Band 5, Heft 1

Glass ionomer cements (GIC) are used in restorative dentistry and their properties (low heat during setting, adhesion to mineralised tissue and surgical metals) make them of great interest for bone applications.However, dental GIC are based on aluminium-containing glasses, and the resulting release of aluminium ions from the cements needs to be avoided for applications as bone cements. Replacing aluminium ions in glasses for use in glass ionomer cements is challenging, as aluminium ions play a critical role in the required glass degradation by acid attack as well as in GIC mechanical stability. Magnesium ions have been used as an alternative for aluminium in the glass component, but so far no systematic study has looked into the actual role of magnesium ions. The aim of the present study is therefore the systematic comparison of the effect of magnesium ions compared to calcium ions in GIC glasses. It is shown that by partially substituting MgO for CaO in simple SiO2-CaO-CaF2 glasses, ion release from the glass and, subsequently, GIC setting behaviour can be adjusted. Magnesium ions act as typical network modifiers here but owing to their larger field strength compared to calcium ions reduce ion release from the glasses significantly. By choosing an optimum ratio of magnesium and calcium ions in the glass, GIC setting and subsequently compressive strength can be controlled.

The physical, mechanical, and biological behaviour of copper containing glass polyalkenotare cements were investigated, where copper (Cu2+) was incorporated into a SiO2-ZnO-CaO-SrO-P2O5 based glass system. Three GPCs were formulated for this study, a Control and two Cu-GPCs with 6 (Cu-1) and 12 (Cu-2) Mol.% of CuO substituted for the SiO2 in the glass. Rheological evaluation of GPCs determined that the addition of the Cu decreases the working and setting times in the cements. The mechanical properties of the cements were evaluated after 1 - 21 days incubation in DI water. The compressive strength of the cements were found to range between 21-36 MPa, with Cu-1 having the highest compressive strength. Biaxial flexural strength and Shear Bond Strength of the GPCs were found to increase with respect to time and were higher for the Cu-GPCs at 14 MPa and 2.1 MPa respectively. Bioactivity testing was conducted using Simulated Body Fluid (SBF) which revealed CaP precipitants on each of the GPCs surfaces. The effect o f Cu addition to the GPCs greatly enhanced the antibacterial inhibition zone (IZ) when tested in E.coli (3mm), S.aureus (24mm) and S.epidermidis (22mm). Cytocompatibility testing revealed more favorable MC3T3 osteoblast cell viability when compared to the Control GPC.

The biocompatibility of photosensitive glasses allows various biomedical applications; one is the field of tissue engineering and more precisely microengineered tissue-on-a-chip platforms to study the tissue microenvironment and disease modelling. Three dimensional architectures of adapted components are required for modern materials. A photosensitive lithiumalumosilicate glass FS21 was investigated regarding the interaction with a Ti:Sapphire laser systemto build three dimensional buried channels inside the glass. Femtosecond laser radiation with a wavelength of 800 nm and pulse duration of 140 fs was used to modify the glass structure. Subsurface channel geometries were achieved by a subsequent thermal treatment and were formed into capillaries using wet chemical etching of the exposed and crystallised channels. Contrary to ultraviolet (UV) exposure, spectral optical investigations showed that fs laser exposure caused various radiation induced defects in the base glass coupled with the generation of photoelectrons for the photochemical modification of silver ions. We observed an outgassing of different species coming from raw materials of the original glass batch during the glass crystallisation process. Etch rate ratios differ between 1:25 and 1:45 and are dependent on: stoichiometric deviation between surface and bulk, crystal size and distribution and exchange of the etching agent in narrow capillaries.

The crystallization process of a bioactive silicate glass with 47.5SiO 2 -10Na 2 O-10K 2 O-10MgO-20CaO-2.5P 2 O 5 molar composition was investigated by using nonisothermal differential t hermal a nalysis (DTA). T he DTA plots recorded at different heating rates exhibited a single crystallization peak. The activation energy for crystallization was estimated by applying the equations proposed by Kissinger and Matusita-Sakka. The Johnson-Mehl-Avrami exponent (n) was assessed by using the Ozawa and Augis-Bennett methods. The analyses suggest that a surface crystallization mechanism with one-dimensional crystal growth is predominant. The activation energy for viscous flow was also assessed (176 kJ/mol) and was found lower than the activation energy for crystallization (271 kJ/mol). This confirms the stability of 47.5B against crystallization and its good sinterability, which is a highly attractive feature for producing glass products of biomedical interest, such as bioactive porous scaffolds for bone repair.

Four phosphate-based glass formulations in the system P 45 Mg 24 Ca 16 Na (15− x ) Zn x , referred to as P45Znx (x = 0, 5, 10 and 15 mol%), were prepared using a melt quenching process. The effect of ZnO addition on density, molar volume, thermal properties and degradation rates were studied. An increase in the glass transition, crystallisation, melting and liquidus temperatures were seen when replacing Na 2 O with ZnO. The molar volume of the bulk glasses was seen to decrease with increasing ZnO content. The dissolution rate of the zinc-free glass was 2.48 × 10 −8 kg m −2 s −1 and addition of 5 mol% ZnO resulted in a reduction of the dissolution rate to 1.68 × 10 −8 kg m −2 s −1 . However, further addition of ZnO from 5 mol% to 15 mol% increased the dissolution rate of the glass system. The glasses were deliberately crystallised and XRD studies identified the Z n 2 P 2 O 7 phase for glass code P45Zn5, and Zn(PO 3 ) 2 phase for P45Zn10 and P45Zn15 glasses. Cyto-compatibility studies were conducted using MG63 cells for 14 days. An overall increase in the metabolic activity and DNA concentration of cells was seen from day 1 to day 14 for all glass formulations investigated. However, increasing ZnO content from 0 to 15 mol% seemed to have a negative effect on the cellular activity. Interestingly, a remarkably higher ALP activity was seen at day 14 for glass codes P45Zn5 and P45Zn10 in comparison with the TCP control and the P45Zn0 glass.

Bioactive glass was first developed in the late 1960’s as a compound that would facilitate bone re-growth. In more recent years, this technology has been used to promote wound healing through its ability to stimulate soft tissue growth, angiogenesis, reduce inflammation, and prevent infection. Chronically infected wounds, which result from biofilm formation, affect millions of patients in the Unites States each year and cost billions of dollars to treat. The present studies demonstrate exposure of pre-formed biofilms to bioactive glass, under simulated body conditions, resulted in significant reduction in bacterial load. Additionally, specific therapeutically active metal ions such as copper and zinc were added to a borate bioactive glass formulation through a process of ion doping and found to further enhance the anti-biofilm activity. Based on the present findings, the antibiofilm agents released by borate bioactive glasses may prove effective to eradicate the biofilm infections that prevent healing in patients with chronic wounds.

Here, molecular dynamics simulations have been carried out on phosphate glasses to clarify the previously debated influence of fluoride on the bioactivity of these glasses. We developed a computationally advanced inter-atomic force field including polarisation effects of the fluorine and oxygen atoms. Structural characterisations of the simulated systems showed that fluoride ions exclusively bond to the calcium modifier cations creating clusters within the glass structure and therefore decreasing the bioactivity of fluoridated phosphate glasses, making them less suitable for biomedical applications.

Present work explores the relationship between the composition, dissolution rate, ion release and cytocompatibility of a series of borophosphate glasses. While, the base glass was selected to be 40mol%P 2 O 5- 16mol%CaO-24mol%MgO-20mol%Na 2 O, three B 2 O 3 modified glass compositions were formulated by replacing Na 2 O with 1, 5 and 10 mol% B 2 O 3 . Ion release study was conducted using inductively coupled plasma atomic emission spectroscopy (ICP-AES). The thermal scans of the glasses as determined by differential scanning calorimetry (DSC) revealed an increment in the thermal properties with increasing B 2 O 3 content in the glasses. On the other hand, the dissolution rate of the glasses decreased with increasing B 2 O 3 content. To identify the effect of boron ion release on the cytocompatibility properties of the glasses, MG63 cells were cultured on the surface of the glass discs. The in vitro cell culture study suggested that glasses with 5 mol% B 2 O 3 (P40B5) showed better cell proliferation and metabolic activity as compares to the glasses with 10 mol% (P40B10) or with no B 2 O 3 (P40B0). The confocal laser scanning microscopy (CLSM) images of live/dead stained MG63 cells attached to the surface of the glasses also revealed that the number of dead cells attached to P40B5 glasses were significantly lower than both P40B0 and P40B10 glasses.

Sol-gel derived bioactive borate glasses (SGBGs) rapidly convert to hydroxycarbonated apatite (HCA) in simulated body fluid (SBF), in vitro . While previous studies have examined the influence of processing and composition on bioactivity, the effect of the in vitro dissolution media has not been well examined for these glasses. In this study, the mineral conversion of a SGBG substituted 45S5 Bioglass ® formulation (“B46”, (46.1)B 2 O 3 -(26.9)CaO-(24.4)Na 2 O-(2.6)P 2 O 5 , mol%), was examined in six different dissolution media: SBF, tris(hydroxymethyl)aminomethane (TRIS, pH 7.4) buffer, Dulbecco’s phosphate buffered saline (PBS, 1X), Dulbecco’s Modified Eagle Medium (DMEM, 1X), 0.9% Saline (SAL), and deionized water (DIW) at 1.5 mg/mL for 10 min, 2h, and 1d. All media underwent a rapid increase in pH as a result of glass dissolution and ion release. B46 in SBF, TRIS, and PBS converted to HCA while B46 in DMEM, SAL, and DIW converted to calcite according to attenuated total reflectance-Fourier-transform infrared spectroscopy, X-ray diffraction, and scanning electron microscopy. The ratio of B46 to SBF was also examined at 3, 6, 12, and 24 mg/mL for 1d. These results help elucidate the dissolution and mineral conversion of borate glasses and help provide insights into optimizing pre-conditioning treatments for both in vitro and in vivo analyses.

Bioactive glasses are important for biomedical and dental applications. The controlled release of key ions, which elicit favourable biological responses, is known to be the first key step in the bioactivity of these materials. Properties such as bioactivity and solubility can be tailored for specific applications. The addition of fluoride ions is particularly interesting for dental applications as it promotes the formation of fluoro-apatite. To date there have been mixed reports in the literature on how fluorine is structurally incorporated into bioactive glasses. To optimize the design and subsequent bioactivity of these glasses, it is important to understand the connections between the glass composition, structure and relevant macroscopic properties such as apatite formation and glass degradation in aqueous media. Using neutron diffraction, high energy X-ray diffraction, 29 Si NMR, FTIR and XPS we have investigated the atomic scale structure of mixed calcium oxide / calcium fluoride silicate based bioactive glasses. No evidence of direct Si-F bonding was observed, instead fluorine was found to bond directly to calcium resulting in mixed oxygen/fluoride polyhedra. It was therefore concluded that the addition of fluorine does not depolymerise the silicate network and that the widely used network connectivity models are valid in these oxyfluoride systems.

The present study reports the dissolution studies of a family of boron-doped bioactive glasses based on the composition ICIE16. Simulated body fluid (SBF), Tris-buffered solution and lactic acid were used as dissolution media for studies under static and dynamic conditions. The leaching of ions from the glasses under the evaluated conditions and media was compared and the bioactive behaviour of the glasses was evaluated. Influence of the incorporation of boron in the thermal properties of the glass was also analysed. Glasses exhibited faster bioactivity under dynamic dissolution configuration compared to static conditions. Moreover, the glass dissolution rate was faster in acidic conditions than in SBF or Tris solutions. It was found that at increasing boron content the dissolution of the glass is faster.

Since the discovery of 45S5 Bioglass ® by Larry Hench, bioactive glasses have been widely studied as bone substitute materials and, in more recent years, have also shown great promise for producing three-dimensional scaffolds. The development of additive manufacturing techniques and their application in bone tissue engineering allows the design and fabrication of complex structures with controlled porosity. However, achieving strong and mechanically-reliable bioactive glass scaffolds is still a great challenge. Furthermore, there is a relative paucity of studies reporting an exhaustive assessment of other mechanical properties than compressive strength of glass-derived scaffolds. This research work aimed at determining key mechanical properties of silicate SiO 2 -Na 2 O-K 2 OMgO-CaO-P 2 O 5 glass scaffolds fabricated by robocasting and exhibiting a porosity gradient. When tested in compression, these scaffolds had a strength of 6 MPa, a Young’s modulus around 340 MPa, a fracture energy of 93 kJ/m 3 and a Weibull modulus of 3, which provides a quantification of the scaffold reliability and reproducibility. Robocasting was a suitable manufacturing method to obtain structures with favorable porosity and mechanical properties comparable to those of the human cancellous bone, which is fundamental regarding osteointegration of bone implants.

After five decades of research on bioactive glasses and glass-ceramics, these materials became of considerable interest due to their revolutionary potential for numerous health applications, including cancer treatment. One advantage of glass-ceramics compared with other materials – such as metallic alloys and polymers – is their capability of being highly bioactive and, if desired, containing magnetic phases. Hyperthermia (HT) is an alternative for treating cancer; the strategy is to increase the temperature of the tumor using an external magnetic field that increases the temperature of an implanted magnetic material, which works as an internal heat source. This local increase of temperature, ideally to ~43°C, could kill cancer cells in situ without damaging the healthy surrounding tissue. To achieve such goal, a material that presents a balance between proper magnetic properties and bioactivity is necessary for the safe applicability and successful performance of the HT treatment. Certainly, achieving this ideal balance is the main challenge. In this article we review the state-of-the-art on glass-ceramics intended for HT, and explore the current difficulties in their use for cancer treatment, starting with basic concepts and moving onto recent developments and challenges.

In 1969, fifty years ago, a young professor of ceramic engineering created a 4-component glass to be used as a bone replacement material. That material became known as “Bioglass” and more generally as a class of materials known as bioactive glass. Those first experiments conducted by Dr. Larry Hench completely shifted the paradigm of how the biomaterials and medical communities look at the interactions between inorganic materials and tissues in the body. This article will touch on just a few highlights of the development of bioactive glasses and relate those to the concepts of bioactivity and tissue bonding.

Synthesis and use of novel compositions of bioactive glasses (BGs) for hard tissue engineering are of important significance in the biomedical field. In this study, we successfully synthesized a series of 58S-based BGs containing fluoride (F − ) and silver (Ag + ) ions through a sol-gel method for possible use in bone/dental regeneration and antibacterial strategies. Characterizations of samples were performed by using thermal analyses (thermogravimetric analysis (TGA) and differential scanning calorimetry (DSC)), X-ray diffraction (XRD), Fourier-transform infrared spectroscopy (FTIR), textural analysis (N 2 adsorption-desorption), and morphological observations by transmission electron microscopy (TEM) and scanning electron microscopy (SEM). The obtained data revealed that the fabricated BGs are in a glassy state before incubation in the Kokubo’s simulated body fluid (SBF), and an apatite-like layer is formed on their surface after 7 days of immersion in SBF. The size of the glass particles was in the nano-range (about 100 nm or below), and their pore size was in the mesoporous range (15-25 nm). These early results suggest that the F- and Ag-doped glasses show promise as multifunctional bioactive materials for bone/dental tissue engineering.