Effects of Mg and Zn on the surface of doped melt-derived glass for biomaterials applications

Bioactive glasses in the system SiO₂-CaO-Na₂O-P₂O₅ were synthesized pure and doped with magnesium or zinc by melt-derived method. The bioactivity was studied during in vitro assays: the ability of hydroxycarbonate apatite (HCA) layer to form on the glass surface was examined after contact with simulated body fluid (SBF). The X-ray diffraction (XRD), Fourier transform infrared spectroscopy (FTIR) and scanning electron microscopy (SEM) studies were performed before and after immersion in vitro assays. The SBF solutions were also analyzed using inductively coupled plasma-optical emission spectroscopy (ICP-OES).Introduction of magnesium and zinc as trace element induces several modifications on the observed phenomena at the glass surface and in SBF solution after immersion of the samples. The chemical durability of the glasses, the formation of the silica-rich layer and the crystallization of the HCA layer were affected, but not present the same modifications as the introduced doping element.     

Study on the surface bioactivity of novel magnetic A-W glass ceramic in vitro

Novel magnetic A-W glass ceramic (M GC) in the system MgO-CaO-SiO₂-P₂O₅-CaF₂-MnO-ZnO-Fe₂O₃ was synthesized by doping Mn-Zn ferrite to apatite-wollastonite glass ceramic. The phase composition was investigated by XRD. The magnetic property was measured by VSM. The in vitro bioactivity was tested by immersion in simulated body fluid. The result shows apatite, wollastonite, fluorapatite and Zn_0.75Mn_0.75Fe_1.5O₄ are the main phases of M GC. Under a magnetic field of 10,000 Oe, the saturation magnetization and coercive force of the material are 6 emu g⁻ and 180 Oe, respectively. After soaking in SBF for 14 days, the surface of M GC is coated by a hydroxycarbonate apatite layer.     

In vitro bioactivity and biocompatibility of calcium phosphate cements using Hydroxy-propyl-methyl-Cellulose (HPMC)

In this study, the bioactivity and biocompatibility of new calcium phosphate bone cements (CPC) using Hydroxy-propyl-methyl-Cellulose (HPMC) was evaluated to understand the effect of HPMC on bone-bonding apatite formation and biocompatibility. In vitro bioactivity was investigated by incubating the CPC samples containing different ratios of HPMC (0%, 2% and 4% HPMC) in simulated body fluid (SBF) for 2, 7, 14 and 28 days. The formation of bone like apatite was confirmed on CPC surfaces by SEM and XRD analysis. Higher HPMC content of CPC showed faster apatite deposition in SBF. A high Ca ion dissolution profile was also reported with an increase of pH in all samples in SBF. The apatite formation ability of these CPC samples was found to be dependent on both surface chemistry and immersion time in SBF. The In vitro cytotoxicity test showed that the CPC samples with 4% HPMC were fairly cytocompatible for fibroblast L-929 cells. SEM images showed that MG-63 cells were successfully attached to the CPC samples and well proliferated.     

Bioactivity of SiO2-CaO-P2O5-Na2O glasses containing zinc-iron oxide

Glasses with composition x(ZnO,Fe₂O₃)(65 − x)SiO₂20(CaO,P₂O₅)15Na₂O (6 ≤ x ≤ 21 mol%) were prepared by melt-quenching technique. Bioactivity of the glasses was investigated in vitro by examining apatite formation on the surface of glasses treated in acellular simulated body fluid (SBF) with ion concentrations nearly equal to those in human blood plasma. Formation of bioactive apatite layer on the samples treated in SBF was confirmed by using Fourier transform infrared reflection (FTIR) spectroscopy, grazing incidence X-ray diffraction (GI-XRD) and scanning electron microscope (SEM) equipped with energy dispersive X-ray spectrometer. Development of an apatite structure on the surface of the SBF treated glass samples as functions of composition and time could be established using the GI-XRD data. FTIR spectra of the glasses treated in SBF show features at characteristic vibration frequencies of apatite after 1-day of immersion in SBF. SEM observations revealed that the spherical particles formed on the glass surface were made of calcium and phosphorus with the Ca/P molar ratio being close to 1.67, corresponding to the value in crystalline apatite. Increase in bioactivity with increasing zinc-iron oxide content was observed. The results have been used to understand the evolution of the apatite surface layer as a function of glass composition and immersion time in SBF.     

Compositional dependence of in-vitro bioactivity in sodium calcium borate glasses

Borate glasses with composition xCaO (100−x) B₂O₃ (20≤x≤50), where x is in mole percent) and 50CaO·45B₂O₃·5Na₂O have been prepared using conventional melt quench technique. Samples were submerged in simulating body fluid solution (SBF) at 37 °C for various periods of time. After storage the samples were analyzed in order to investigate if a surface layer of hydroxyl carbonate apatite layer (HCA layer/Ca-P layer) had formed. The analysis technique used included Fourier-Transform Infrared Spectroscopy (FTIR). The rate of HCA layer formation on the surface of exposed glass samples is determined by FTIR, percentage weight loss measurements of glass samples in SBF and variation of pH of SBF as a function of time. Increase in calcium content in the glass matrix has shown to decrease the rate of HCA formation on glass surfaces. The borate glass with x=20 has shown HCA layer formation on glass surface within two days of dipping. The bone like apatite formation of glass surface demonstrates the potential of glass for integration with bone.     

Immersion behaviour of calcium polyphosphate in simulated body fluid

This work documents an investigation into the immersion behaviour of calcium polyphosphate (CPP) in simulated body fluid (SBF) for various periods. The results showed that with the increase of soaking time in SBF, a number of tiny particles were observed on the surface of samples by scanning electron microscope (SEM). The results of X-ray diffraction (XRD) indicated that the particles were contributed to apatite. And the changes of PO₄³⁻ and Ca²⁺ concentrations in SBF were detected by phospho-vanado-molybdate method and inductively coupled plasma atomic emission spectroscopy (ICP) methods respectively. The results indicated that the concentrations of PO₄³⁻ and Ca²⁺ in SBF reached the maximum value after 25 days of immersion, and then decreased with further increase of the soaking time. It is suggested that the degradation and ion exchange of CPP samples are dominant during the early stage of soaking, and then the precipitates begin to form and increase gradually as the soaking time increases. This study has demonstrated that apatite could be formed on the surface of CPP samples, and CPP would be used as bone substitution material.     

Investigation on bio-mineralization of melt and sol-gel derived bioactive glasses

The bio-mineralization properties of the melt-derived bioactive glass 45S5 and the sol-gel derived bioactive glasses 58S and 77S were investigated and compared using in vitro test combined with BET, XRD, FTIR and SEM techniques. It was found that the surfaces of the three bioactive glasses could be mineralized by immersion in a simulated body fluid (SBF) at 37 °C for several hours. The bio-mineralized products on the surfaces of the bioactive glasses were apatite microcrystals with a low crystallinity, but the composition and morphologies of the apatite microcrystals on three glasses were different.     

Investigation of the surface reactivity of a sol-gel derived glass in the ternary system SiO2-CaO-P2O5

A new glass formulation, with the molar composition 60% SiO₂-35% CaO-5% P₂O₅, was synthesized using the sol-gel process, for applications as biomaterial in orthopaedic or maxillo facial surgery. Pellets, made of glass powder, were uniaxially compacted and soaked in simulated body fluid (SBF) for up to 7 days at 37 °C to evaluate glass bioactivity. Ionic exchanges at the interface glass-SBF were evaluated by studying evolutions of calcium, phosphorus and silicon concentrations in SBF using ICP-OES. Changes in glass surface, and the formation of crystalline phases were analyzed using XRD, SEM, EDS and FTIR methods.Results form ICP-OES showed a high reactivity of the glass surface with a very high and continuous release of calcium, a limited glass dissolution and an uptake of phosphorous from SBF. Results from both FTIR and XRD analysis indicated that the glass surface was progressively covered by two different phases: CaCO₃ as calcite and a carbonated apatite layer. The formation of these phases, following two different schemas, was observed after 2 h of immersion and confirmed after 7 days. SEM micrographs and EDS analysis demonstrated that the main phase, a carbonated apatite, was present as micro-spheroids and the secondary phase, calcite, was materialized by agglomerates which have diameters up to 10-15 μm. These results are in accordance with a bioactive feature of the glass studied.     

In vitro biological performance of nano-particles on the surface of hydroxyapatite coatings

The biocompatibility of a kind of heat-treated bilayer hydroxyapatite (HA) coatings with nano-particles was investigated, mainly in terms of the immersion in simulated body fluid (SBF) and osteoblast adhesion. Scanning electron microscopy (SEM) was used to observe the morphology of coatings and cellular adhesion. The phases present in the coatings were determined by X-ray diffraction (XRD). Calcium ion (Ca²⁺) concentration in SBF was measured by Atomic absorption spectrophotometer. The results show nano-HA heat-treated at 650 °C for 0.5 h (BBCs) is comparatively stable during immersion in SBF and favor of the adhesion of osteoblasts. Cellular filopodia adhere firmly to the nano-particles and stretch in various direction.     

Bioactive glass (type 45S5) nanoparticles: in vitro reactivity on nanoscale and biocompatibility

Bioactive glasses represent important biomaterials being investigated for the repair and reconstruction of diseased bone tissues, as they exhibit outstanding bonding properties to human bone. In this study, bioactive glass (type 45S5) nanoparticles (nBG) with a mean particle size in the range of 20?C60?nm, synthesised by flame spray synthesis, are investigated in relation to in vitro bioreactivity in simulated body fluid (SBF) and response to osteoblast cells. The structure and kinetics of hydroxyapatite formation in SBF were investigated using transmission electron microscopy (TEM), X-ray diffraction (XRD) and Fourier-transform infrared spectroscopy (FT-IR) revealing a very rapid transformation (after 1?day) of nBG to nanocrystalline bone-like carbonated HAp. Additionally, calcite is formed after 1?day of SBF immersion because of the high surface reactivity of the nBG particles. In the initial state, nBG particles were found to exhibit chain-like porous agglomerates of amorphous nature which are transformed on immersion in SBF into compact agglomerates covered by hydroxyapatite with a reduced size of the primary nanoparticles. In vitro studies revealed high cytocompatibility of nBG with human osteoblast cells, indicated through high lactatedehydrogenase (LDH) and mitochondrial activity as well as alkaline phosphatase activity. Hence, this study contributes to the understanding of the structure and bioactivity of bioactive glass (type 45S5) nanoparticles, providing insights to the phenomena occurring at the nanoscale after immersion in SBF. The results are relevant in relation to the understanding of the nanoparticles?? bioreactivity required for applications in bone tissue engineering.     

In vitro evaluation of bioactivity of CaO-SiO2-P2O5-Na2O-Fe2O3 glasses

Glasses with compositions 41CaO(52 − x)SiO₂4P₂O₅·xFe₂O₃3Na₂O (2 ≤ x ≤ 10 mol.%) were prepared by melt quenching method. Bioactivity of the different glass compositions was studied in vitro by treating them with simulated body fluid (SBF). The glasses treated for various time periods in SBF were evaluated by examining apatite formation on their surface using grazing incidence X-ray diffraction, Fourier transform infrared reflection spectroscopy, scanning electron microscopy and energy dispersive spectroscopy techniques. Increase in bioactivity with increasing iron oxide content was observed. The results have been used to understand the evolution of the apatite surface layer as a function of immersion time in SBF and glass composition.     

Increased strontium uptake in trabecular bone of ovariectomized calcium‐deficient rats treated with strontium ranelate or strontium chloride

Based on clinical trials showing the efficacy to reduce vertebral and non‐vertebral fractures, strontium ranelate (SrR) has been approved in several countries for the treatment of postmenopausal osteoporosis. Hence, it is of special clinical interest to elucidate how the Sr uptake is influenced by dietary Ca deficiency as well as by the formula of Sr administration, SrR versus strontium chloride (SrCl₂). Three‐month‐old ovariectomized rats were treated for 90 days with doses of 25 mg kg^?1 d^?1 and 150 mg kg^?1 d^?1 of SrR or SrCl₂ at low (0.1% Ca) or normal (1.19% Ca) Ca diet. Vertebral bone tissue was analysed by confocal synchrotron‐radiation‐induced micro X‐ray fluorescence and by backscattered electron imaging. Principal component analysis and k‐means clustering of the acquired elemental maps of Ca and Sr revealed that the newly formed bone exhibited the highest Sr fractions and that low Ca diet increased the Sr uptake by a factor of three to four. Furthermore, Sr uptake in bone of the SrCl₂‐treated animals was generally lower compared with SrR. The study clearly shows that inadequate nutritional calcium intake significantly increases uptake of Sr in serum as well as in trabecular bone matrix. This indicates that nutritional calcium intake as well as serum Ca levels are important regulators of any Sr treatment.     

Gamow-Teller β transition from the 2− ground state of88Rb to the 3− excited state of88Sr

The Gamow-Tellerβ-transition from the ground state 2^? of⁸⁸Rb to the 3^? level at 2.734 MeV of⁸⁸Sr is studied. The nuclear matrix element 〈σ〉 and the lofft value are calculated using complete nuclear wave functions for the initial and final states. It is shown that, contrary to the normal assumption, the component ¦π2p ₃ ^2/?1 π1g _9/2〉 of the final state does give a very important contribution to 〈σ〉 due to the presence of strong cancellation effects. Although our calculations favour a wave function for the 3^? level⁸⁸Sr where neutron 1h—1p configurations are not included, there are still some facts which make that our results cannot be taken as conclusive. Nuclear Structure⁸⁸Rb,⁸⁸Sr, calculated the Gamow-Teller nuclear matrix element 〈σ〉 and the logft value using a shell model.     

Effect of Sr concentration on microstructure and magnetic properties of (Ba1−xSrx)(Ti0.3Fe0.7)O3 ceramics

Fe-doped (Ba_1−xSr_x)TiO₃ ceramics were prepared by solid-state reaction, and ferromagnetism was realized at room temperature. The microstructure and magnetism were modified by the Sr concentration control (0≤x≤75 at%) at a fixed Fe concentration, and the relevant magnetic exchange mechanism was discussed. All the samples are shown to have a single perovskite structure. When increasing the Sr concentration, the phase structure is transformed from a hexagonal perovskite into a cubic perovskite, with a monotonic decrease in lattice parameters induced by ionic size effect. The room-temperature ferromagnetism is expected to originate from the super-exchange interactions between Fe³⁺ on pentahedral and octahedral Ti sites mediated by the O²⁻ ions. The increase in Sr addition modifies two main influencing factors in magnetic properties: the ratio of pentahedral to octahedral Fe³⁺ and the concentration of oxygen vacancies, leading to a gradually enhanced saturation magnetization. The highest value, obtained for Fe-doped (Ba_0.25Sr_0.75)TiO₃, is an order of magnitude higher than that of the Fe-doped BaTiO₃ system with similar Fe concentration and preparation conditions, which may indicate (Ba_1−xSr_x)TiO₃ as a more suitable matrix material for multiferroic research.     

Effect of akermanite morphology on precipitation of bone-like apatite

Bioactivity in vivo of ceramic materials has been related to their surface micro-topography and may be estimated by means of simulated body fluid method in vitro. In order to investigate the effect of surface topographies of akermanite ceramics on bioactivity in vitro, akermanite ceramics were synthesized by sol-gel method and different surface topographies of disc-shaped akermanite ceramics were prepared by polishing with different SiC sandpapers. Atomic force microscopy (AFM) was used to evaluate the surface morphology and roughness. The bioactivity in vitro of ceramics with different surface states was evaluated by soaking the ceramics in simulated body fluid (SBF). And the samples after being soaked were characterized by scanning electron microscopy (SEM), X-ray diffraction (XRD) and energy dispersive spectrometry (EDS). The results showed that the amounts of precipitated apatite on the ceramics with different surface roughness after being soaked in SBF were different and the bioactivity in vitro of ceramic with rough surface was significantly higher than that of ceramic with smooth surface. The study suggested that suitable surface roughness may improve the bioactivity in vitro of akermanite ceramics.     

Structure,dielectric and bioactivity of P2O5–CaO–Na2O–B2O3 bioactive glass

Bioactive phosphate glasses have been widely investigated for bone repair. Phosphate glass system of 47P₂O₅–30.5CaO–(22.5?x)Na₂O–xB₂O₃ has been prepared by melt quenching technique. From the Raman analysis, it is confirmed that phosphate network form metaphosphate structure. Bioactivity of the glass is studied by immersing the prepared glass in simulated body fluid (SBF). All the glasses exhibited bioactivity after soaking in SBF. Addition of B₂O₃ to the glass by replacing the Na₂O produces considerable effect on the dielectric and bioactivity of the glass. Ion dynamics are also analyzed through imaginary modulus and imaginary dielectric permittivity.     

Discovery of radioactive silver (110mAg) in spiders and other fauna in the terrestrial environment after the meltdown of Fukushima Dai-ichi nuclear power plant

Six months after the explosion of TEPCO’s Fukushima Dai-ichi nuclear power plant, radioactive silver (^110mAg), was detected in concentrations of 3754 Bq/kg in Nephila clavata (the orb-web spider; Joro-gumo in Japanese) collected at Nimaibashi, Iitate village in Fukushima Prefecture, whereas ^110mAg in the soil was 43.1 Bq/kg. A survey of 35 faunal species in the terrestrial environment during the 3.5 years after the accident showed that most of Anthropoda had two orders higher ^110mAg in their tissues than soils, although silver is not an essential element for their life. However, tracing of the activity of ^110mAg detected in spider Atypus karschi collected regularly at a fixed location showed that it declined much faster than the physical half-life. These results suggest that ^110mAg was at once biologically concentrated by faunal species, especially Arthropoda, through food chain. The factors affecting the subsequent rapid decline of ^110mAg concentration in faunal species are discussed.     

Biomimetic apatite induction on Ca-containing titania

To understand the apatite induction mechanism in SBF, Ca-containing titania film without CaTiO₃ phase was fabricated by micro-arc oxidation (MAO) at low voltage (230 V) in an electrolytic solution containing calcium acetate monohydrate. Macro-porous, Ca-containing titania film was formed on the titanium substrate and the oxidized layer was composed of anatase and rutile phase. When immersed in 1.5SBF, no apatite was induced in the MAO specimen similar to the CaTiO₃-containing titania. However, after hydrothermal treatment at 250 °C for 2 h, numerous precipitates, presumably calcium phosphates, were formed on the surface of the titania after 7 day immersion and titania surface was entirely covered with apatite after 14 days of immersion. This study clearly showed that Ca-containing titania has the capability to induce apatite in SBF and hydrothermal treatment plays a decisive role in apatite induction, particularly producing surface hydroxyl groups such as Ca–OH or Ti–OH.     

Corrosion resistance and blood compatibility of lanthanum ion implanted pure iron by MEVVA

Pure iron is a potential material applying for coronary artery stents based on its biocorrodible and nontoxic properties. However, the degradation characteristics of pure iron in vivo could reduce the mechanical stability of iron stents prematurely. The purpose of this work was to implant the lanthanum ion into pure iron specimens by metal vapor vacuum arc (MEVVA) source at an extracted voltage of 40 kV to improve its corrosion resistance and biocompatibility. The implanted fluence was up to 5 × 10¹⁷ ions/cm². The X-ray photoelectron spectroscopy (XPS) was used to characterize the chemical state and depth profiles of La, Fe and O elements. The results showed lanthanum existed in the +3 oxidation state in the surface layer, most of the oxygen combined with lanthanum and form a layer of oxides. The lanthanum ion implantation layer could effectively hold back iron ions into the immersed solution and obviously improved the corrosion resistance of pure iron in simulated body fluids (SBF) solution by the electrochemical measurements and static immersion tests. The systematic evaluation of blood compatibility, including in vitro platelets adhesion, prothrombin time (PT), thrombin time (TT), indicated that the number of platelets adhesion, activation, aggregation and pseudopodium on the surface of the La-implanted samples were remarkably decreased compared with pure iron and 316L stainless steel, the PT and TT were almost the same as the original plasma. It was obviously showed that lanthanum ion implantation could effectively improve the corrosion resistance and blood compatibility of pure iron.     

Physical properties of double perovskite compounds ALaVMoO6 (A=Ca, Sr, Ba)—a possible half-metallic antiferromagnetic system

Double perovskite compounds ALaVMoO₆ (A=Ca, Sr, Ba) have been synthesized and their electrical and magnetic properties have been investigated. Magnetization measurements have indicated the possible antiferromagnetic transitions at 120 and 130 K for A=Ca and Sr samples, respectively. Electrical resistivity ρ for this system shows metallic temperature dependence from 300 to 20 K, though the sample with A=Ca shows weak semiconducting behavior in the low temperature region (<70 K). Considering the magnetic and electrical properties and assuming the V³⁺S=1 and Mo⁴⁺S=1 valence and spin states, the samples with A=Ca and Sr can be promising candidates for half-metallic antiferromagnets.