In situ Raman spectroscopy investigation of bioactive glass reactivity: Simulated body fluid solution vs TRIS-buffered solution

In the present contribution, the innovative in situ Raman micro-spectroscopy was applied to investigate the in vitro reactivity of various bioactive glasses. All the investigated glasses belonged to the Na2O\K2O–CaO–P2O5–SiO2 system, but contained sensibly different percentages of network modifiers. The glasses were immersed for increasing times, up to 96 h, in simulated body fluid (SBF) and in tris-buffered (TRIS) solution. In this way, two fundamental items were addressed, i.e. the effect of the glass composition and the nature of the soaking fluid on the overall reactivity. As regards the SBF, all the glasses were able to promote the formation of a hydroxyl-carbonate apatite (HCA) surface layer in very short times. The reaction rate was particularly quick for the 45S5 Bioglass® and for its potassium-based variant (BioK), however all the glasses could form a continuous HCA layer already after 96 h. The observed difference in reaction kinetics may be due to the glass composition, since the glasses relatively poor in Na ions (BG_Ca) experience slower ion release in the first stages of the HCA formation, while the glasses relatively poor in Ca ions (BG_Na) undergo slower nucleation and growth of HCA. The development of HCA was also observed in TRIS, but the reaction rate was generally slower than in SBF. In fact, while the SBF is a complicated solution supersaturated in apatite, which favours the precipitation of HCA, the TRIS is a simple tris(hydroxymethyl)aminomethane solution in water, which does not provide the ions for the HCA formation. As a consequence, the aforementioned effects due to the glass composition were even more evident in TRIS than in SBF. Nevertheless the TRIS could represent a valuable alternative to the standard SBF whenever a slow reaction rate might be beneficial, such as, for example, in order to better observe the samples evolution.

► The in situ Raman micro-spectroscopy is applied to study the in vitro reactivity of bioglasses.
► The Raman spectra were acquired directly on immersed samples during in vitro tests.
► Glass modifications were followed directly in solution.
► It was possible to go deep inside into the reaction mechanisms.