Thermal properties and surface reactivity in simulated body fluid of new strontium ion-containing phosphate glasses

In this paper, we investigate the effect of SrO substitution for CaO in 50P₂O₅–10Na₂–(40?x)CaO–xSrO glass system (x from 0 to 40) on the thermal and structural properties and also on the glass reactivity in simulated body fluid (SBF) in order to find new glass candidates for biomedical glass fibers. The addition of SrO at the expense of CaO seems to restrain the leaching of phosphate ions in the solution limiting the reduction of the solution pH. We observed the formation of an apatite layer at the surface of the glasses when in contact with SBF. SrO and MgO were found in the apatite layer of the strontium ion-containing glasses, the concentration of which increases with an increase of SrO content. We think that it is the presence of MgO and SrO in the layer which limits the leaching of phosphate in the solution and thus the glass dissolution in SBF.     

The effect of Sr concentration on bioactivity and biocompatibility of sol–gel derived glasses based on CaO–SrO–SiO2–P2O5 quaternary system

In the present study, sol–gel derived glasses based on CaO–SrO–SiO₂–P₂O₅ system were prepared and the effect of Sr concentration on in vitro bioactivity and cellular properties of the glasses were investigated. SrO was substituted for CaO in the glass formula up to 10 mol% and in vitro bioactivity of the samples was evaluated by soaking them in simulated body fluid followed by structural characterization using XRD, FTIR and SEM techniques. The effects of various glass compositions on proliferation and differentiation of osteoblastic cells were also evaluated. The results showed that the substitution of Sr for Ca in the glass composition retarded formation of apatite layer onto the glass surfaces. Morphologies of the apatite layers were also different in which abundance of the crystals decreased with increasing Sr concentration. The bioactive glasses did not exert cytotoxic effect on the cells, however the proliferation and alkaline phosphatase activity of the cells on the samples containing low doses of Sr were higher than those of control and the samples with high dose of Sr. Glass specimen with 5 mol% of Sr exhibited appropriate bioactivity with optimal cell proliferation and ALP activity.     

Effects of boron oxide substitution on the structure and bioactivity of SrO-containing bioactive glasses

B₂O₃/SiO₂ substitution in 55S4.3 bioactive glasses with 5 mol% of SrO has been synthesized and characterized to understand their structure and bioactivity as a function of composition by combining experimental and computer simulation techniques. Raman spectrometry, X-ray diffraction (XRD) and Fourier transform infrared spectrometry (FTIR) were utilized to characterize the structural changes induced by boron content and to identify the formation of hydroxyapatite (HAp). In vitro bioactivity tests were performed in simulated body fluid with a fixed glass mass to solution volume ratio and a particle size range. Needle-like HAp was found to form on the surface of the 55S4.3 with SrO sample from scanning electron microscopy and confirmed from XRD and FTIR. In addition to the experimental efforts, these glasses were also simulated using classical molecular dynamics simulations with partial charge potentials and recently developed parameters for boron oxide to understand their short- and medium-range structures. The glasses from simulations were analyzed in terms of the local structure around the glass network formers, especially the boron coordination number, and found to agree well with theoretical models. The medium-range structural information such as Q _n distribution and network connectivity was also obtained and used to understand the compositional dependence of property and bioactivity. The results show that additional boron oxide increased the network connectivity of the 55S4.3 glass and inhibited or delayed the formation of HAp in vitro.     

Synthesis and dissolution behaviour of CaO/SrO-containing sol–gel-derived 58S glasses

The effect of the substitution of strontium for calcium in the tertiary the SiO₂–CaO–P₂O₅ sol–gel bioactive glass 58S (60SiO₂·36CaO·4P₂O₅, mol%) on its structure and its chemical durability on soaking in simulated body fluids was investigated. 58S was selected as a starting composition, and substitution for calcium was carried out from 0 to 100% with an increment of 25%. A novel phosphate source of diethylphosphatoethyltriethoxysilane, which consists of Si and P connected with ethylene group, was used in this work. XRD and FTIR showed that the gels obtained following drying at 130 °C had a typical sol–gel structure, where a continuous amorphous silica gel network and surface bound mineral salts of Ca(NO₃)₂ and Sr(NO₃)₂. Once the gels were heat stabilised to decompose nitrates and incorporate the cations into the network, samples containing Sr formed a strontium silicate crystalline phase. With increasing levels of Sr in the composition, the overall crystallinity of the glass–ceramic increased, while, at the maximum substitution of 100% SrO, macroscopic phase separation was observed, characterised by needle-like crystals of strontium apatite (Sr₅(PO₄)₃OH) and strontium silicate (Sr₂SiO₄) phases in addition to amorphous regions. Dissolution experiments in Tris-buffered solution showed Sr successfully released into the media even though it existed as a crystalline phase in the glass–ceramic. Further, the glass–ceramics induced nucleation and growth of carbonated hydroxyapatite (HA) on their surface suggesting potential bioactivity of the materials. At higher substitutions (75 and 100% SrO for CaO), HA nucleation was not found to occur this may have been due to low amount of phosphate released from the original glass–ceramic as a result of it being locked up in the strontium apatite phase.     

The processing,mechanical properties and bioactivity of strontium based glass polyalkenoate cements

The suitability of zinc-based glass polyalkenoate cements (GPCs) for use in orthopaedics can be improved by the substitution of strontium into the glass phase which should impart improved radiopacity and bone forming properties to the cements without retarding strength. The purpose of this research was to produce novel GPCs based on calcium–strontium–zinc-silicate glasses and to evaluate their mechanical properties and biocompatibility with the ultimate objective of developing a new range of cements for skeletal applications. Three glass compositions, based on incremental substitutions of strontium for calcium, were synthesized; BT100 (0.16CaO, 0.36ZnO, 0.48SiO₂), BT101 (0.04SrO, 0.12CaO, 0.36ZnO, 0.48SiO₂) and BT102 (0.08SrO 0.08CaO, 0.36ZnO, 0.48SiO₂). Each glass was then mixed with varying concentrations and molecular weights of polyacrylic acids in order to determine the working times, setting times, compressive strengths and biaxial flexural strengths of the novel cements. The maximum working time and setting time achieved was 29 and 110 s respectively; which, at present is inadequate for current clinical procedures. However, the optimum compressive and biaxial flexural strengths were up to 75 and 34 MPa respectively indicating that these formulations have potential in load bearing applications. Importantly, the substitution of Ca with Sr in the glasses did not have a deleterious effect on strengths or working times. Finally, the bioactivity of the best performing cements was determined in vitro using simulated body fluid. It was found that all cements facilitate the formation of an amorphous calcium phosphate at their surface which increases in density and coverage with time, indicating that these cement will bond directly to bone in vivo.     

含锶硼硅酸盐生物玻璃的降解性能及体外生物活性

研究了含锶硼硅酸盐玻璃的体外生物活性和降解性。采用熔融法制备不同锶含量(SrO含量为0、2%、4%、6%、8%、10%、12%(摩尔分数))的硼硅酸盐生物玻璃粉末,粒径范围为150～300μm。将各组玻璃样品浸泡在0.02mol/L的K2HPO4溶液中,置于37℃恒温条件下,进行体外生物矿化反应。通过对反应样品的质量损失以及浸泡液pH值进行测定,并用XRD、FTIR以及SEM对反应过程和反应后产物进行表征。结果表明,含锶的硼硅酸盐玻璃在体外生物矿化反应中被生物降解,并转化为含锶羟基磷灰石,具有很好的生物活性和降解性;同时也观察到玻璃中引入锶元素后,在一定程度上控制玻璃的降解速度,进而控制硼的溶出速度,从一定程度上避免硼溶出速度过高可能带来的风险;ICP的结构也表明,当SrO为6%(摩尔分数),样品中硼元素溶出的速度最低。因此,用锶的含量可控制硼硅酸盐玻璃的降解速度,这种方法将在组织工程领域具有广阔的应用前景。     

Influence of strontium for calcium substitution on the glass–ceramic network and biomimetic behavior in the ternary system SiO<Subscript>2</Subscript>–CaO–MgO

Strontium (Sr) enhances bone formation both in vitro and in vivo, while it reduces bone resorption. Thus, Sr incorporation in bioactive glass–ceramic scaffolds for bone tissue regeneration could further enhance osteogenesis. The aim of this work was the synthesis, characterization and investigation of the apatite-forming ability in inorganic environment of two sol–gel-derived bioactive Sr-containing glass–ceramic materials with 5 and 10% of SrO. The thermal properties of the synthesized materials were studied using differential thermal analysis (TG–DTA). The apatite-forming ability test was conducted in SBF for various immersion times for both thermally treated and untreated samples. The characterization of the samples before and after immersion in SBF was performed with Fourier transform infrared spectroscopy (FTIR), X-ray powder diffraction (XRD) and scanning electron microscopy with associated energy-dispersive spectroscopy. FTIR spectra revealed that all synthesized glass–ceramic materials presented the characteristic bands of silicate glasses, while XRD identified various crystalline phases, mostly calcium silicates. Strontium is present in the form of strontium silicate in both as-received and thermally treated specimens, and Sr-diopside in the thermally treated specimens. The apatite-forming ability of the glass–ceramic materials was confirmed by the formation of a hydroxyapatite layer after 3 and 5 days of immersion in SBF on the surface of the untreated and thermally treated samples, respectively. The apatite layer, also, became thicker as the immersion time increased.     

Functionally graded bioactive glass coating on magnesia partially stabilized zirconia (Mg-PSZ) for enhanced biocompatibility

The coating of magnesia partially stabilized zirconia (Mg-PSZ) with a bioactive glass was investigated for enhancing the bioactivity and bone-bonding ability of Mg-PSZ orthopedic implants. Individual coatings of three different bioactive glasses were prepared by depositing a concentrated suspension of the glass particles on Mg-PSZ substrates, followed by sintering at temperatures between 750 °C and 850 °C. Two silicate-based glass compositions (designated 13–93 and 6P68), and a borosilicate glass composition (H12) were investigated. The microstructure and adhesive strength of the coatings were characterized, and the in vitro bioactivity of the glasses was compared by measuring their conversion kinetics to hydroxyapatite in an aqueous phosphate solution at 37 °C. The 6P68 glass provided the highest adhesive strength (40 ± 2 MPa) but showed very limited bioactivity, whereas the H12 glass had lower adhesive strength (18 ± 2 MPa) but the highest bioactivity. A functionally graded coating, consisting of a 6P68 interfacial layer and an H12 surface layer, was developed to provide a coating with high adhesive strength coupled with rapid in vitro bioactivity.     

Thermal,structural and in vitro dissolution of antimicrobial copper-doped and slow resorbable iron-doped phosphate glasses

This paper focuses on investigating and comparing the effects of CuO and Fe₂O₃ addition on the bioactive response of glass having composition [xCuO or Fe₂O₃ + (100 ? x) (0.2CaO + 0.2SrO + 0.1Na₂O + 0.5P₂O₅)] (in mol%), where x is ranging from 0 up to 5. The addition of CuO was found to increase the hot processing window and the dissolution rate leading to a fast surface layer precipitation. Using IR and Raman spectroscopies, we related this change in the bioactive response of this glass to the progressive depolymerization of the glass network induced by the addition of CuO. On the other hand, the addition of Fe₂O₃ was found to reduce the hot processing window and the dissolution rate as no depolymerization of the network occurs due to the formation of P–O–Fe bonds at the expense of P–O–P bonds. All the glasses were found to dissolve congruently and in a controlled manner. Finally, the antimicrobial properties of the copper-doped glasses were examined and compared to bioactive glasses which are known to exhibit good antimicrobial properties. The CuO addition leads to higher antimicrobial properties than the commercial bioactive glass S53P4 and total bacterial elimination could be obtained.     

SrO/CaO比对无碱铝硼硅酸盐玻璃热膨胀系数与低温特征粘度参考点的影响

恒定无碱铝硼硅酸盐玻璃中碱土金属氧化物的质量百分比不变,研究了SrO和CaO的相互替代对玻璃的热膨胀系数、应变点温度、玻璃转变温度、退火点温度、膨胀软化点温度等低温特征粘度参考点的影响。结果表明:玻璃的热膨胀系数随着n(SrO)/n(CaO)比值的增大而逐渐减小,低温特征粘度参考点在n(RO)/n(Al2O3)=0.96时达到极大值。     

Do properties of bioactive glasses exhibit mixed alkali behavior?

The effect of substituting K₂O for Na₂O on the physical and chemical properties of 15 glasses in the system Na₂O–K₂O–CaO–P₂O₅–SiO₂ was studied for three series: low (52 mol% SiO₂), medium (60 mol% SiO₂) and high (66 mol% SiO₂) silica. The SiO₂ content expressed as weight-% varied from 46 to 64 wt%, thus suggesting that the compositions were either bioactive or biocompatible. The crystallization tendency and sintering behavior were studied using differential thermal analysis and hot stage microscopy. Formation of silica- and hydroxy-apatite-rich layers were studied for glass plates immersed in static simulated body fluid. The release of inorganic ions into Tris buffer solution was analyzed using inductively coupled plasma optical emission spectrometer in dynamic and static conditions. Substitution of K₂O for Na₂O suggested mixed alkali effect (MAE) for the thermal properties with a minimum value around 25% substitution. With increased share of K₂O in total alkali oxides, the hot working window markedly expanded in each series. Silica and hydroxyapatite layers were seen only on the low silica glasses, while a thin silica-rich layer formed on the other glasses. In each series, greater dissolution of alkali and alkali earth ions was seen from K-rich glasses. Clear MAE and preferential ion dissolution were recorded for medium and high silica series, while for low silica glasses, the initial MAE dissolution trends become rapidly covered by other simultaneous surface reactions. MAE enables designing especially low silica bioactive glasses for improved hot working properties and medium and high silica glasses for controlled dissolution.     

含Zn、Mg生物玻璃的制备及性能研究

采用溶胶-凝胶法,在58S生物玻璃的基础上,分别用0.5wt％的氧化镁和氧化锌取代氧化钙制备了含镁和含锌的生物玻璃.压制的试样分别在600、700和800℃煅烧以做强度测试,并分析了600和800℃煅烧后的物相组成.结果表明,三种试样煅烧至800℃仍为玻璃态,而镁锌的掺入大幅度提高了生物玻璃的强度,这主要是因为Mg-O和Zn-O具有比Ca-O高的键能.模拟体液浸泡试验表明,镁和锌降低了羟基磷灰石的早期成核速度,但并不影响其后期的生长.浸泡三天后所有样品表面都被羟基磷灰石覆盖,表明了样品具有良好的生物活性.     

Cerium-doped bioactive 45S5 glasses: spectroscopic,redox, bioactivity and biocatalytic properties

The ability of Ce-containing bioactive glasses, based on 45S5 Bioglass^®, to inhibit oxidative stress in terms of reduction in hydrogen peroxide and superoxide (O₂ ^?), by mimicking the catalase and superoxide dismutase activity is reported in this work. The characterization is performed on the powders of pristine glasses and after the soaking in H₂O₂ solutions and simulated body fluid. The glass samples are analysed by XPS, XRD, UV–Vis and FT-IR. The best catalyst activities are obtained for the glass with the highest content of cerium (H_5.3 = 5.3 mol% of CeO₂ in the nominal glass composition), and the best Ce³⁺/Ce⁴⁺ ratio in terms of catalase mimetic activity is found to be a function of H₂O₂ concentration. Moreover, the detailed study of the surface during the mimic enzymatic activity tests shows the formation of a Ca-P-rich layer on the glass surface, where the presence of Ce ions favours the formation of CePO₄. The phosphate in turn inhibits the formation of hydroxyapatite, decreasing the bioactivity of the glass with the highest of CeO₂ in the glass composition. This work shows the effect of Ce³⁺/Ce⁴⁺ ratio towards the catalase mimetic activity and for the first time the superoxide dismutase mimetic activity of Ce-containing 45S5-derived glasses.     

The effects of Sr concentration on physicochemical properties,bioactivity and biocompatibility of sub-micron bioactive glasses spheres

We synthetized a series of strontium-substituted submicron bioactive glasses spheres (Sr-SBG, SiO₂-P₂O₅-CaO-SrO) in which strontium was substituted for calcium on a mole percentage basis, then investigated the effect of strontium-substituted amount on morphologies, physicochemical properties, apatite-forming bioactivity of SBG and evaluated the proliferation, differentiation and mineralization of Sr-SBG with different strontium substitution amounts by co-cultured with human dental pulp cells (HDPCs). Results showed that Sr-SBG with different strontium substitution amounts were successfully fabricated and substituting different strontium amounts did not affect the morphology and particle size of SBG. All the Sr-SBG possessed good apatite-forming ability, but substituting a certain amount of strontium for calcium would weaken the apatite-forming ability of SBG. Additionally, all the Sr-SBG extractions promoted proliferation, early odontogenic differentiation and mineralization of HDPCs, however, the cell proliferation, differentiation and mineralization abilities would be reduced when the substituted amount of strontium was excess (15 mol%). This study suggests that Sr-SBG with moderate strontium substitution amounts can be used as a more promising biomaterial for dental repair.     

Characterisation of the bioactive behaviour of sol–gel hydroxyapatite–CaO and hydroxyapatite–CaO–bioactive glass composites

The fabrication and characterization of sol–gel derived hydroxyapatite–calcium oxide (HAp–CaO) material is investigated focusing on the effect of the addition of a bioactive glass on the material bioactive behaviour through the fabrication of a novel HAp–CaO (70 wt.%)–bioactive glass (30 wt.%) composite material. The bioactive behaviour of the materials was assessed by immersion studies in Simulated Body Fluid (SBF) and the alterations of the materials surfaces after soaking periods in SBF were characterized by Scanning Electron Microscopy (SEM) and Fourier Transform Infrared Spectroscopy (FTIR). A brittle and weakly crystalline carbonate hydroxyapatite (HCAp) layer was found to develop on the surface of all samples, few hours after immersion in SBF, confirming the high bioactivity of the material. Alterations of the morphology of the developed HCAp layer, which led to a more compact structure, were observed on the surface of composite samples after 7 days of immersion in SBF. The presence of the CaO phase seems to accelerate the formation of HCAp, while the bioactive glass affects both the morphology and cohesion of the developed layer.     

The use of advanced diffraction methods in the study of the structure of a bioactive calcia: silica sol-gel glass

Sol-gel derived calcium silicate glasses may be useful for the regeneration of damaged bone. The mechanism of bioactivity is as yet only partially understood but has been strongly linked to calcium dissolution from the glass matrix. In addition to the usual laboratory-based characterisation methods, we have used neutron diffraction with isotopic substitution to gain new insights into the nature of the atomic-scale calcium environment in bioactive sol-gel glasses, and have also used high energy X-ray total diffraction to probe the nature of the processes initiated when bioactive glass is immersed in vitro in simulated body fluid. The data obtained point to a complex calcium environment in which calcium is loosely bound within the glass network and may therefore be regarded as facile. Complex multi-stage dissolution and mineral growth phases were observed as a function of reaction time between 1 min and 30 days, leading eventually, via octacalcium phosphate, to the formation of a disordered hydroxyapatite (HA) layer on the glass surface. This methodology provides insight into the structure of key sites in these materials and key stages involved in their reactions, and thereby more generally into the behaviour of bone-regenerative materials that may facilitate improvements in tissue engineering applications.     

Investigating the effect of SiO2–TiO2–CaO–Na2O–ZnO bioactive glass doped hydroxyapatite: characterisation and structural evaluation

The effects of increasing bioactive glass additions, SiO₂–TiO₂–CaO–Na₂O–ZnO up to 25 wt% in increments of 5 wt%, on the physical and mechanical properties of hydroxyapatite (HA) sintered at 900, 1000, 1100 and 1200 °C for 2 h was investigated. Increasing both the glass content and the temperature resulted in increased HA decomposition. This resulted in the formation of a number of bioactive phases. However the presence of the liquidus glass phase did not result in increased densification levels. At 1000 and 1100 °C the additions of 5 wt% glass resulted in a decrease in density which never recovered with increasing glass content. At 1200 °C a cyclic pattern resulted from increasing glass content. There was no direct relationship between strength and density with all samples experiencing no change or a decrease in strength with increasing glass content. Weibull statistics displayed no pattern with increasing glass content.     

The role of Sr<Superscript>2+</Superscript> on the structure and reactivity of SrO–CaO–ZnO–SiO<Subscript>2</Subscript> ionomer glasses

The suitability of Glass Polyalkenoate Cements (GPCs) for use in orthopaedics is retarded by the presence in the glass phase of aluminium, a neurotoxin. Unfortunately, the aluminium ion plays an integral role in the setting process of GPCs and its absence is likely to hinder cement formation. However, the authors have previously shown that aluminium free GPCs may be formulated based on calcium zinc silicate glasses and these novel materials exhibit significant potential as hard tissue biomaterials. To further improve their potential, and given that Strontium (Sr) based drugs have had success in the treatment of osteoporosis, the authors have substituted Calcium (Ca) with Sr in the glass phase of a series of aluminium free GPCs. However to date little data exists on the effect SrO has on the structure and reactivity of SrO–CaO–ZnO–SiO₂ glasses. The objective of this work was to characterise the effect of the Ca/Sr substitution on the structure of such glasses, and evaluate the subsequent reactivity of these glasses with an aqueous solution of Polyacrylic acid (PAA). To this end ²⁹Si MAS-NMR, differential scanning calorimetry (DSC), X-ray diffraction, and network connectivity calculations, were used to characterize the structure of four strontium calcium zinc silicate glasses. Following glass characterization, GPCs were produced from each glass using a 40 wt% solution of PAA (powder:liquid = 2:1.5). The working times and setting times of the GPCs were recorded as per International standard ISO9917. The results acquired as part of this research indicate that the substitution of Ca for Sr in the glasses examined did not appear to significantly affect the structure of the glasses investigated. However it was noted that increasing the amount of Ca substituted for Sr did result in a concomitant increase in setting times, a feature that may be attributable to the higher basicity of SrO over CaO.     

Sol–gel-derived manganese-releasing bioactive glass as a therapeutic approach for bone tissue engineering

Sol–gel processing allows the production of bioactive glasses (BG) with flexible compositions and the incorporation of different metallic ions with therapeutic benefits into the glass network. Manganese is among several previously studied therapeutically beneficial ions and has been shown to favour osteogenic differentiation, in addition to playing an important role in cell adhesion. The incorporation of Mn into bioactive glasses for tissue engineering has been previously conducted using the conventional melting route, whereas the sol–gel route has not yet been explored. Sol–gel technology has great versatility, allowing the preparation of BG with various compositions, sizes, morphologies and a large surface area that could provide improved cellular responses and enhanced bioactivity when compared to melt-derived glasses. In this context, this work developed new compositions of sol–gel bioactive glasses (on the SiO₂–P₂O₅–CaO–MnO system) and explored the effects of incorporating MnO on the structure, texture, in vitro bioactivity and cytocompatibility of these materials. Our results show that Mn-containing bioactive glasses present an amorphous character, high surface area and mesoporous structure. The formation of a hydroxycarbonate apatite (HCA) layer after immersion in simulated body fluid (SBF) revealed the high bioactivity of the glasses. Ion release evaluation indicated that the Si, Ca, P and Mn release levels could be adjusted within therapeutic limits, and cytotoxic analysis demonstrated that the ionic products of all samples generated a cell-friendly environment. Therefore, Mn incorporation into the bioactive glass network appears to be a potential strategy to develop superior materials with sustained ion release for tissue engineering.     

In vitro behaviour of three biocompatible glasses in composite implants

Poly(l,dl-lactide) composites containing filler particles of bioactive glasses 45S5 and S53P4 were compared with a composite containing a slowly dissolving glass S68. The in vitro reactivity of the composites was studied in simulated body fluid, Tris-buffered solution, and phosphate buffered saline. The high processing temperature induced thermal degradation giving cavities in the composites containing 45S5 and S53P4, while good adhesion of S68 to the polymer was observed. The cavities partly affected the in vitro reactivity of the composites. The degradation of the composites containing the bioactive glasses was faster in phosphate buffered saline than in the two other solutions. Hydroxyapatite precipitation suggesting bone tissue bonding capability was observed on these two composites in all three solutions. The slower dissolution of S68 glass particles and the limited hydroxyapatite precipitation suggested that this glass has potential as a reinforcing composition with the capability to guide bone tissue growth in biodegradable polymer composites.