Djordje Veljović

Corrosion Stability and Bioactivity in Simulated Body Fluid of Silver/Hydroxyapatite and Silver/Hydroxyapatite/Lignin Coatings on Titanium Obtained by Electrophoretic Deposition

Hydroxyapatite is the most suitable biocompatible material for bone implant coatings. However, its brittleness is a major obstacle, and that is why, recently, research focused on creating composites with various biopolymers. In this study, hydroxyapatite coatings were modified with lignin in order to attain corrosion stability and surface porosity that enables osteogenesis. Incorporating silver, well known for its antimicrobial properties, seemed the best strategy for avoiding possible infections. The silver/hydroxyapatite (Ag/HAP) and silver/hydroxyapatite/lignin (Ag/HAP/Lig) coatings were cathaphoretically deposited on titanium from ethanol suspensions, sintered at 900 °C in Ar, and characterized by X-ray diffraction, scanning electron microscopy, field emission scanning electron microscopy, attenuated total reflection Fourier transform infrared, and X-ray photoelectron spectroscopy. The corrosion stability of electrodeposited coatings was evaluated in vitro in Kokubos simulated body fluid (SBF) at 37 °C using electrochemical impedance spectroscopy. Bioactivity was estimated by immersion in SBF to evaluate the formation of hydroxyapatite on the coating surface. A microcrystalline structure of newly formed plate-shaped carbonate-hydroxyapatite was detected after only 7 days, indicating enhanced bioactive behavior. Both coatings had good corrosion stability during a prolonged immersion time. Among the two, the Ag/HAP/Lig coating had a homogeneous surface, less roughness, and low values of contact angle.

Further insight into the mechanism of heavy metals partitioning in stormwater runoff.

Various particles and materials, including pollutants, deposited on urban surfaces are washed off by stormwater runoff during rain events. The interactions between the solid and dissolved compounds in stormwater runoff are phenomena of importance for the selection and improvement of optimal stormwater management practices aimed at minimizing pollutant input to receiving waters. The objective of this research was to further investigate the mechanisms responsible for the partitioning of heavy metals (HM) between the solid and liquid phases in urban stormwater runoff. The research involved the collection of samples from urban asphalt surfaces, chemical characterization of the bulk liquid samples, solids separation, particle size distribution fractionation and chemical and physico-chemical characterization of the solid phase particles. The results revealed that a negligible fraction of HM was present in the liquid phase (less than 3% by weight), while there was a strong correlation between the total content of heavy metals and total suspended solids. Examinations of surface morphology and mineralogy revealed that the solid phase particles consist predominantly of natural macroporous materials: alpha quartz (80%), magnetite (11.4%) and silicon diphosphate (8.9%). These materials have a low surface area and do not have significant adsorptive capacity. These materials have a low surface area and do not have significant adsorptive capacity. The presence of HM on the surface of solid particles was not confirmed by scanning electron microscopy and energy dispersive X-ray microanalyses. These findings, along with the results of the liquid phase sample characterization, indicate that the partitioning of HM between the liquid and solid phases in the analyzed samples may be attributed to precipitation processes.

Effect of hydroxyapatite spheres, whiskers, and nanoparticles on mechanical properties of a model BisGMA/TEGDMA composite initially and after storage

This study investigated the effect of shape, size, and surface modification of hydroxyapatite (HAP) fillers on the degree of conversion (DC) and mechanical properties of a model BisGMA/TEGDMA composite initially and after 4 weeks of storage. Ten percent of conventional glass fillers were replaced by HAP spheres (Sph), silicon-doped spheres (SphSi), whiskers (Wh), silicon-doped whiskers (WhSi), and nanosized HAP particles (Nano). Spheres were specifically structured agglomerates consisting of a central void and radially orientated primary particles, whereas whiskers were compact monocrystals. DC, Vickers hardness (HV), flexural strength (Fs), flexural modulus (Ef), compressive strength (Cs), and compressive modulus (Ec) were tested. There were no significant differences in the DC between all tested groups. HV decreased by 5.4-17% with the addition of HAP, while Fs increased by 13.9-29% except in Nano group (decrease by 13%). After storage, Sph and SphSi groups showed similar HV, Ef, Cs and Ec and higher Fs than the control. The fracture mode of HAP spheres was through the central void whereas whiskers showed longitudinal delamination, transverse, and mixed fractures. HAP spheres with or without silicon- doping have a potential to be part of the filler content of dental composites.

Electrophoretic Deposition of Biocomposite Lignin/Hydroxyapatite Coatings on Titanium

In this work, electrophoretic deposition (EPD) was applied to obtain novel hydroxyapatite (HAP)/lignin (Lig) biocomposite coatings on titanium substrate. Nanosized hydroxyapatite powder, prepared by using the modified chemical precipitation method, was used for the fabrication of HAP/Lig composite coatings. EPD was performed at different values of constant voltage and constant deposition time. It was confirmed that control over deposited mass can be achieved by applied voltage and time. The uniform and compact coatings were successfully deposited at applied voltage of 60 V in various deposition times lower than 1 minute. The effect of lignin as natural non-toxic polymer on microstructure, morphology and thermal behavior of biocomposite HAP/Lig coatings was characterized by X-ray diffraction (XRD), Fourier transform infrared spectroscopy (FT-IR), X-ray photoelectron spectroscopy (XPS), scanning electron microscopy (SEM) and thermogravimetric analysis (TGA). The electrophoretically deposited HAP/Lig coating has been successfully sintered at lower sintering temperature of 900°C, producing non-fractured coating and indicating that lignin may exhibit adhesive role, strengthening the bonding between HAP particles and substrate surface.

Cross-linking of highly methoxylated pectin with copper: the specific anion influence

The aim of this work was to investigate the influence of specific anions on the cross-linking process of highly methoxylated pectin using the following copper salts CuSO4; Cu(C2H3O2)2; CuCl2; and Cu(NO3)2 wherein the initial salt concentrations were varied from 0.5 up to 10 g l−1. It was found that the anions affected the sorption capacity wherein the Cu2+ sorption capacity from the sulphate solution was the highest, while it decreased in the presence of CH3COO−, Cl− and NO3− ions, respectively. This difference was mostly pronounced at the higher initial salt concentrations (c0(Cu2+) > 2 g l−1). The obtained beads were characterized by FTIR, AAS, SEM/EDS microanalysis and mechanical compression tests up to 80% of deformation. The sorption data were applied to the Langmuir and Freundlich isotherm models and various calculated parameters confirmed the sulphate anion supportive nature in metal ion binding. The value of the Kf parameter for the cross-linking process of pectin in the presence of acetate, chloride and nitrate was approximately the same (Kf ≈ 0.027 g g−1), while it was higher in the presence of sulphate anions by more than 20% (Kf = 0.0352 g g−1). The predicted 1/n values (1/n 1, 1/n = 1 for the sulphate, nitrate and acetate, and chloride anions, respectively) were the quantitative confirmation of the specific interactions involved in the cross-linking mechanism caused by different anions. The established anion influence was in accordance with the typical ion-specific influence on macromolecules in aqueous systems proposed by Hofmeister.

The effect of grain size on the biocompatibility, cell–materials interface, and mechanical properties of microwave‐sintered bioceramics

The effect of decreasing the grain size on the biocompatibility, cell-material interface, and mechanical properties of microwave-sintered monophase hydroxyapatite bioceramics was investigated in this study. A nanosized stoichiometric hydroxyapatite powder was isostatically pressed at high pressure and sintered in a microwave furnace in order to obtain fine grained dense bioceramics. The samples sintered at 1200°C, with a density near the theoretical one, were composed of micron-sized grains, while the grain size decreased to 130 nm on decreasing the sintering temperature to 900°C. This decrease in the grain size certainly led to increases in the fracture toughness by much as 54%. An in vitro investigation of biocompatibility with L929 and human MRC-5 fibroblast cells showed noncytotoxic effects for both types of bioceramics, while the relative cell proliferation rate, cell attachment and metabolic activity of the fibroblasts were improved with decreasing of grain size. An initial in vivo investigation of biocompatibility by the primary cutaneous irritation test showed that both materials exhibited no irritation properties.

Shear bond strength to dentine of dental adhesives containing hydroxyapatite nano-fillers

Abstract The aim of this study was to compare the effect of hydroxyapatite (HAP) nano-rods (HAProds) and HAP nano-sticks (HAPsticks) added to commercial adhesives on the macro-shear bond strength (SBS) to dentine and morphology of the adhesive–dentine interface. HAP was added to Single Bond Universal (SBU, 3M ESPE) and Te-Econom Bond (TeE; Ivoclar Vivadent), in the form of water suspensions to avoid agglomeration of nano-particles and to achieve HAP concentrations of 0.5, 1.0 and 1.5 wt%. Following a ‘total-etch’ or a ‘self-etch’ protocol, the adhesives were applied to flat dentine surface of 162 intact human, third molars (N = 6/group). Composite (Z250, 3M ESPE) was built-up using a split stainless steel mould, 3 mm in diameter. SBS was tested using a universal testing machine at 1 mm/min until fracture. Data were statistically analysed using two-way and one-way analysis of variance with Tukey’s post-test (α = 0.05). HAProds had no significant effect on SBS of the tested adhesives while HAPsticks improved bond strength to dentine only of adhesives applied following the ‘total-etch’ total-etch protocol. SBS values of SBU containing 1% HAPsticks (15.10 ± 2.96 MPa) and TeE containing 0.5% HAPsticks applied following the total-etch protocol (12.96 ± 4.48 MPa) were higher than those of their respective control groups (10.36 ± 2.68 and 7.97 ± 3.64 MPa). Samples with higher SBS showed more ‘mixed’ failures. HAP nano-fillers may improve bond strength of total-etch adhesives without an adverse effect on adhesive dispersion on dentine and its ability to infiltrate dentinal tubules.