An array of magic-angle spinning (MAS) nuclear magnetic resonance (NMR) spectroscopy experiments is applied to explore the surface reactions of a mesoporous bioactive glass (MBG) of composition Ca0.10Si0.85P0.04O1.90 when subjected to a simulated body fluid (SBF) for variable intervals. Powder X-ray diffraction and 31P NMR techniques are employed to quantitatively monitor the formation of an initially amorphous calcium phosphate surface layer and its subsequent crystallization into hydroxycarbonate apatite (HCA). Prior to the onset of HCA formation, 1H → 29Si cross-polarization (CP) NMR evidence dissolution of calcium ions; a slightly increased connectivity of the speciation of silicate ions is observed at the MBG surface over 1 week of SBF exposure. The incorporation of carbonate and sodium ions into the bioactive orthophosphate surface layer is explored by 1H → 13C CPMAS and 23Na NMR, respectively. We discuss similarities and distinctions in composition−bioactivity relationships established for traditional melt-prepared bioglasses compared to MBGs. The high bioactivity of phosphorus-bearing MBGs is rationalized to stem from an acceleration of their surface reactions due to presence of amorphous calcium orthophosphate clusters of the MBG pore wall.
By combining molecular dynamics (MD) simulations with 29 Si and 27 Al magic-angle spinning nuclear magnetic resonance (NMR) spectroscopy, we present a comprehensive structural report on rare-earth (RE) aluminosilicate (AS) glasses of the RE 2 O 3 −Al 2 O 3 −SiO 2 (RE = Y, Lu) systems, where the latter is studied for the first time. The structural variations stemming from changes in the glass composition within each RE systemas well as the effects of the increased cation field-strength (CFS) of Lu 3+ relative to Y 3+ are explored and correlated to measured physical properties, such as density, molar volume, glass transition temperature, and Vickers hardness (H V ). 29 Si NMR reveals a pronounced network ordering for an increase in either the RE or Al content of the glass. Al mainly assumes tetrahedral coordination, but significant AlO 5 and AlO 6 populations are present in all structures, with elevated amounts in the Lu-bearing glasses compared to their Y analogues. The MD-derived oxygen speciation comprises up to 3% of free O 2− ions, as well as non-negligible amounts (4−19%) of O [3] coordinations ("oxygen triclusters"). While the SiO 4 groups mainly accommodate the nonbridging oxygen ions, a significant fraction thereof is located at the AlO 4 tetrahedra, in contrast to the scenario of analogous alkali-and alkaline-earth metal-based AS glasses. The average coordination numbers (CNs) of Al and RE progressively increase for decreasing Si content of the glass, with the average CN of the RE 3+ ions depending linearly on both the amount of Si and the fraction of AlO 5 groups in the structure. The Vickers hardness correlates strongly with the average CN of Al, in turn dictated by the CFS and content of the RE 3+ ions. This is to our knowledge the first structural rationalization of the well-known compositional dependence of H V in RE bearing AS glasses.
The short and intermediate range structures of a large series of bioactive borophosphosilicate (BPS) glasses were probed by solid-state nuclear magnetic resonance (NMR) spectroscopy and atomistic molecular dynamics (MD) simulations. Two BPS glass series were designed by gradually substituting SiO by BO in the respective phosphosilicate base compositions 24.1NaO-23.3CaO-48.6SiO-4.0PO ("S49") and 24.6NaO-26.7CaO-46.1SiO-2.6PO ("S46"), the latter constituting the "45S5 Bioglass" utilized for bone grafting applications. The BPS glass networks are built by interconnected SiO, BO, and BO moieties, whereas P exists mainly as orthophosphate anions, except for a minor network-associated portion involving P-O-Si and P-O-B motifs, whose populations were estimated by heteronuclear P{B} NMR experimentation. The high Na/Ca contents give fragmented glass networks with large amounts of nonbridging oxygen (NBO) anions. The MD-generated glass models reveal an increasing propensity for NBO accommodation among the network units according to BO < SiO < BO ≪ PO. The BO/BO intermixing was examined by double-quantum-single-quantum correlation B NMR experiments, which evidenced the presence of all three BO-BO, BO-BO, and BO-BO connectivities, with B-O-B bridges dominating. Notwithstanding that B-O-B linkages are disfavored, both NMR spectroscopy and MD simulations established their presence in these modifier-rich BPS glasses, along with non-negligible B-NBO contacts, at odds with the conventional structural view of borosilicate glasses. We discuss the relative propensities for intermixing of the Si/B/P network formers. Despite the absence of pronounced preferences for Si-O-Si bond formation, the glass models manifest subtle subnanometer-sized structural inhomogeneities, where SiO tetrahedra tend to self-associate into small chain/ring motifs embedded in BO/BO-dominated domains.
By employing 31P multiple-quantum
coherence-based solid-state
nuclear magnetic resonance spectroscopy, we present the first comprehensive
experimental assessment of the nature of the orthophosphate-ion distributions
in silicate-based bioactive glasses (BGs). Results are provided both
from melt-prepared BG and evaporation-induced self-assembly-derived
mesoporous bioactive glass (MBG) structures of distinct compositions.
The phosphate species are randomly dispersed in melt-derived BGs (comprising
44–55 mol % SiO2) of the Na2O–CaO–SiO2–P2O5 system, whereas a Si-rich
(86 mol % SiO2) and Ca-poor ordered MBG structure exhibits
nanometer-sized amorphous calcium phosphate clusters, conservatively
estimated to comprise at least nine orthophosphate groups. A Ca-richer
MBG (58 mol % SiO2) reveals a less pronounced phosphate
clustering. We rationalize the variable structural role of P in these
amorphous biomaterials.
The
physiological responses of silicate-based bioactive glasses (BGs)
are known to depend critically on both the P content (nP) of the glass and its silicate network connectivity
(N̅BOSi). However, while the bioactivity generally
displays a nonmonotonic dependence on nP itself, recent work suggest that it is merely the net orthophosphate
content that directly links to the bioactivity. We exploit molecular
dynamics (MD) simulations combined with 31P and 29Si solid-state nuclear magnetic resonance (NMR) spectroscopy to explore
the quantitative relationships between N̅BOSi, nP, and the silicate and phosphate speciations in a series
of Na2O–CaO–SiO2–P2O5 glasses spanning 2.1 ≤ N̅BOSi ≤
2.9 and variable P2O5 contents up to 6.0 mol
%. The fractional population of the orthophosphate groups remains
independent of nP at a fixed N̅BOSi-value,
but is reduced slightly as N̅BOSi increases. Nevertheless, P
remains predominantly as readily released orthophosphate ions, whose
content may be altered essentially independently of the network connectivity,
thereby offering a route to optimize the glass bioactivity. We discuss
the observed composition-structure links in relation to known composition-bioactivity
correlations, and define how Na2O–CaO–SiO2–P2O5 compositions exhibiting
an optimal bioactivity can be designed by simultaneously altering
three key parameters: the silicate network connectivity, the (ortho)phosphate
content, and the nNa/nCa molar ratio.
By
using double-quantum–single-quantum correlation 11B nuclear magnetic resonance (NMR) experiments and atomistic
molecular dynamics (MD) simulations, we resolve the long-standing
controversy of whether directly interlinked BO4–BO4 groups exist in the technologically ubiquitous class of alkali/alkaline-earth
based borosilicate (BS) glasses. Most structural models of Na2O–B2O3–SiO2 glasses assume the absence of B[4]–O–B[4] linkages, whereas they have been suggested to exist in
Ca-bearing BS analogs. Our results demonstrate that while B[4]–O–B[4] linkages are disfavored relative
to their B[3]–O–B[3]/B[4] counterparts, they are nevertheless abundant motifs in Na2O–B2O3–SiO2 glasses
over a large composition space, while the B[4]–O–B[4] contents are indeed elevated in Na2O–CaO–B2O3–SiO2 glasses. We discuss the
compositional and structural parameters that control the degree of
B[4]–O–B[4] bonding.
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