Proton Environments in Biomimetic Calcium Phosphates Formed from Mesoporous Bioactive CaO–SiO<sub>2</sub>–P<sub>2</sub>O<sub>5</sub> Glasses <i>in Vitro</i>: Insights from Solid-State NMR

  1. Mathew, Renny 1
  2. Turdean-Ionescu, Claudia 1
  3. Yu, Yang 1
  4. Stevensson, Baltzar 1
  5. Izquierdo-Barba, Isabel 234
  6. García, Ana 234
  7. Arcos, Daniel 234
  8. Vallet-Regí, María 234
  9. Edén, Mattias 1
  1. 1 Department of Materials and Environmental Chemistry, Arrhenius Laboratory, Stockholm University, SE-106 91 Stockholm, Sweden
  2. 2 Departamento de Quı́mica Inorgánica y Bioinorgánica, Facultad de Farmacia, Universidad Complutense de Madrid
  3. 3 Instituto de Investigación Sanitaria Hospital 12 de Octubre i+12, 28040 Madrid, Spain
  4. 4 Networking Research Center on Bioengineering, Biomaterials and Nanomedicine (CIBER-BBN), Madrid, Spain
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Revista:
The Journal of Physical Chemistry C

ISSN: 1932-7447,  1932-7455

Año de publicación: 2017

Volumen: 121

Número: 24

Páginas: 13223-132388

Tipo: Artículo

DOI: 10.1021/ACS.JPCC.7B03469 GOOGLE SCHOLAR lock_openAcceso abierto editor

Otras publicaciones en: The Journal of Physical Chemistry C

Resumen

When exposed to body fluids, mesoporousbioactive glasses (MBGs) of the CaO−SiO2−P2O5 systemdevelop a bone-bonding surface layer that initially consists ofamorphous calcium phosphate (ACP), which transforms intohydroxy-carbonate apatite (HCA) with a very similarcomposition as bone/dentin mineral. Information from various1H-based solid-state nuclear magnetic resonance (NMR)experiments was combined to elucidate the evolution of theproton speciations both at the MBG surface and within eachACP/HCA constituent of the biomimetic phosphate layerformed when each of three MBGs with distinct Ca, Si, and Pcontents was immersed in a simulated body fluid (SBF) forvariable periods between 15 min and 30 days. Directly excited magic-angle-spinning (MAS) 1H NMR spectra mainly reflect theMBG component, whose surface is rich in water and silanol (SiOH) moieties. Double-quantum−single-quantum correlation 1HNMR experimentation at fast MAS revealed their interatomic proximities. The comparatively minor H species of each ACP andHCA component were probed selectively by heteronuclear 1H−31P NMR experimentation. The initially prevailing ACP phasecomprises H2O and “nonapatitic” HPO42−/PO43− groups, whereas for prolonged MBG soaking over days, a well-progressed ACP→ HCA transformation was evidenced by a dominating O1H resonance from HCA. We show that 1H-detected 1H → 31P crosspolarization NMR is markedly more sensitive than utilizing powder X-ray diffraction or 31P NMR for detecting the onset of HCAformation, notably so for P-bearing (M)BGs. In relation to the long-standing controversy as to whether bone mineral comprisesACP and/or forms via an ACP precursor, we discuss a recently accepted structural core−shell picture of both synthetic andbiological HCA, highlighting the close relationship between the disordered surface layer and ACP.

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Información de financiación

Financiadores

  • Vetenskapsrådet
    • 2010-4943
    • 2014-4667
  • Carl Tryggers Stiftelse för Vetenskaplig Forskning
    • CTS 12:110
  • Fondo Europeo de Desarrollo Regional (FEDER)
    • MAT 2013-43299-R
    • MAT 2015-64831-R
    • MAT 2016-75611-R
  • European Research Council
    • Advanced Grant VERDI; ERC-2015-AdG Proposal 694160
  • Ministerio de Economía y Competitividad, Agencia Estatal de Investigación (AEI)

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