Proton Environments in Biomimetic Calcium Phosphates Formed from Mesoporous Bioactive CaO–SiO(2)–P(2)O(5) Glasses in Vitro: Insights from Solid-State NMR

[Image: see text] When exposed to body fluids, mesoporous bioactive glasses (MBGs) of the CaO–SiO(2)–P(2)O(5) system develop a bone-bonding surface layer that initially consists of amorphous calcium phosphate (ACP), which transforms into hydroxy-carbonate apatite (HCA) with a very similar composition as bone/dentin mineral. Information from various (1)H-based solid-state nuclear magnetic resonance (NMR) experiments was combined to elucidate the evolution of the proton speciations both at the MBG surface and within each ACP/HCA constituent of the biomimetic phosphate layer formed when each of three MBGs with distinct Ca, Si, and P contents was immersed in a simulated body fluid (SBF) for variable periods between 15 min and 30 days. Directly excited magic-angle-spinning (MAS) (1)H NMR spectra mainly reflect the MBG component, whose surface is rich in water and silanol (SiOH) moieties. Double-quantum–single-quantum correlation (1)H NMR experimentation at fast MAS revealed their interatomic proximities. The comparatively minor H species of each ACP and HCA component were probed selectively by heteronuclear (1)H–(31)P NMR experimentation. The initially prevailing ACP phase comprises H(2)O and “nonapatitic” HPO(4)(2–)/PO(4)(3–) groups, whereas for prolonged MBG soaking over days, a well-progressed ACP → HCA transformation was evidenced by a dominating O(1)H resonance from HCA. We show that (1)H-detected (1)H → (31)P cross-polarization NMR is markedly more sensitive than utilizing powder X-ray diffraction or (31)P NMR for detecting the onset of HCA formation, notably so for P-bearing (M)BGs. In relation to the long-standing controversy as to whether bone mineral comprises ACP and/or forms via an ACP precursor, we discuss a recently accepted structural core–shell picture of both synthetic and biological HCA, highlighting the close relationship between the disordered surface layer and ACP.