Sol-gel Bioactive Glasses Research Articles

The influence of processing parameters on morphology and granulometry of a wet-milled sol-gel glass powder

A quaternary bioactive sol-gel glass of high silica content was heat treated at different temperatures, and then wet ball milled under different balls-to-powder ratios. A total of sixteen experiments were performed to study in detail the effects of both experimental variables on the structure, morphology, particle size distributions and nitrogen adsorption isotherms. The balls–to–powder ratio exerts a tremendous influence on the final particle size distribution of the powders, while its effects on the pore volume and morphology are minimal. These structural features are mostly governed by the changes in calcination temperature. Therefore, understanding the specific roles of each experimental parameter is of paramount importance towards achieving optimum powders with the desired properties. This work sheds light on the importance of using a suitable combination of these two parameters for tuning the morphology and the granulometry of the sol-gel derived bioactive glass powders.

Role of the Short Distance Order in Glass Reactivity.

In 2005, our group described for the first time the structural characterization at the atomic scale of bioactive glasses and the influence of the glasses’ nanostructure in their reactivity in simulated body fluids. In that study, two bioactive sol-gel glasses with composition 80%SiO2–20%CaO and 80%SiO2–17%CaO–3%P2O5 (in mol-%) were characterized by High-Resolution Transmission Electron Microscopy (HRTEM). Such characterization revealed unknown features of the glasses’ structure at the local scale that allowed the understanding of their different in vitro behaviors as a consequence of the presence or absence of P2O5. Since then, the nanostructure of numerous bioactive glasses, including melt-prepared, sol-gel derived, and mesoporous glasses, was investigated by HRTEM, Nuclear Magnetic Resonance (NMR) spectroscopy, Molecular Dynamics (MD) simulations, and other experimental techniques. These studies have shown that although glasses are amorphous solids, a certain type of short distance order, which greatly influences the in vitro and in vivo reactivity, is always present. This paper reviews the most significant advances in the understanding of bioactive glasses that took place in the last years as a result of the growing knowledge of the glasses’ nanostructure.

Magnesium Alloys Implants Coated with 58S Sol-Gel Bioactive Glass to Retard First Stage Corrosion

Two compositions of 58S (60 mol% SiO2, 36 mol% CaO, 4 mol% P2O5) glass coatings were made by sol-gel and applied by dip coating onto two commercial magnesium alloys (AZ31 and AZ91) as a strategy to retard the hydrogen evolution and accelerate the deposition of a hydroxyapatite layer to enhance bioactivity. Surface studies with x-ray photoelectron spectroscopy, Raman spectroscopy, and scanning electronic microscopy techniques are presented after coating deposition and after immersion in Hanks’ balanced salt solution (HBSS) at 37°C. Electrochemical tests were also conducted to evaluate the evolution of the coating with immersion. It is observed that even though the coating presents defects, it is able to retard substrate degradation, and this effect is more pronounced for AZ91 as substrate. Coating performance is mainly governed by the substrate because of defective nature of the film.

Preparation and characterization of bioactive glass tablets and evaluation of bioactivity and cytotoxicity in vitro

In this study, the SiO2CaOP2O5 ternary component of bioactive glass particles were successfully synthesized by sol-gel method, then the bioactive glass particles were pressed into tablets with dry pressing molding technology. The physicochemical structure, in-vitro bioactivity and biocompatibility of BG tablets were characterized by various methods, such as XRD、SEM、FTIR, etc. The results showed that the sol-gel bioactive glass particle was distinguished with its amorphous structure and micron-size. After being soaked in Tris-Hcl solution for 15 d, the bioactive glass tablets didn't collapse. Also, the mineralization assay in vitro showed that the bioactive glass tablets had good capability of inducing the formation of hydroxycarbonate apatite (HCA) after being immersed in simulated body fluid (SBF). In addition, the cytotoxicity assay indicated that the osteoblast (MC3T3) grew well on the surface of bioactive glass tablets. According to the above results, the bioactive glass tablets presented good mechanical strength, excellent apatite-forming activity and high biocompatibility, which demonstrated their potential applications in the field of bone defect repairing.

Influence of network modifiers in an acetate based sol-gel bioactive glass system

The aim of this study was to assess the influence of CaO/Na2O ratio on the structural and textural properties of mesoporous bioactive glasses generated from an acetic acid catalysed acetate based sol-gel system. The glass network formers (SiO2 and P2O5) were fixed and the network modifiers were varied [75SiO2:XCaO:(15-X)Na2O:10P2O5 where X = 5, 10, 15, in mole percent] such that increasing alkaline earth oxide is compensated by decreasing alkali oxide. The glass properties were assessed using techniques such as XRF, XRD, FTIR, BET/BJH, SEM, TEM and ICP. The rapid gelling of the sol resulted in the deposition of the calcium and sodium acetate precursors on the particle surface which required thermal treatment to facilitate their entry into the glass network. The results of our study demonstrated that the porosity was clearly driven by CaO in the composition possibly due to its inferior fluxing effect in comparison to Na2O. The sample with highest CaO content reached a high surface area and pore volume (535 m2 g−1 and 0.33 cm3 g−1) even in a non-surfactant based preparation suggesting that acetic acid catalysed acetate system favours improved textural properties. In vitro SBF tests confirmed the potential of the sample with highest CaO for earlier apatite formation.

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.

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.

Influence of Calcium on the Initial Stages of the Sol-Gel Synthesis of Bioactive Glasses.

Understanding how calcium interacts with silica sources and influences their polycondensation in aqueous solutions is of central importance for the development of more effective biomaterials by sol-gel approaches. For this purpose, the atomic-scale evolutions of a calcium-containing precursor solution corresponding to a typical sol-gel bioactive glass and of a corresponding Ca-free solution were compared using reactive molecular dynamics simulations. The simulations highlight a significantly faster rate of condensation when calcium is present in the initial solution, resulting in the formation of large and ramified silica clusters within 5 ns, which are absent in the Ca-free system. This different behavior has been analyzed and interpreted in terms of the Ca-induced nanosegregation in calcium-rich and silica-rich regions, which promotes the condensation reactions within the latter. By identifying a possible mechanism behind the limited incorporation of calcium in the silica nanoclusters formed in the early stages of the sol-gel process, these results could guide further studies aimed at identifying favorable experimental conditions to enhance initial calcium incorporation and thus produce sol-gel biomaterials with improved properties.

Bioactivity characterization of 45S5 bioglass using TL, OSL and EPR: Comparison with the case of 58S sol-gel bioactive glass

The current work exploits the effective application of thermoluminescence (TL), optically stimulated luminescence (OSL) and the possibility of applying Electron Paramagnetic Resonance (EPR) for the discrimination between different bioactive responses in the case of the 45S5 bioactive glass (SiO2 45, Na2O 24.5, CaO 24.5, P2O5 6 in wt%), which was synthesized through melting process. These techniques are suggested mainly due to their low spectroscopic detection thresholds. The original 45S5 in grain size range of 20–40μm was immersed in the Simulated Body Fluid (SBF) for various different immersion times ranging over one week. In this work the 110°C TL peak, a specific OSL component and the EPR signal at g=2.013 ascribed to oxygen hole center (OHC) are used due to their sensitivity to the different bioactive responses. For all luminescence and EPR components, the intensity plot versus immersion time yields sharp discontinuities, resulting in effective probes regarding the timescale for both the beginning as well as the end of the procedure of the crystalline HCAp formation respectively. On the contrary to the smooth decreasing pattern of both luminescence entities, the peak to peak amplitude of the EPR signal indicates an initial increase for the initial 16min of immersion, followed by a further decrease throughout the immersion time duration. The discontinuities monitored for both sensitivity of TL, OSL and EPR, in conjunction with the discontinuities monitored for the sensitization of TL and OSL, when plotted versus immersion time, provide an individual time scale for each one of the chemical reactions involved in the five steps of the aforementioned procedure. According to the authors' best knowledge, scarce characterization techniques could provide this time scale frame, while it is the first time that such an application of OSL and EPR is attempted. Finally, the bioactive response of the 45S5 bioglass was compared with that of the 58S sol-gel bioactive glass, in terms of the timescale of these five stages required for the final formation of the HCAp. The techniques of luminescence and EPR which take advantage of trapped charges are proposed as alternative cheap and prompt effective techniques towards discrimination between different bioactive responses in bioactive glasses.

Electrospun Polyhydroxybutyrate/Poly(ε-caprolactone)/58S Sol-Gel Bioactive Glass Hybrid Scaffolds with Highly Improved Osteogenic Potential for Bone Tissue Engineering.

Electrospinning of biopolymer and inorganic substances is one of the efficient ways to combine various advantageous properties in one single fibrous structure with potential for tissue engineering applications. In the present study, to integrate the high stiffness of polyhydroxybutyrate (PHB), the flexibility of poly(ε-caprolactone) (PCL) and the bioactivity of 58S bioactive glass, PHB/PCL/58S sol-gel bioactive glass hybrid scaffolds were fabricated using combined electrospinning and sol-gel method. Physical features such as fiber diameter distribution, mechanical strength and Young's modulus were characterized thoroughly. FTIR analysis demonstrated the successful incorporation of 58S bioactive glass into the blend polymers, which greatly improved the hydrophilicity of PHB/PCL fibermats. The primary biological response of MG-63 osteoblast-like cells on the prepared fibrous scaffolds was evaluated, proving that the 58S glass sol containing hybrid scaffold were not only favorable to MG-63 cell adhesion but also slightly enhanced cell viability and significantly increased alkaline phosphate activity .

Compressive Strength of Bioactive Sol–Gel Glass Foam Scaffolds

Larry Hench's 45S5 Bioglass® has been used in more than a million patients as a synthetic bone graft, in the form of a particulate. Bioglass is able to stimulate more bone regeneration than other bioactive ceramics. However, it is not commercially available as a porous scaffold with amorphous glass structure because the 45S5 composition crystallizes during sintering. The sol–gel foaming process was developed in Hench's laboratory to overcome this problem. Here, we concisely review the work on scaffold development from Hench's group and report new data that show maximum compressive strengths in excess of 5 MPa can be achieved while maintaining the interconnected pore networks required for vascularized bone ingrowth. This was achieved through optimization of sintering of the sol–gel foams. Sintering of the sol–gel foams was correlated to the network connectivity and silanol content. Changes in strength after immersion in simulated body fluid were found to be small over the times investigated. Relating the dissolution results to in vivo studies indicates that the scaffolds degrade more rapidly in vivo than in vitro.

Bioactive Sol-Gel Glasses at the Atomic Scale: The Complementary Use of Advanced Probe and Computer Modeling Methods

Sol–gel‐synthesized bioactive glasses may be formed via a hydrolysis condensation reaction, silica being introduced in the form of tetraethyl orthosilicate (TEOS), and calcium is typically added in the form of calcium nitrate. The synthesis reaction proceeds in an aqueous environment; the resultant gel is dried, before stabilization by heat treatment. These materials, being amorphous, are complex at the level of their atomic‐scale structure, but their bulk properties may only be properly understood on the basis of that structural insight. Thus, a full understanding of their structure‐property relationship may only be achieved through the application of a coherent suite of leading‐edge experimental probes, coupled with the cogent use of advanced computer simulation methods. Using as an exemplar a calcia–silica sol–gel glass of the kind developed by Larry Hench, in the memory of whom this paper is dedicated, we illustrate the successful use of high‐energy X‐ray and neutron scattering (diffraction) methods, magic‐angle spinning solid‐state NMR, and molecular dynamics simulation as components to a powerful methodology for the study of amorphous materials.

Effect of the incorporation of cobalt on the in vitro apatite formation of sol-gel bioactive glasses

Effect of the incorporation of cobalt on the in vitro apatite formation of sol-gel bioactive glasses

Comparative Study of Nanobioactive Glass Quaternary System 46S6

Different bioactive glass systems have been prepared by sol-gel. However, the production of Na2O-containing bioactive glasses by sol–gel methods has proved to be difficult as the sodium nitrate used in the preparation could be lost from the glass structure during filtration and washing. The aim of this study was to prepare the quaternary system 46S6 of bioactive glass by modified sol-gel techniques with a decrease in the time of gelation. In addition, compare the behaviour of the prepared sol-gel bioactive glass system by its corresponding prepared by melting. The obtained glasses were characterized by using several physicochemical techniques; XRD, FTIR, TEM and SEM beside the effect of the glass particles on the viability of osteoblast like cells (Saos-2). Results show that nanopowders 40-60 nm of 46S6 glass system had been prepared by modified sol-gel (acid-base reaction) method at 600°C in just three days at 600°C. Cell viability by MTT assay confirmed the effectiveness of the prepared nanobioactive glass.

Cytotoxicity of resin composites containing bioactive glass fillers

ObjectiveTo determine the in vitro cytotoxicity of dental composites containing bioactive glass fillers. MethodsDental composites (50:50 Bis-GMA/TEGDMA resin: 72.5wt% filler, 67.5%Sr–glass and 5% OX50) containing different concentrations (0, 5, 10 and 15wt%) of two sol–gel bioactive glasses, BAG65 (65mole% SiO2, 31mole% CaO, 4mole% P2O5) and BAG61 (3mole% F added) were evaluated for cytotoxicity using Alamar Blue assay. First, composite extracts were obtained from 7 day incubations of composites in cell culture medium at 37°C. Undifferentiated pulp cells (OD-21) were exposed to dilutions of the original extracts for 3, 5, and 7 days. Then freshly cured composite disks were incubated with OD-21 cells (n=5) for 2 days. Subsequently, fresh composite disks were incubated in culture medium at 37°C for 7 days, and then the extracted disks were incubated with OD-21 cells for 2 days. Finally, fresh composites disks were light cured for 3, 5, and 20s and incubated with OD-21 cells (n=5) for 1, 3, 5, and 7 days. To verify that the three different curing modes produced different levels of degree of conversion (DC), the DC of each composite was determined by FTIR. Groups (n=5) were compared with ANOVA/Tukey's (α≤0.05). ResultsExtracts from all composites significantly reduced cell viability until a dilution of 1:8 or lower, where the extract became equal to the control. All freshly-cured composites showed significantly reduced cell viability at two days. However, no reduction in cell viability was observed for any composite that had been previously soaked in media before exposure to the cells. Composites with reduced DC (3s vs. 20s cure), as verified by FTIR, showed significantly reduced cell viability. SignificanceThe results show that the composites, independent of composition, had equivalent potency in terms of reducing the viability of the cells in culture. Soaking the composites for 7 days before exposing them to the cells suggested that the “toxic” components had been extracted and the materials were no longer cytotoxic. The results demonstrate that the cytotoxicity of composites with and without BAG must predominantly be attributed to the release of residual monomers, and not to the presence of the BAG.

Mesoporous bioactive glasses: Relevance of their porous structure compared to that of classical bioglasses

AbstractIn the last decade, the development of third generation bioceramics for Bone Tissue Regeneration has experienced significant progress with the emergence of a new generation of nanostructured materials named mesoporous bioactive glasses (MBG). This new generation of materials, also known as “templated glasses”, presents chemical compositions similar to those of conventional bioactive sol–gel glasses and the added value of an ordered mesopore arrangement. This article shows an indepth comparative study of the ordered porous structures of MBGs compared to conventional glasses (melt and solgel) andhowthese properties influence the bioactivity process. Moreover, the possibility to tailor the textural and structural properties of these nanostructured materials by an exhaustive control of the different synthesis parameters is also discussed. A brief overview regarding the possibility of using these materials as controlled drug delivery systems and as starting materials for the fabrication of 3D scaffolds for bone tissue regeneration is also given.

Incorporation of sol–gel bioactive glass into PLGA improves mechanical properties and bioactivity of composite scaffolds and results in their osteoinductive properties

In this study, 3D porous bioactive composite scaffolds were produced and evaluated for their physico-chemical and biological properties. Polymer poly-L-lactide-co-glycolide (PLGA) matrix scaffolds were modified with sol–gel-derived bioactive glasses (SBGs) of CaO–SiO2–P2O5 systems. We hypothesized that SBG incorporation into PLGA matrix would improve the chemical and biological activity of composite materials as well as their mechanical properties. We applied two bioactive glasses, designated as S2 or A2, differing in the content of SiO2 and CaO (i.e. 80 mol% SiO2, 16 mol% CaO for S2 and 40 mol% SiO2, 52 mol% CaO for A2). The composites were characterized for their porosity, bioactivity, microstructure and mechanical properties. The osteoinductive properties of these composites were evaluated in human bone marrow stromal cell (hBMSC) cultures grown in either standard growth medium or treated with recombinant human bone morphogenetic protein-2 (rhBMP-2) or dexamethasone (Dex). After incubation in simulated body fluid, calcium phosphate precipitates formed inside the pores of both A2-PLGA and S2-PLGA scaffolds. The compressive strength of the latter was increased slightly compared to PLGA. Both composites promoted superior hBMSC attachment to the material surface and stimulated the expression of several osteogenic markers in hBMSC compared to cells grown on unmodified PLGA. There were also marked differences in the response of hBMSC to composite scaffolds, depending on chemical compositions of the scaffolds and culture treatments. Compared to silica-rich S2-PLGA, hBMSC grown on calcium-rich A2-PLGA were overall less responsive to rhBMP-2 or Dex and the osteoinductive properties of these A2-PLGA scaffolds seemed partially dependent on their ability to induce BMP signaling in untreated hBMSC. Thus, beyond the ability of currently studied composites to enhance hBMSC osteogenesis, it may become possible to modulate the osteogenic response of hBMSC, depending on the chemistry of SBGs incorporated into polymer matrix.

Synthesis and characterization of europium-containing luminescent bioactive glasses and evaluation of in vitro bioactivity and cytotoxicity

Luminescent europium-containing bioactive glasses (EuBG) based on the 58 %SiO2–33 %CaO–9 %P2O5 (in mass, %) system were synthesized using sol–gel technique by adding Eu2O3 in silica network. The structural, textural and optical properties, as well as in vitro bioactivity and biocompatibility of the material were characterized using various methods. The results show that all the Eu-containing bioactive glass materials exhibit an amorphous structure, large specific surface area, relatively uniform pore size distribution and high in vitro bioactivity, similar to the conventional sol–gel bioactive glass. More importantly, the addition of Eu2O3 endow the material with a luminescent property even after immersion in aqueous solution and the luminescent intensity increases with the increase of Eu2O3 content. The cytotoxicity assay indicates that pure EuBG extract significantly inhibit the growth of rat marrow mesenchymal stem cells (rMSCs), while 25 % concentration of the extract diluted by culture medium could significantly improve the proliferation of rMSCs in comparison with pure medium. According to the above results, the material presents excellent apatite-forming activity, luminescent property and biocompatibility, demonstrating their potential applications in the fields of bone regeneration and drug delivery system.

Preparation and Development of Bioglass by Sol-Gel Method

Bioglass is a good bioactive material and has been used in many medical fields, include drug delivery systems, non-load-bearing implants and bone cements. Sol-gel is a good method in the preparation of coating materials. It also can be used in the preparation of bioactive glass. In this paper, the principles and technical processes are introduced. The effects on characteristics of bioactive glasses of the factors such as H2O dosage, ethanol dosage, gel temperature and activator are analyzed in detail. The research progress in preparation of sol-gel bioactive glasses is summarized. Finally the development foreground of sol-gel bioglass is also expected.

New sol‐gel bioactive glass and titania composites with enhanced physico‐chemical and biological properties

We developed TiO2 matrix composites modified by sol-gel bioactive glasses (SBG) of either high CaO content (A2) or high SiO2 content (S2). The latter were mixed with titanium dioxide (TiO2) at 75:25, 50:50, and 25:75 weight ratios and sintered at 1250°C for 2 h. We examined the effects of various types (A2 or S2) and compositional TiO2 :SBG ratios on the mechanical properties of resulting composites, their bioactivity and human bone marrow mesenchymal stem cells (MSC) response. The chemistry of SBGs influenced the phase composition, mechanical and biological properties of the composites. Rutile and titanite prevailed in A2-TiO2 composites, and rutile and crystobalite in S2-TiO2 composites. Compressive strength increased significantly for 25A2-TiO2 composites (140 MPa) compared to matrix TiO2 (58 MPa). Composites containing 50-75 wt % of either SBG displayed bioactive properties as determined by simulated body fluid test. Compared to TiO2, human bone marrow stromal cell (BMSC) viability was enhanced on the composites containing 25 wt % of either SBG, whereas the composites modified by 25 wt % of S2 enhanced alkaline phosphatase activity and mineralization in cultures treated with osteogenic inducers-dexamethasone (Dex) or bone morphogenetic protein. Increasing amounts of A2 in TiO2 matrix decreased cell viability but increased collagen deposition and mineralized matrix production by BMSC. Considering the physico-chemical and biological properties of the presented composites, the modification of TiO2 with SBG may prove useful strategy in several bone tissue related regeneration strategies.