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Rapid-Setting Mesoporous Bioactive Glass Cements That Induce Accelerated

In Vitro Apatite FormationBy Qihui Shi, Jianfang Wang, Jinping Zhang, Jie Fan, and Galen D. Stucky*

Supporting Information

Figure S1. a) Small-angle and b) wide-angle XRD patterns of calcined MBGs with varyingcompositions. In our experiments, the molar fraction of P with respect to the total molar amountof Si, Ca, and P in MBGs was kept fixed at 4 % and those of Si and Ca were varied. MBG andMBGC samples were named according to the molar fraction of Si. These MBGs have a two-dimensional hexagonal mesostructure. When MBGs contain less than ~ 21 mol% Ca, small-angle XRD patterns exhibit three diffraction peaks, which can be indexed to the (100), (110), and(200) diffractions of a two-dimensional hexagonal mesostructure. For MBG-80S, d(100) = 7.30nm, d(110) = 4.37 nm, d(200) = 3.81 nm, and the lattice constant a = 8.66 nm. For MBG-75S, d(100)= 7.01 nm, d(110) = 4.21 nm, d(200) = 3.62 nm, and the lattice constant a = 8.29 nm. Themesostructural ordering of MBGs decreases with increasing molar fraction of Ca. As the molarfraction of Ca increases to ~ 26 %, only a single broad diffraction peak is observed in the small-angle regime. For MBG-70S, d(100) = 6.9 nm, and the lattice constant a = 8.0 nm. For MBG-65S,d(100) = 6.7 nm, and the lattice constant a = 7.7 nm. For MBG-60S, d(100) = 6.7 nm, and the latticeconstant a = 7.7 nm. The presence of a broad diffraction peak around 2� = 25� in b) is due to theamorphous nature of MBG walls. The appearance of a weak diffraction peak at 2� = 32� on thediffraction patterns of MBG-65S and MBG-60S indicates that a crystalline phase starts to formas the molar fraction of Ca in MBGs increases to more than 30 %.

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Figure S2. TEM image of calcined MBG-80S, showing a two-dimensional hexagonalmesostructure. The particle shown in the image contains both the domains with the [100] zoneaxis oriented parallel to the electron beam and those with the [001] zone axis oriented parallel tothe electron beam.

Figure S3. FT-IR spectra of MBGs with varying compositions. The weak absorption bands at557 cm-1 and 602 cm-1, as pointed with arrows, can be assigned to the phosphate group in acrystalline phase, which, together with the observation of a weak diffraction peak at 2� = 32�(Fig. S1b), indicates that a crystalline phase of calcium phosphate starts to form as the molarfraction of Ca in MBGs increases to more than 30 %.

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Figure S4. a) Small-angle XRD patterns of a) calcined MBG-80S and b) MBGC-80S. Theyexhibit a two-dimensional hexagonal mesostructure. For MBG-80S, d(100) = 7.30 nm, d(110) = 4.37nm, d(200) = 3.81 nm, and the lattice constant a = 8.66 nm. For MBGC-80S, d(100) = 7.3 nm, andthe lattice constant a = 8.4 nm.

Figure S5. TEM image of MBGC-80S, showing a two-dimensional hexagonal mesostructure.The particle shown in the image contains the domains with the [001] zone axis oriented parallelto the electron beam.

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Figure S6. Nitrogen sorption isotherms of a) MBG-80S and b) MBGC-80S. c) and d) are poresize distributions obtained from the adsorption branches of a) and b), respectively. Crosses andcircles represent the adsorption and desorption branches, respectively. The isotherms weremeasured at 77 K using a Micromeritics TriStar 3000 system and analyzed using the Barrett-Joyner-Halenda method with the Halsey equation for multilayer thickness. The nitrogen sorptionisotherms exhibit H1-type hysteresis loops, which are typical for one-dimensional pore channels.For MBG-80S, the surface area is 420 m2/g, the pore volume is 0.48 cm3/g, and the porediameter is 5.3 nm. For MBGC-80S, the surface area is 166 m2/g, the pore volume is 0.21 cm3/g,and the pore diameter is 5.2 nm. The decrease of specific surface areas and pore volumes can beascribed to the addition of the ammonium phosphate buffer solution. These observations indicatethat a majority of the pore channels in MBGCs remain unblocked and accessible from theoutside and that HA nanocrystals form on the surfaces of glass powders.

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Figure S7. FT-IR spectra of a) MBGC-80S, b) MBGC-80S soaked in SBF for 0.5 h, c) MBGC-80S soaked in SBF for 1 d, and d) MBGC-60S soaked in SBF for 1 d. The absorption bands at562 cm-1, 602 cm-1, and 960 cm-1, as pointed with arrows, arise from the phosphate group in thecrystalline HA phase.

Figure S8. Wide-angle XRD patterns of MBG-80S after being soaked in SBF for differentperiods of time. Two diffraction peaks at around 26° and 32° can be assigned to the (002) and(211) diffractions of the crystalline HA phase.

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Figure S9. FT-IR spectra of MBG-80S after being soaked in SBF for different periods of time.The absorption bands at 568 cm-1, 606 cm-1, and 960 cm-1, as pointed with arrows, arise from thephosphate group in a crystalline phase. The absorption bands at 870 cm-1, 1443 cm-1, and 1504cm-1, as pointed with arrows, are from the carbonate group.