Novel biopolymer-coated hydroxyapatite foams for removing heavy-metals from polluted water

3D-macroporous biopolymer-coated hydroxyapatite (HA) foams have been developed as potential devices for the treatment of lead, cadmium and copper contamination of consumable waters. These foams have exhibited a fast and effective ion metal immobilization into the HA structure after an in vitro treatment mimicking a serious water contamination case. To improve HA foam stability at contaminated aqueous solutions pH, as well as its handling and shape integrity the 3D-macroporous foams have been coated with biopolymers polycaprolactone (PCL) and gelatine cross-linked with glutaraldehyde (G/Glu). Metal ion immobilization tests have shown higher and fast heavy metals captured as function of hydrophilicity rate of biopolymer used. After an in vitro treatment, foam morphology integrity is guaranteed and the uptake of heavy metal ions rises up to 405 μmol/g in the case of Pb²⁺, 378 μmol/g of Cu²⁺ and 316 μmol/g of Cd²⁺. These novel materials promise a feasible advance in development of new, easy to handle and low cost water purifying methods.     

Pore characteristics of Ca(OH)2 foams: Impact of surfactant–mineral interaction

Slake lime (Ca(OH)₂) foams were prepared via a mechanical foaming and gelcasting method. The Ca(OH)₂ foams were systematically characterized in terms of pore size and porosity according to expansion ratio (E_R). The results showed that the physical properties of the Ca(OH)₂ foams increased with E_R. Additionally, the Ca(OH)₂ foams with E_R = 4 showed considerably larger pore size (727.5 μm) as compared to those with smaller E_R (8.8 and 20.1 μm for E_R = 2 and 3, respectively). In order to further elucidate the mechanism, SiO₂ and Al₂O₃ foams with same E_R were prepared and compared. Additional experiments were also conducted, such as rheological behavior of slurry, electrical property of starting materials, and surfactant (sodium lauryl sulfate, SLS)–mineral adsorption capacity. The results showed that the pore size of the SiO₂ and Al₂O₃ foams was much smaller than that of the Ca(OH)₂ foams. The discrepancy in the pore size between three foams was due to the difference in the adsorption capacity of SLS onto mineral surfaces. Specifically, the loss of SLS from aqueous phase by the SLS–Ca(OH)₂ interaction resulted in the decrease in the surface tension of the Ca(OH)₂ slurry, and consequently led to the increase in bubble size (i.e., final pore size).     

Fabrication and characterization of novel hydroxyapatite/porous carbon composite scaffolds

Novel hydroxyapatite (HA)/porous carbon composite scaffolds were prepared by applying sonoelectrodeposition and a subsequent hydrothermal treatment to previous carbonized phenolic resin coated polyurethane sponges. The interconnected pore network and morphology of HA/porous carbon composite scaffolds were determined by scanning electron microscope (SEM), and the whole surface of porous carbons were evenly coated with the deposited HA layer which was confirmed by EDS and XRD. The porosity (83.5 ± 0.3%) and the bulk density (0.297 ± 0.009 g·cm⁻³) of HA/porous carbon scaffolds were detected by the Archimedes method. The compressive and flexural strength of the scaffolds is 1.187 ± 0.064 MPa and 0.607 ± 0.268 MPa, respectively. Compared with the polymeric surface of 24-well cell culture plates, these novel scaffolds significantly promote the proliferation of human osteoblast-like MG-63 cells, indicating that this novel HA/porous carbon composite scaffold could be used for in vitro 3D culture of osteoblasts.     

Preparation of adsorbent for phosphate recovery from aqueous solutions based on condensed tannin gel

We have synthesized an iron-loaded tannin gel as an adsorbent for phosphate recovery in aqueous solutions. The use of the tannin gel prepared from condensed tannin, which is a ubiquitous and inexpensive natural polymer, is not only cost effective and environment-friendly, but interesting because the phosphate-adsorbed gel can be expected to use directly as a fertilizer. The amount of iron loaded into the tannin gel oxidized by nitric acid was much larger than that into the non-oxidized tannin gel. This increase in the amount of the loaded iron resulted in the significant increase in the adsorption amount of phosphate onto the gel. Mössbauer spectroscopy indicated that the morphology of iron in the gel is a mono-type complex, which is formed as a result of the reaction between Fe(III) and the oxidized tannin gel with carbonyl groups. The iron-loaded tannin gel showed the adsorption selectivity for phosphate over other anions and the pH independence of phosphate adsorption in the wide range of initial pH 3-12. The phosphate adsorption isotherm for the iron-loaded tannin gel followed the Freundlich equation with constants of K_F = 2.66 and 1/n = 0.31, rather than the Langmuir equation. The adsorption amount of phosphate on iron weight basis for the iron-loaded tannin gel is 31.3 mg-P/g-Fe, which indicates that iron in the gel was efficiently used for the phosphate adsorption compared with other phosphate adsorbents, such as iron hydroxides.     

Novel in-situ synthesis and characterization of nanostructured magnesium substituted β-tricalcium phosphate (β-TCMP)

Tricalcium phosphate (TCP, Ca₃(PO₄)₂) in its pure form cannot be synthesized under physiological conditions in normal aqueous solutions due to phase instability, resulting in its transformation to hydroxyapatite (HA, Ca₁₀(PO₄)₆(OH)₂) in the presence of water. However, substituting magnesium in lieu of calcium is known to stabilize TCP, preventing its conversion to hydroxyapatite. There are several methods known for synthesizing magnesium substituted tricalcium phosphate (TCMP). In the present study, a novel in-situ method has been developed to synthesize β-TCMP using magnesium substituted brushite as a precursor.Substitution of 50% of calcium by magnesium results in the formation of semi-spherical nanocrystalline particles (～ 100 nm) of brushite. Boiling the nanocrystalline brushite powder in aqueous condition for only 30 min results in the generation of rosette shaped nanocrystals (～ 80 nm) of β-TCMP that emerge from the original brushite spheres. The β-TCMP particles exhibit a specific surface area of ～ 200 m²/g. Details about the synthesis procedure and the possible mechanisms involved in the formation of β-TCMP from Mg-substituted brushite is further discussed.     

Brushite (CaHPO4·2H2O) to octacalcium phosphate (Ca8(HPO4)2(PO4)4·5H2O) transformation in DMEM solutions at 36.5 °C

The purpose of this study was to investigate the transformation of brushite (dicalcium phosphate dihydrate, DCPD, CaHPO₄·2H₂O) powders at 36.5 °C in DMEM (Dulbecco's Modified Eagle Medium) solutions. Two sets of brushite powders with different particle shapes were synthesized to use in the above DMEM study. The first of these brushite powders was prepared by using a method which consisted of stirring calcite (CaCO₃) powders in a solution of ammonium dihydrogen phosphate (NH₄H₂PO₄) from 6 to 60 min at room temperature. These powders were found to consist of dumbbells of water lily-shaped crystals. The second one of the brushite powders had the common flat-plate morphology. Both powders were separately tested in DMEM-immersion experiments. Monetite (DCPA, CaHPO₄) powders were synthesized with a unique water lily morphology by heating the water lily-shaped brushite crystals at 200 °C for 2 h. Brushite powders were found to transform into octacalcium phosphate (OCP, Ca₈(HPO₄)₂(PO₄)₄·5H₂O) upon soaking in DMEM (Dulbecco's Modified Eagle Medium) solutions at 36.5 °C over a period of 24 h to 1 week. Brushite powders were known to transform into apatite when immersed in synthetic (simulated) body fluid (SBF) solutions. This study found that DMEM solutions are able to convert brushite into OCP, instead of apatite.     

Low temperature fabrication of spherical brushite granules by cement paste emulsion

Secondary protonated calcium phosphates such as brushite (CaHPO₄·2H₂O) or monetite (CaHPO₄) have a higher resorption potential in bone defects than sintered ceramics, e.g. tricalcium phosphate or hydroxyapatite. However, processing of these phosphates to monolithic blocks or granules is not possible by sintering due to thermal decomposition of protonated phosphates at higher temperatures. In this study a low temperature technique for the preparation of spherical brushite granules in a cement setting reaction is presented. These granules were synthesized by dispersing a calcium phosphate cement paste composed of β-tricalcium phosphate and monocalcium phosphate together with a surfactant to an oil/water emulsion. The reaction products were characterized regarding their size distribution, morphology, and phase composition. Clinically relevant granule sizes ranging from 200?μm to 1?mm were obtained, whereas generally smaller granules were received with higher oil viscosity, increasing temperature or higher powder to liquid ratios of the cement paste. The hardened granules were microporous with a specific surface area of 0.7?m²/g and consisted of plate-like brushite (>95?% according to XRD) crystals of 0.5–7?μm size. Furthermore it was shown that the granules may be also used for drug delivery applications. This was demonstrated by adsorption of vancomycin from an aqueous solution, where a load of 1.45–1.88?mg drug per g granules and an almost complete release within 2?h was obtained.     

Synthesis and electrochemical characterization of myoglobin-antibody protein immobilized self-assembled gold nanoparticles on ITO-glass plate

We report a protein immobilized self-assembled monolayer (SAM) of gold nanoparticles (GNPs) on indium-tin-oxide (ITO) coated glass plate. The protein-antibody, Mb-Ab, was covalently immobilized over the self-assembly of GNPs through a mixed SAM of 11-mercapto undecanoic acid (MUA) and 3-mercapto propionic acid (MPA) via carbodiimide coupling reaction using N-(3-dimethylaminopropyl)-N′-ethyl carbodiimide (EDC) and N-hydroxy succinimide (NHS). The whole assembly was constructed on 0.25 cm² area of ITO-glass plate (Mb-Ab/MUA-MPA/GNPs/APTES/ITO-glass) and an impedimetric study was carried out for its application in myoglobin detection. This prototype assembly was characterized by scanning electron microscopy, atomic force microscopy and electrochemical techniques. The modified electrode showed an increased electron-transfer resistance on coupling with protein antigen, Mb-Ag, in the presence of a redox probe [Fe(CN)₆]^3−/4−. Its exhibits an electrochemical impedance response to protein myoglobin-antigen, Mb-Ag, concentration in a linear range from 0.01 μg to 1.65 μg mL⁻¹ with a lowest detection limit of 1.4 ng mL⁻¹.     

Effects of argon and oxygen flow rate on water vapor barrier properties of silicon oxide coatings deposited on polyethylene terephthalate by plasma enhanced chemical vapor deposition

Plasma polymer coatings were deposited from hexamethyldisiloxane on polyethylene terephthalate (PET) substrates while varying the operating conditions, such as the Ar and O₂ flow rates, at a fixed radio frequency power of 300 W. The water vapor transmission rate (WVTR) of the untreated PET was 54.56 g/m²/day and was decreased after depositing the silicon oxide (SiO_x) coatings. The minimum WVTR, 0.47 g/m²/day, was observed at Ar and O₂ flow rates of 4 and 20 sccm, respectively, with a coating thickness of 415.44 nm. The intensity of the peaks for the Si-O-Si bending at 800-820 cm^− 1 and Si-O-Si stretching at 1000-1150 cm^− 1 varied depending on the Ar and O₂ flow rates. The contact angle of the SiO_x coated PET increased as the Ar flow rate was increased from 2 to 8 sccm at a fixed O₂ flow rate of 20 sccm. It decreased gradually as the oxygen flow rate increased from 12 to 28 sccm at a fixed Ar carrier gas flow rate. The examination by atomic force microscopy revealed a correlation of the SiO_x morphology and the water vapor barrier performance with the Ar and O₂ flow rates. The roughness of the deposited coatings increased when either the O₂ or Ar flow rate was increased.     

Silica/potassium ferrite nanocomposite: Structural,morphological, magnetic,thermal and in vitro cytotoxicity analysis

The coating of silica on potassium ferrite (KFeO₂) nanoparticles has been reported in the present study. The X-ray diffraction pattern revealed the formation of orthorhombic structure of bare potassium ferrite nanoparticles, which was also retained after the silica coating, along with a broad band near 2θ ∼ 20–25° pertaining to the presence of amorphous silica. The size of bare and coated potassium ferrite nanoparticles was found to be 4–8 nm and 10–22 nm, respectively, as observed from transmission electron microscope. The presence of silica was also revealed by the Fourier transform infrared spectrum and high resolution transmission electron microscope. In vibrating sample magnetometer analysis, both bare as well as coated potassium ferrite nanoparticles exhibited superparamagnetic behaviour with magnetic saturation values, 49.01 and 21.17 emu/g, respectively. Dose-dependent cellular toxicity was observed in the in vitro MTT (3-(4,5-dimethylthiazol-2-yl)-2,5-diphenyltetrazolium bromide, a tetrazole) – assay study on Jurkat cells, where both bare as well as silica coated nanoparticles exhibited non-toxicity below 250 μg/ml. An augmentation of cell viability was observed in case of silica coated potassium ferrite nanoparticles. The nanosize, superparamagnetic behaviour and enhanced cell viability make silica coated potassium ferrite nanoparticles a potential claimant for biomedical applications.     

Synthesis, characterization and magnetic properties of hexagonal (VO)0.09V0.18Mo0.82O3 · 0.54H2O microrods

(VO)_0.09V_0.18Mo_0.82O₃ · 0.54H₂O microrods have been synthesized for the first time via a hydrothermal treatment of aqueous peroxomolybdic acid and vanadyl sulfate. The compound crystallizes in hexagonal rods with space group P6₃, and lattice constants a = 10.586 Å, and c = 3.698 Å. The single crystalline rods exhibit diameters of 1-2 μm and lengths up to 45 μm. A variety of techniques, including X-ray diffraction, scanning electron microscopy, high-resolution transmission electron microscope, Fourier-transform infrared spectroscopy, differential scanning calorimetry and static magnetometry were used to characterize the product.     

In situ composite coating of titania-hydroxyapatite on titanium substrate by micro-arc oxidation coupled with electrophoretic deposition processing

In situ composite coating of hydroxyapatite (HA)/TiO₂ were produced on titanium (Ti) substrate by micro-arc oxidation coupled with electrophoretic deposition (MAO&EPD) technique with different concentrations of HA particles in the 0.2 M NaOH electrolyte solution. The surface morphology and chemical composition of the hybrid coating were effected by HA concentration. The amount of HA particles incorporated into coating layer increased with increasing HA concentration used in the electrolyte solution. The corrosion behavior of the coating layer in simulated body fluids (SBF) was evaluated using a potentiodynamic polarization test. The corrosion resistance of the coated sample was increased compared to the untreated Ti sample. The in vitro bioactivity assessment showed that the MAO&EPD treated Ti substrate possessed higher apatite-forming ability than the untreated Ti. Moreover, the apatite-forming ability had a positive correlation with HA concentration. In addition, the cell behavior was also examined using cell proliferation assay and alkaline phosphatase ability. The coating formed at HA concentration of 5 g/L exhibited the highest cell ability.     

Incorporation of a controlled-release glass into a calcium phosphate cement

A so-called controlled-release glass was synthesized occurring in the system CaO-Na₂O-P₂O₅. A certain sieve fraction of this glass was incorporated in a calcium phosphate cement, of which the powder contained -tricalcium phosphate (-TCP), dicalcium phosphate (DCP) and precipitated hydroxyapatite (HA). The glass appeared to retard the cement setting slightly and it reduced considerably the compressive strength after aging in aqueous solutions which were continuously refreshed. Scanning electron microscope (SEM) pictures and X-ray diffraction (XRD) patterns of the samples after 5 weeks of aging showed that the glass was not dissolved but that large brushite crystals were formed. Thereby, aging in CaCl₂ solutions resulted in more brushite formation than aging in NaCl solutions. The brushite crystals did not reinforce the cement. Neither was the aged glass-containing cement weaker than it was before the brushite formation right after complete setting. In conclusion, the incorporation of controlled-release glasses into a calcium phosphate cement and subsequent aging in aqueous solutions did not result in the formation of macropores in the cement structure, but that of brushite crystals. This incorporation reduced the compressive strength of the cement considerably. © 1999 Kluwer Academic Publishers     

High-rate deposition by microwave RPECVD at atmospheric pressure

The post-discharge of a microwave resonant cavity working at atmospheric pressure is used to enhance deposition of SiO_x thin films from HMDSO by chemical vapor deposition. Maximum static deposition rates are close to 150 μm h^− 1 for low power consumption per unit of coated width (~ 100 W/cm). Dynamic deposition rates are close to 3.5 nm m s^− 1. The distribution of the coating thickness is heterogeneous over an area of 150 × 90 mm². The influence of the main parameters of the process is systematically studied to show how the key reactions, i.e. gas phase synthesis of powders and surface deposition, are correlated.     

Effect of TiO2-SiO2 sol-gel coating on the cpTi-porcelain bond strength

The effects of TiO₂-SiO₂ sol-gel coating with different firing temperatures (300 °C, 500 °C, and 750 °C) on the cpTi-porcelain bond strength were investigated in the present study. Prior to applying the low-fusing dental titanium porcelain, the phase, surface morphology, surface roughness and static water contact angle of the intermediate layer were evaluated. The cpTi-porcelain bond strength was measured using the three-point flexure test according to ISO 9693 standard. Statistical analyses were made using one-way ANOVA and Dunnett-t test. Significantly higher bond strength of TiO₂-SiO₂/750 °C (specimens coated with TiO₂-SiO₂ sol-gel coating and fired at 750 °C for 1 h) when compared to the control group was observed (p < 0.05). No rutile phase was found in all the tested specimens coated with TiO₂-SiO₂ sol-gel coating. The surface morphology of the intermediate layer was apparently different with different firing temperatures. It was found that the static water contact angle of TiO₂-SiO₂/750 °C significantly decreased (p < 0.05). However, no markedly different R_a of TiO₂-SiO₂/500 °C and TiO₂-SiO₂/750 °C in comparison to that of the control group was observed (p > 0.05). The results show that the TiO₂-SiO₂ sol-gel coating fired at 750 °C for 1 h can notably improve the cpTi-porcelain bond strength and may be suitable for clinical use.     

Membrane optode for mercury(II) determination in aqueous samples

A color changeable optode for Hg(II) was prepared by the immobilization of a dye 4-(2-pyridylazo)resorcinol (PAR) and a liquid ion-exchanger trioctylmethylammonium chloride (Aliquat-336) in the tri-(2-ethylhexyl) phosphate plasticized cellulose triacetate matrix. Hg(II) and CH₃Hg⁺ from aqueous samples could be quantitatively preconcentrated in this transparent optode producing a distinct color change (λ_max = 520 nm) within 5 min equilibration time in bicarbonate aqueous medium or 30 min in natural water. Whereas optode sample without Aliquat-336 did not change its color corresponding to Hg–PAR complex on equilibrium with the same aqueous solution containing Hg(II) ions. The uptake of Hg(II) was found to be pH dependant with a maximum (>90%) at a pH 7.5. The uptake of ions like Cu(II), Fe(II), Zn(II) and Pb(II) was negligible in the optode where as the uptake of Cd(II) and Zn(II) ions was 10–15% at pH 7.5. The optode developed in the present work was studied for its analytical application for Hg(II) in the aqueous samples by spectrophotometry, radiotracer (²⁰³Hg), Energy Dispersive X-ray Fluorescence (EDXRF) analyses and Instrumental Neutron Activation Analysis (INAA). The minimum amount of Hg(II) required to produce detectable response by spectrophotometry, INAA and EDXRF were found to be 5.5, 1 and 12 μg, respectively. This optode showed a linear increase in the absorbance at λ_max = 520 nm over a concentration range of 0.22–1.32 μg/mL of Hg(II) ions in aqueous solution for 5 min. The preconcentration of Hg(II) from large volume of aqueous solution was used to extend the lower limit of concentration range that can be quantified by the spectrophotometry of optode. It was observed that preconcentration of 11 μg Hg(II) in 100 mL (0.11 μg/mL) in aqueous samples gives a distinct color change and absorbance above 3σ of the blank absorbance. The optode developed in the present work was found to be reusable.     

Poly-silicon thin films by aluminium induced crystallisation of microcrystalline silicon

Al-induced crystallisation of microcrystalline Si thin films prepared by electron cyclotron resonance plasma-enhanced chemical vapour deposition (ECR-PECVD) on glass and SiO₂ coated Si wafers has been studied. The starting structure was substrate/μc-Si/Al. Annealing this structure in the temperature range 370-520 °C, immediately following deposition of the Al layer, resulted in successful layer exchange and the formation of a substrate/Al+Si layer/poly-Si geometry. The top poly-Si layer exhibited grain sizes generally in the range ∼2-6 μm, although larger grains were also sparsely present. The films did not exhibit any appreciable degree of preferred orientation. The surface roughness was relatively high with a R_a value of ∼20 nm.     

Direct growth of carbon nanotubes on hydroxyapatite using MPECVD

For the first time carbon nanotubes (CNTs) have been successfully grown directly on hydroxyapatite (HA) by using microwave plasma enhanced chemical vapor deposition (MPECVD). Such integration has potential to capitalize on the merits of both HA and CNTs. This type of coating could be useful to improve the interface between bone and the implant. Scanning electron microscope SEM investigations show that; the surface of the CNTs is relatively clean and free of amorphous carbon. The CNTs diameters lie in the range 30-70 nm. In addition HA encapsulation by carbon was observed at a growth temperature 750 °C. Raman spectroscopy indicates that the CNTs are of high quality and the I_G/I_D ratio lies between 1.243 and 1.774. The changes in the X-ray diffraction (XRD) patterns give an indication that during the plasma deposition the HA-substrate surface is subjected to a temperature sufficient for partial conversion to the β-tricalcium phosphate via dehydroxylation.     

One-step synthesis of petal-like apatite/titania composite coating on a titanium by micro-arc oxidation

Petal-like apatite/titania (TiO₂) coating was prepared on commercially pure titanium (Ti) by micro-arc oxidation in electrolyte containing calcium and phosphate for the first time. The surface morphology, crystalline structure, chemical composition and binding state of the apatite/TiO₂ composite coating were characterized. The coating consists of a double-layer (apatite layer and TiO₂ layer) structure. The average thickness of the inner TiO₂ layer and the outer apatite layer is about 6 μm and 16 μm respectively. The outer apatite layer is porous and exhibits petal-like pattern. The apatite layer consists of hydroxyapatite (HA) and carbonate-apatite and the inner TiO₂ layer consists of anatase and rutile.     

Morphology of hydroxyapatite coated nanotube surface of Ti-35Nb-xHf alloys for implant materials

The purpose of this research is to study the morphology of hydroxyapatite coated nanotube surface of Ti-35Nb-xHf for implant materials using various experiments. For this study, Ti-35Nb-xHf (x = 0, 3, 7 and 15 wt.%) alloys were prepared by arc melting and heat treated for 12 h at 1000 °C in an argon atmosphere and then water quenching. Nanotube formation on the Ti-35Nb-xHf alloys was achieved by anodizing in H₃PO₄ electrolytes containing 0.8 wt.% NaF at room temperature. Anodization was carried out using an electrochemical method and all experiments were conducted at room temperature. Hydroxyapatite (HA) was deposited on the nanotubular Ti-35Nb-xHf alloys surface for the biomaterials by radio-frequency (RF) magnetron sputtering method. The morphologies of nanotubular and HA coated surface were characterized by X-ray diffractometer (XRD), optical microscopy (OM), field emission scanning electron microscopy (FE-SEM), energy dispersive X-ray spectroscopy (EDS), X-ray photoelectron spectroscopy (XPS) and scanning transmission electron microscopy (STEM). The wettability of HA coated surface was measured by contact angle goniometer.The microstructure of Ti-35Nb-xHf alloys was transformed needle-like to equiaxed structure with Hf content and α″ phase decreased, whereas β phase increased as Hf content increased. HA coating surface was affected by microstructure of bulk and morphology of nanotube formation. In case of low Hf content, tip of nanotube formed at β phase was coated with HA film, whereas α″ phase was not coated with HA film. In case of high Hf content, nanotube surface was coated uniformly with HA film. The wettability of HA coated nanotubular surface was higher than that of non coated samples.