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Transition metal ions are essential micronutrients for all living organisms and play an important role in bone metabolism. In the present study, we investigated the impact of transition metal ions (Cu, Co, Mn, Fe) on the structure and bioactivity of bioactive glasses. The emphasis was laid on understanding their influence on the chemical dissolution behavior of glasses and its impact on their vitro bioactivity, osteoblast proliferation and oxidative stress levels. The structure of glasses was studied by using molecular EXAFS in combination with Raman spectroscopy. The apatite-forming ability of glasses has been investigated by X-ray diffraction, infrared spectroscopy after immersion of glass powders in simulated body fluid (SBF) for time durations varying between 1 and 7 days. A significant effect on the bioactivity was observed with addition of transition metal ions. The cellular responses were observed in vitro on glass powders using human osteosarcoma MG63 cell line. The dose-dependent cytoprotective effect of glasses with respect to the concentration of transition metal ions (Cu, Co, Mn, Fe) released from the glasses is also discussed.

Alpha-tricalcium phosphate (α-TCP) is a component of particular interest in the formulation of apatitic calcium phosphate based bone cements. During the setting reaction of this type of cements, a calcium deficient hydroxyapatite with composition similar to bone hydroxyapatite is formed. But the purity levels of the commercially available products based on α-TCP are generally low, and their prices are prohibitive. Such stringent conditions are pushing most of the researchers in the area of bone cements towards preparing α-TCP in their own laboratories. The low degree of purity of α-TCP based products is generally due to an incomplete β-TCP → α-TCP phase transformation and/or to a partial α-TCP → β-TCP reversal during cooling. Despite extensive research efforts, contradictory reports exist about the effects of composition of the starting material, cooling rates and the importance of quenching for maintaining α-TCP purity. The present work aims at shedding further light on this issue by controlling the relevant parameters of wet synthesis of the starting β-TCP powders and their heat treatment schedule in order to transform them in high purity α-TCP products. The key experimental variables investigated included the composition of the starting β-TCP powders, namely the Ca/P ratio, the maximum heat treatment temperatures, and the cooling rates.

Structural and optical properties of antimony-containing sodium borate glasses were studied and their ultrafast third-order nonlinear optical (NLO) properties have been evaluated using Z-scan measurements with femtosecond (fs) pulses (?150 fs, 80 MHz) at 750, 800, and 880 nm wavelengths. Glasses in the (mol ) 20Na 2 O-(80 - x)B 2 O 3 -xSb 2 O 3 (where x = 0, 10, 20, and 30) system have been fabricated via melt quench technique. The structural modifications were analyzed using the Raman and magic angle spinning (MAS)-nuclear magnetic resonance (NMR) ( 11 B MAS-NMR and 23 Na MAS-NMR) techniques. The optical absorption spectra revealed that the absorption edge was red-shifted, suggesting the decrease in band gap energy with increase of antimony content in the glasses. Raman scattering results revealed that the boroxol rings are depressed with the incorporation of Sb 2 O 3 for replacing B 2 O 3 . 11 B MAS-NMR results showed a progressive increase of B 4 units at the expense of B 3 units. The Raman and 11 B MAS-NMR results support the formation of Sb 5+ ions due to oxidation of Sb 3+ that played the role of charge compensation. 23 Na MAS-NMR spectra revealed a decreasing trend in the average of bond lengths of Na-O with increasing Sb 2 O 3 contents. This suggested that sodium changed its role from charge compensator to modifier cation. The antimony-containing glasses demonstrated a reverse saturable absorption in open-aperture Z-scan mode due to two-photon absorption, while closed-aperture Z-scan signatures depicted positive nonlinear refraction due to self-focusing effect. The NLO coefficients were found to increase with Sb 2 O 3 due to the increased nonbridging oxygens and also due to the hyperpolarizability of Sb 3+ and Sb 5+ ions. The observed NLO data clearly suggest that the investigated glasses are beneficial for optical limiting applications.

The present work aims at evaluating the potential gains derived from partially replacing calcium in resorbable &beta, tricalcium phosphate (&beta, TCP) by two different molar percentages of strontium (5, 10) and zinc (1, 2), concomitantly with a fixed molar percentage (0.5) of manganese. Synthetic granular composite bone filling grafts consisting of doped &beta, TCP and an alkali-free bioactive glass were prepared and implanted in ~4 mm diameter bone defects drilled in the calvaria of Wistar rats used as animal models. The animals were sacrificed after 9 weeks of implantation and the calvaria was excised. Non-manipulated bone was used as positive control, while empty defects were used as a negative control group. The von Kossa staining revealed an enhanced new bone formation with increasing doping levels, supporting the therapeutic effects exerted by the doping elements. The percentage of newly formed bone was similar when the defects were filled with autologous bone, BG (previous results) or 3TCP2/7BG, which indicates that the latter two are excellent candidates for replacement of autologous bone as bone regeneration material. This finding confirms that doping with suitable doses of therapeutic ions is a good strategy towards transposing the bone graft materials to biomedical applications in humans.

The discovery of bioactive glasses (BGs) in the late 1960s by Larry Hench et al. was driven by the need for implant materials with an ability to bond to living tissues, which were intended to replace inert metal and plastic implants that were not well tolerated by the body. Among a number of tested compositions, the one that later became designated by the well-known trademark of 45S5 Bioglass® excelled in its ability to bond to bone and soft tissues. Bonding to living tissues was mediated through the formation of an interfacial bone-like hydroxyapatite layer when the bioglass was put in contact with biological fluids in vivo. This feature represented a remarkable milestone, and has inspired many other investigations aiming at further exploring the in vitro and in vivo performances of this and other related BG compositions. This paradigmatic example of a target-oriented research is certainly one of the most valuable contributions that one can learn from Larry Hench. Such a goal-oriented approach needs to be continuously stimulated, aiming at finding out better performing materials to overcome the limitations of the existing ones, including the 45S5 Bioglass®. Its well-known that its main limitations include: (i) the high pH environment that is created by its high sodium content could turn it cytotoxic; (ii) and the poor sintering ability makes the fabrication of porous three-dimensional (3D) scaffolds difficult. All of these relevant features strongly depend on a number of interrelated factors that need to be well compromised. The selected chemical composition strongly determines the glass structure, the biocompatibility, the degradation rate, and the ease of processing (scaffolds fabrication and sintering). This manuscript presents a first general appraisal of the scientific output in the interrelated areas of bioactive glasses and glass-ceramics, scaffolds, implant coatings, and tissue engineering. Then, it gives an overview of the critical issues that need to be considered when developing bioactive glasses for healthcare applications. The aim is to provide knowledge-based tools towards guiding young researchers in the design of new bioactive glass compositions, taking into account the desired functional properties.