carcinoma cell line (HCT 116). TPP⊕-conjugates with betulin showed antimicrobial properties against Gram-positive reference Staphylococcus aureus ATCC 25923 and Staphylococcus epidermidis ATCC 12228 bacteria, at a 200 µM concentration in water. Hence, the conjugation of betulin's parent backbone with a triphenylphosphonium moiety promotes transport through the hydrophobic barriers of the mitochondrial membrane, making it a promising strategy to improve the bioavailability of natural substances.

Comparison of Physicochemical, Mechanical, and (Micro-)Biological Properties of Sintered Scaffolds Based on Natural- and Synthetic Hydroxyapatite Supplemented with Selected Dopants.

The specific combinations of materials and dopants presented in this work have not been previously described. The main goal of the presented work was to prepare and compare the different properties of newly developed composite materials manufactured by sintering. The synthetic- (SHAP) or natural- (NHAP) hydroxyapatite serves as a matrix and was doped with: (i) organic: multiwalled carbon nanotubes (MWCNT), fullerenes C60, (ii) inorganic: Cu nanowires. Research undertaken was aimed at seeking novel candidates for bone replacement biomaterials based on hydroxyapatite-the main inorganic component of bone, because bone reconstructive surgery is currently mostly carried out with the use of autografts; titanium or other non-hydroxyapatite -based materials. The physicomechanical properties of the developed biomaterials were tested by Scanning Electron Microscopy (SEM), Dielectric Spectroscopy (BSD), Nuclear Magnetic Resonance (NMR), and Differential Scanning Calorimetry (DSC), as well as microhardness using Vickers method. The results showed that despite obtaining porous sinters. The highest microhardness was achieved for composite materials based on NHAP. Based on NMR spectroscopy, residue organic substances could be observed in NHAP composites, probably due to the organic structures that make up the tooth. Microbiology investigations showed that the selected samples exhibit bacteriostatic properties against Gram-positive reference bacterial strain S. epidermidis (ATCC 12228); however, the property was much less pronounced against Gram-negative reference strain E. coli (ATCC 25922). Both NHAP and SHAP, as well as their doped derivates, displayed in good general compatibility, with the exception of Cu-nanowire doped derivates.

Novel Antibacterial Copolymers Based on Quaternary Ammonium Urethane-Dimethacrylate Analogues and Triethylene Glycol Dimethacrylate.

The growing scale of secondary caries and occurrence of antibiotic-resistant bacterial strains require the development of antibacterial dental composites. It can be achieved by the chemical introduction of quaternary ammonium dimethacrylates into dental composites. In this study, physicochemical and antibacterial properties of six novel copolymers consisting of 60 wt. % quaternary ammonium urethane-dimethacrylate analogues (QAUDMA) and 40 wt. % triethylene glycol dimethacrylate (TEGDMA) were investigated. Uncured compositions had suitable refractive index (RI), density (dm), and glass transition temperature (Tgm). Copolymers had low polymerization shrinkage (S), high degree of conversion (DC) and high glass transition temperature (Tgp). They also showed high antibacterial effectiveness against S. aureus and E. coli bacterial strains. It was manifested by the reduction in cell proliferation, decrease in the number of bacteria adhered on their surfaces, and presence of growth inhibition zones. It can be concluded that the copolymerization of bioactive QAUDMAs with TEGDMA provided copolymers with high antibacterial activity and rewarding physicochemical properties.

Biodegradable and Bioactive Carriers Based on Poly(betulin disuccinate-co-sebacic Acid) for Rifampicin Delivery.

This paper describes the preparation and characterization of polymer-drug systems based on polymeric microspheres obtained from poly(betulin disuccinate-co-sebacic acid). The active compound that was coupled to the betulin-based carriers was rifampicin (RIF), an ansamycin drug used in the treatment of tuberculosis. Poly(betulin disuccinate-co-sebacic acid) microspheres were prepared using a solvent evaporation technique from copolymers obtained by polycondensation of betulin disuccinate (DBB) and sebacic acid (SEB). The content of sebacic acid in the copolymers was 20, 40, 60 and 80 wt%, respectively. Small and large rifampicin-loaded microspheres were obtained for each of the copolymers. The initial amount of drug was 10, 30 or 50 wt%, based on the weight of the polymer. Particles obtained in this study were round in shape with diameter in the range of 2-21 µm and of orange to red colour originating from rifampicin. The RIF encapsulation efficacy varied from 7% to 33%. Drug loading varied from 2% to 13% and increased at a higher RIF ratio. The highest degree of drug loading was observed for large particles, in which the initial amount of drug (at the particle preparation stage) was 50 wt%. Microspheres prepared from betulin-based polyanhydrides may have significant applications in drug delivery systems. The concentration of loaded drug was enough to obtain bactericidal effects against reference S. Aureus ATCC 25923 bacteria.

Boron Removal by Sorption on Modified Chitosan Hydrogel Beads.

An excess concentration of boron in irrigation and drinking water can negatively affect the yield of plants and the human nervous system, respectively. To meet the recommended levels, hybrid biosorbent hydrogel beads based on chitosan and manganese (II-IV) were employed for the removal of boron from aqueous media. The results showed that the biosorbent effectively removed boric acid from the aqueous medium at neutral pH over a sorption time of 2 h and the liquid/hydrogel ratio of 20 mL/g, achieving a maximum sorption capacity near 190 mg/g. The modeling of the sorption equilibrium data indicated that the Freundlich isotherm equation gave the best fit out of the isotherm models examined. A pseudo-second-order model was found to best describe the sorption kinetics. The favorable attachment of manganese to the chitosan structure enabled the sorption of boron and was confirmed by FTIR, RS, XRD, SEM and ICP-OES methods. Boron desorption from the spent biosorbent was successfully achieved in three cycles using a NaOH solution. In general, the results of this research indicate that this method is one of the possibilities for improving water quality and may contribute to reducing pollution of the aquatic environment.

Corrosion Inhibitor-Modified Plasma Electrolytic Oxidation Coatings on 6061 Aluminum Alloy.

There are many methods for incorporating organic corrosion inhibitors to oxide coatings formed on aluminum alloys. However, typically they require relatively concentrated solutions of inhibitors, possibly generating a problematic waste and/or are time-/energy-consuming (elevated temperature is usually needed). The authors propose a three-step method of oxide layer formation on 6061-T651 aluminum alloy (AAs) via alternating current (AC) plasma electrolytic oxidation (PEO), impregnation with an 8-hydroxyquinoline (8-HQ) solution, and final sealing by an additional direct current (DC) polarization in the original PEO electrolyte. The obtained coatings were characterized by scanning electron microscopy, roughness tests, contact angle measurements, X-ray diffraction, Raman spectroscopy, and X-ray photoelectron spectroscopy. Additionally, corrosion resistance was assessed by potentiodynamic polarization in a NaCl solution. Two types of the coating were formed (A-thicker, more porous at 440 mA cm-2; B-thinner, more compact at 220 mA cm-2) on the AA substrate. The 8-HQ impregnation was successful as evidenced by XPS. It increased the contact angle only for the B coatings and improved the corrosion resistance of both coating systems. Additional DC treatment destroyed superficially adsorbed 8-HQ. However, it served to block the coating pores (contact angle ≈ 80°) which improved the corrosion resistance of the coating systems. DC sealing alone did not bring about the same anti-corrosion properties as the combined 8-HQ impregnation and DC treatment which dispels the notion that the provision of the inhibitor was a needless step in the procedure. The proposed method of AA surface treatment suffered from unsatisfactory uniformity of the sealing for the thicker coatings, which needs to be amended in future efforts for optimization of the procedure.

Key Properties of a Bioactive Ag-SiO2/TiO2 Coating on NiTi Shape Memory Alloy as Necessary at the Development of a New Class of Biomedical Materials.

Recent years have seen the dynamic development of methods for functionalizing the surface of implants using biomaterials that can mimic the physical and mechanical nature of native tissue, prevent the formation of bacterial biofilm, promote osteoconduction, and have the ability to sustain cell proliferation. One of the concepts for achieving this goal, which is presented in this work, is to functionalize the surface of NiTi shape memory alloy by an atypical glass-like nanocomposite that consists of SiO2-TiO2 with silver nanoparticles. However, determining the potential medical uses of bio(nano)coating prepared in this way requires an analysis of its surface roughness, tribology, or wettability, especially in the context of the commonly used reference coat-forming hydroxyapatite (HAp). According to our results, the surface roughness ranged between (112 ± 3) nm (Ag-SiO2)-(141 ± 5) nm (HAp), the water contact angle was in the range (74.8 ± 1.6)° (Ag-SiO2)-(70.6 ± 1.2)° (HAp), while the surface free energy was in the range of 45.4 mJ/m2 (Ag-SiO2)-46.8 mJ/m2 (HAp). The adhesive force and friction coefficient were determined to be 1.04 (Ag-SiO2)-1.14 (HAp) and 0.247 ± 0.012 (Ag-SiO2) and 0.397 ± 0.034 (HAp), respectively. The chemical data showed that the release of the metal, mainly Ni from the covered NiTi substrate or Ag from Ag-SiO2 coating had a negligible effect. It was revealed that the NiTi alloy that was coated with Ag-SiO2 did not favor the formation of E. coli or S. aureus biofilm compared to the HAp-coated alloy. Moreover, both approaches to surface functionalization indicated good viability of the normal human dermal fibroblast and osteoblast cells and confirmed the high osteoconductive features of the biomaterial. The similarities of both types of coat-forming materials indicate an excellent potential of the silver-silica composite as a new material for the functionalization of the surface of a biomaterial and the development of a new type of functionalized implants.

Effects of the sources of calcium and phosphorus on the structural and functional properties of ceramic coatings on titanium dental implants produced by plasma electrolytic oxidation.

Plasma Electrolytic Oxidation (PEO) is as a promising technique to modify metal surfaces by application of oxide ceramic coatings with appropriate physical, chemical and biological characteristics. Therefore, objective of this research was to find the simplest settings, yet able to produce relevant bioactive implant surfaces layers on Ti implants by means of PEO. We show that an electrolyte containing potassium dihydrogen phosphate as a source of P and either calcium hydroxide or calcium formate as a source of Ca in combination with a chelating agent, ethylenediamine tetraacetic acid (EDTA), is suitable for PEO to deliver coatings with desired properties. We determined surface morphology, roughness, wettability, chemical and phase composition of titanium after the PEO process. To investigate biocompatibility and bacterial properties of the PEO oxide coatings we used microbial and cell culture tests. The electrolyte based on Ca(OH)2 and EDTA promotes active crystallization of apatites after PEO processing of the Ti implants. The PEO layers can increase electrochemical corrosion resistance. The PEO can be potentially used for development of bioactive surfaces with increased support of eukaryotic cells while inhibiting attachment and growth of bacteria without use of antibacterial agents.

Analysis of the Calcium Phosphate-Based Hybrid Layer Formed on a Ti-6Al-7Nb Alloy to Enhance the Ossseointegration Process.

This paper reports on hybrid, bioactive ceramic Ca-P-based coating formation on a Ti-6Al-7Nb alloy substrate to enhance the osseointegration process. The Ti alloy was anodized in a Ca3(PO4)2 suspension and then the additional layer was formed by the sol-gel technique to obtain a mixture of the calcium phosphate compounds. The oxide layer was porous and additional ceramic particles were formed after sol-gel treatment (scanning electron microscopy analysis coupled with energy-dispersive x-ray spectroscopy). The ceramic particles were formed on some parts of the oxide layer and did not completely fill the pores. The layer thickness of the anodized Ti alloy was comprised between 3.01 and 5.03 µm and increased to 7.52-12.30 µm after the formation of an additional layer. Post-treatment of the anodized Ti alloys caused a decrease in surface roughness, and the layer became strongly hydrophilic. Crystalline phase analysis (X-ray diffraction, XRD) showed that the hybrid layer was composed of TiO2 (anatase), Ca3(PO4)2, Ca10(PO4)6(OH)2 and a partially amorphous phase; thus, the layer was also analyzed by Raman spectroscopy. The hybrid layer showed worse adhesion to the substrate than the anodized layer only; however, the coating was not brittle, and the first delamination of the layer was determined at 1.84 ± 0.11 N during scratch-test measurement. The hybrid coating was favorable for collagen type I and lactoferrin adsorption, strongly influencing the proliferation of osteoblast-like MG-63 cells. The coatings were cytocompatible and may find applications in formation of the functional layers on long-term implants' surface after.

In Vitro Biological Characterization of Silver-Doped Anodic Oxide Coating on Titanium.

Despite the high biocompatibility and clinical effectiveness of Ti-based implants, surface functionalization (with complex osteointegrative/antibacterial strategies) is still required. To enhance the dental implant surface and to provide additional osteoinductive and antibacterial properties, plasma electrolytic oxidation of a pure Ti was performed using a nitrilotriacetic acid (NTA)-based Ag nanoparticles (AgNP)-loaded calcium-phosphate solution. Chemical and structural properties of the surface-modified titanium were assessed using scanning electron microscopy (SEM) with energy dispersive X-ray (EDX) and contact angle measurement. A bacterial adhesion test and cell culture biocompatibility with collagen production were performed to evaluate biological effectiveness of the Ti after the plasma electrolytic process. The NTA-based calcium-phosphate solution with Ag nanoparticles (AgNPs) can provide formation of a thick, porous plasma electrolytic oxidation (PEO) layer enriched in silver oxide. Voltage elevation leads to increased porosity and a hydrophilic nature of the newly formed ceramic coating. The silver-enriched PEO layer exhibits an effective antibacterial effect with high biocompatibility and increased collagen production that could be an effective complex strategy for dental and orthopedic implant development.

Formation of a Bacteriostatic Surface on ZrNb Alloy via Anodization in a Solution Containing Cu Nanoparticles.

High strength, excellent corrosion resistance, high biocompatibility, osseointegration ability, and low bacteria adhesion are critical properties of metal implants. Additionally, the implant surface plays a critical role as the cell and bacteria host, and the development of a simultaneously antibacterial and biocompatible implant is still a crucial challenge. Copper nanoparticles (CuNPs) could be a promising alternative to silver in antibacterial surface engineering due to low cell toxicity. In our study, we assessed the biocompatibility and antibacterial properties of a PEO (plasma electrolytic oxidation) coating incorporated with CuNPs (Cu nanoparticles). The structural and chemical parameters of the CuNP and PEO coating were studied with TEM/SEM (Transmission Electron Microscopy/Scanning Electron Microscopy), EDX (Energy-Dispersive X-ray Dpectroscopy), and XRD (X-ray Diffraction) methods. Cell toxicity and bacteria adhesion tests were used to prove the surface safety and antibacterial properties. We can conclude that PEO on a ZrNb alloy in Ca-P solution with CuNPs formed a stable ceramic layer incorporated with Cu nanoparticles. The new surface provided better osteoblast adhesion in all time-points compared with the nontreated metal and showed medium grade antibacterial activities. PEO at 450 V provided better antibacterial properties that are recommended for further investigation.