Xiaojing Chen

Bioactivity of Sodium Free Fluoride Containing Glasses and Glass-Ceramics

The bioactivity of a series of fluoride-containing sodium-free calcium and strontium phosphosilicate glasses has been tested in vitro. Glasses with high fluoride content were partially crystallised to apatite and other fluoride-containing phases. The bioactivity study was carried out in Tris and SBF buffers, and apatite formation was monitored by XRD, FTIR and solid state NMR. Ion release in solutions has been measured using ICP-OES and fluoride-ion selective electrode. The results show that glasses with low amounts of fluoride that were initially amorphous degraded rapidly in Tris buffer and formed apatite as early as 3 h after immersion. The apatite was identified as fluorapatite by 19F MAS-NMR after 6 h of immersion. Glass degradation and apatite formation was significantly slower in SBF solution compared to Tris. On immersion of the partially crystallised glasses, the fraction of apatite increased at 3 h compared to the amount of apatite prior to the treatment. Thus, partial crystallisation of the glasses has not affected bioactivity significantly. Fast dissolution of the amorphous phase was also indicated. There was no difference in kinetics between Tris and SBF studies when the glass was partially crystallised to apatite before immersion. Two different mechanisms of apatite formation for amorphous or partially crystallised glasses are discussed.

Novel Highly Degradable Chloride Containing Bioactive Glasses

Abstract Addition of CaF2 to a silicate bioactive glass favours formation of fluorapatite, which is less soluble in acidic environment than hydroxyapatite. However, excess CaF2 in the glass is problematic, owing to the formation of crystalline calcium fluoride rather than fluorapatite on immersion. In this paper we investigate chloride as an alternative to fluoride in bioactive silicate glasses and in particular their bioactivity for the first time. Meltderived bioactive glasses based on SiO2-P2O5-CaO-CaCl2 with varying CaCl2 contents were synthesised and characterised by DSC. Chemical analysis of the chloride content was performed by using an ion selective electrode. Glass density was determined using Helium Pycnometry. The glass bioactivity was investigated in Tris buffer. Ion release measurements were carried out by using ICP-OES. The chemical analysis results indicated that the majority of the chloride is retained in the Q2 type silicate glasses during synthesis. Tg and glass density reduced with increasing CaCl2 content. Apatite-like phase formation was confirmed by FITR, XRD and 31P MAS-NMR. The results of the in vitro studies demonstrated that the chloride containing bioactive glasses are highly degradable and form apatite-like phase within three hours in Tris buffer and, therefore, are certainly suitable for use in remineralising toothpastes. The dissolution rate of the glass was found to increase with CaCl2 content. Faster dissolving bioactive glasses may be attractive for more resorbable bone grafts and scaffolds.

Modeling the Onset of Phase Separation in CaO–SiO2–CaCl2 Chlorine-Containing Silicate Glasses

The addition of chlorine into a bioactive glass composition is expected to reduce its abrasiveness and increase its bioactivity, which is important for dental applications such as toothpastes. There is a lack of information and understanding regarding the structural role of chlorine in chlorine-containing bioactive silicate glasses. This has prompted classical core-shell model molecular dynamics simulations of (50 - x/2)CaO-(50 - x/2)SiO2-xCaCl2 glasses to be performed, where x ranges from x = 0.0 to 43.1 mol % CaCl2. These ternary glasses are advantageous for a fundamental study because they do not have additional network formers (e.g., phosphorus pentoxide) or modifiers (e.g., sodium) typically found in bioactive glass compositions. The (50 - x/2)CaO-(50 - x/2)SiO2-xCaCl2 glasses were seen to become phase-separated around the x = 16.1 mol % CaCl2 composition, and chlorine predominantly coordinated with calcium. These findings provide a solid foundation for further computational modeling work on more complex chlorine-containing bioactive glass compositions.

Sodium is not essential for high bioactivity of glasses

This study aims to demonstrate that excellent bioactivity of glass can be achieved without the presence of an alkali metal component in glass composition. In vitro bioactivity of two sodium-free glasses based on the quaternary system SiO2-P2O5-CaO-CaF2 with 0 and 4.5 mol% CaF2 content was investigated and compared with the sodium containing glasses with equivalent amount of CaF2. The formation of apatite after immersion in Tris buffer was followed by Fourier transform infrared spectroscopy (FTIR), X-ray diffraction (XRD), 31P and 19F solid state MAS-NMR. The dissolution study was completed by ion release measurements in Tris buffer. The results show that sodium free bioactive glasses formed apatite at 3 hours of immersion in Tris buffer, which is as fast as the corresponding sodium containing composition. This signifies that sodium is not an essential component in bioactive glasses and it is possible to make equally degradable bioactive glasses with or without sodium. The results presented here also emphasize the central role of the glass compositions design which is based on understanding of structural role of components and/or predicting the network connectivity of glasses.

New insight into mixing fluoride and chloride in bioactive silicate glasses.

Adding fluoride into bioactive glasses leads to fluorapatite formation and a decrease in glass transition temperature. Recently, chloride has been introduced into glasses as an alternative to fluoride. The presence of the large chloride ion lowers glass crystallisation tendency and increases glass molar volume, which effectively facilitates glass degradation and bone-bonding apatite-like layer formation. However, there is no information regarding the effect of mixing fluoride and chloride on the glass structure and properties. This study aims to synthesize mixed fluoride and chloride containing bioactive glasses; investigate the structural role of fluoride and chloride and their effects on glass properties. The chloride content measurements reveal that 77–90% of chloride was retained in these Q2 type glasses. Glass transition temperature reduced markedly with an increase in CaX2 (X = F + Cl) content, while the glass molar volume increased. 29Si MAS-NMR results show that the incorporation of mixed fluoride and chloride did not cause significant change in the polymerization of the silicate network and no detectable concentration of Si-F/Cl bands were present. This agrees with 19F NMR spectra showing that F existed as F-Ca(n) species.

Molecular Dynamics Investigation of Halide-Containing Phospho-Silicate Bioactive Glasses

Oxyhalide-containing silicate glasses have been receiving increasing attention in recent years due to their extensive medical and dental applications. This manuscript reports the first detailed structural investigation using MD simulations in the context of chloride- and mixed-fluoride/chloride-containing phospho-silicate bioactive glasses. It is shown that adding fluoride, chloride, and mixed fluoride and chloride has not altered the Q n silicate distribution and phosphorus speciation significantly in all of the glasses investigated. The Q2 silicon species is the predominant species with smaller and nearly equal proportions of Q1 and Q3 species, whereas phosphorus is largely present as orthophosphate Q0 units. No Si-F/Cl and P-F/Cl bonds have been observed at room temperature. Both F and Cl anions are present as F-Ca(n) and Cl-Ca(n). MD simulations also indicate opposite effects of fluoride and chloride on the crystallization ability of the glasses. The environment of Cl in chloride-containing glass series is quite different from the chlorapatite and CaCl2 crystals, and a significant structural reorganization is required to observe the appearance of the crystal nuclei. Instead, the environment of fluoride ions in the glasses is quite similar to that present in the FAP and CaF2 crystals and thus F-containing glasses manifest a high crystallization tendency. Moreover, in the mixed-fluoride/chloride-containing glasses, fluorine tends to surround phosphate, whereas chloride moves toward the silicate network. Finally, it was observed that a good correlation exists between the glass transition temperature and the overall strength of the glass network quantified by the Fnet factor.

Dentine Tubule Occlusion by Novel Bioactive Glass-Based Toothpastes

There are numerous over-the-counter (OTC) and professionally applied (in-office) products and techniques currently available for the treatment of dentine hypersensitivity (DH), but more recently, the use of bioactive glasses in toothpaste formulations have been advocated as a possible solution to managing DH. Aim. The aim of the present study, therefore, was to compare several bioactive glass formulations to investigate their effectiveness in an established in vitro model. Materials and Methods. A 45S5 glass was synthesized in the laboratory together with several other glass formulations: (1) a mixed glass (fluoride and chloride), (2) BioMinF, (3) a chloride glass, and (4) an amorphous chloride glass. The glass powders were formulated into five different toothpaste formulations. Dentine discs were sectioned from extracted human teeth and prepared for the investigation by removing the cutting debris (smear layer) following sectioning using a 6% citric acid solution for 2 minutes. Each disc was halved to provide test and control halves for comparison following the brushing of the five toothpaste formulations onto the test halves for each toothpaste group. Following the toothpaste application, the test discs were immersed in either artificial saliva or exposed to an acid challenge. Results. The dentine samples were analyzed using scanning electron microscopy (SEM), and observation of the SEM images indicated that there was good surface coverage following artificial saliva immersion. Furthermore, although the acid challenge removed the hydroxyapatite layer on the dentine surface for most of the samples, except for the amorphous chloride glass, there was evidence of tubular occlusion in the dentine tubules. Conclusions. The conclusions from the study would suggest that the inclusion of bioactive glass into a toothpaste formulation may be an effective approach to treat DH.