Crystallinity and compositional changes in carbonated apatites: Evidence from 31P solid-state NMR, Raman, and AFM analysis

John-David P. McElderry, Peizhi Zhu, Kamal H. Mroue, Jiadi Xu, Barbara Pavan, Ming Fang, Guisheng Zhao, Erin McNerny, David H. Kohn, Renny T. Franceschi, Mark M. Banaszak Holl, Mary M.J. Tecklenburg, Ayyalusamy Ramamoorthy, Michael D. Morris

Research output: Contribution to journalArticleResearchpeer-review

Abstract

Solid-state (magic-angle spinning) NMR spectroscopy is a useful tool for obtaining structural information on bone organic and mineral components and synthetic model minerals at the atomic-level. Raman and 31P NMR spectral parameters were investigated in a series of synthetic B-type carbonated apatites (CAps). Inverse 31P NMR linewidth and inverse Raman PO 4 3- ν1 bandwidth were both correlated with powder XRD c-axis crystallinity over the 0.3-10.3 wt% CO3 2- range investigated. Comparison with bone powder crystallinities showed agreement with values predicted by NMR and Raman calibration curves. Carbonate content was divided into two domains by the 31P NMR chemical shift frequency and the Raman phosphate ν1 band position. These parameters remain stable except for an abrupt transition at 6.5 wt% carbonate, a composition which corresponds to an average of one carbonate per unit cell. This near-binary distribution of spectroscopic properties was also found in AFM-measured particle sizes and Ca/P molar ratios by elemental analysis. We propose that this transition differentiates between two charge-balancing ion-loss mechanisms as measured by Ca/P ratios. These results define a criterion for spectroscopic characterization of B-type carbonate substitution in apatitic minerals.

Original languageEnglish
Pages (from-to)192-198
Number of pages7
JournalJournal of Solid State Chemistry
Volume206
DOIs
Publication statusPublished - 11 Sep 2013
Externally publishedYes

Keywords

  • Bone mineral
  • Carbonated apatite
  • Crystallinity
  • MAS
  • NMR
  • Raman spectroscopy

Cite this

McElderry, John-David P. ; Zhu, Peizhi ; Mroue, Kamal H. ; Xu, Jiadi ; Pavan, Barbara ; Fang, Ming ; Zhao, Guisheng ; McNerny, Erin ; Kohn, David H. ; Franceschi, Renny T. ; Holl, Mark M. Banaszak ; Tecklenburg, Mary M.J. ; Ramamoorthy, Ayyalusamy ; Morris, Michael D. / Crystallinity and compositional changes in carbonated apatites : Evidence from 31P solid-state NMR, Raman, and AFM analysis. In: Journal of Solid State Chemistry. 2013 ; Vol. 206. pp. 192-198.
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title = "Crystallinity and compositional changes in carbonated apatites: Evidence from 31P solid-state NMR, Raman, and AFM analysis",
abstract = "Solid-state (magic-angle spinning) NMR spectroscopy is a useful tool for obtaining structural information on bone organic and mineral components and synthetic model minerals at the atomic-level. Raman and 31P NMR spectral parameters were investigated in a series of synthetic B-type carbonated apatites (CAps). Inverse 31P NMR linewidth and inverse Raman PO 4 3- ν1 bandwidth were both correlated with powder XRD c-axis crystallinity over the 0.3-10.3 wt{\%} CO3 2- range investigated. Comparison with bone powder crystallinities showed agreement with values predicted by NMR and Raman calibration curves. Carbonate content was divided into two domains by the 31P NMR chemical shift frequency and the Raman phosphate ν1 band position. These parameters remain stable except for an abrupt transition at 6.5 wt{\%} carbonate, a composition which corresponds to an average of one carbonate per unit cell. This near-binary distribution of spectroscopic properties was also found in AFM-measured particle sizes and Ca/P molar ratios by elemental analysis. We propose that this transition differentiates between two charge-balancing ion-loss mechanisms as measured by Ca/P ratios. These results define a criterion for spectroscopic characterization of B-type carbonate substitution in apatitic minerals.",
keywords = "Bone mineral, Carbonated apatite, Crystallinity, MAS, NMR, Raman spectroscopy",
author = "McElderry, {John-David P.} and Peizhi Zhu and Mroue, {Kamal H.} and Jiadi Xu and Barbara Pavan and Ming Fang and Guisheng Zhao and Erin McNerny and Kohn, {David H.} and Franceschi, {Renny T.} and Holl, {Mark M. Banaszak} and Tecklenburg, {Mary M.J.} and Ayyalusamy Ramamoorthy and Morris, {Michael D.}",
year = "2013",
month = "9",
day = "11",
doi = "10.1016/j.jssc.2013.08.011",
language = "English",
volume = "206",
pages = "192--198",
journal = "Journal of Solid State Chemistry",
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McElderry, J-DP, Zhu, P, Mroue, KH, Xu, J, Pavan, B, Fang, M, Zhao, G, McNerny, E, Kohn, DH, Franceschi, RT, Holl, MMB, Tecklenburg, MMJ, Ramamoorthy, A & Morris, MD 2013, 'Crystallinity and compositional changes in carbonated apatites: Evidence from 31P solid-state NMR, Raman, and AFM analysis' Journal of Solid State Chemistry, vol. 206, pp. 192-198. https://doi.org/10.1016/j.jssc.2013.08.011

Crystallinity and compositional changes in carbonated apatites : Evidence from 31P solid-state NMR, Raman, and AFM analysis. / McElderry, John-David P.; Zhu, Peizhi; Mroue, Kamal H.; Xu, Jiadi; Pavan, Barbara; Fang, Ming; Zhao, Guisheng; McNerny, Erin; Kohn, David H.; Franceschi, Renny T.; Holl, Mark M. Banaszak; Tecklenburg, Mary M.J.; Ramamoorthy, Ayyalusamy; Morris, Michael D.

In: Journal of Solid State Chemistry, Vol. 206, 11.09.2013, p. 192-198.

Research output: Contribution to journalArticleResearchpeer-review

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T1 - Crystallinity and compositional changes in carbonated apatites

T2 - Evidence from 31P solid-state NMR, Raman, and AFM analysis

AU - McElderry, John-David P.

AU - Zhu, Peizhi

AU - Mroue, Kamal H.

AU - Xu, Jiadi

AU - Pavan, Barbara

AU - Fang, Ming

AU - Zhao, Guisheng

AU - McNerny, Erin

AU - Kohn, David H.

AU - Franceschi, Renny T.

AU - Holl, Mark M. Banaszak

AU - Tecklenburg, Mary M.J.

AU - Ramamoorthy, Ayyalusamy

AU - Morris, Michael D.

PY - 2013/9/11

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N2 - Solid-state (magic-angle spinning) NMR spectroscopy is a useful tool for obtaining structural information on bone organic and mineral components and synthetic model minerals at the atomic-level. Raman and 31P NMR spectral parameters were investigated in a series of synthetic B-type carbonated apatites (CAps). Inverse 31P NMR linewidth and inverse Raman PO 4 3- ν1 bandwidth were both correlated with powder XRD c-axis crystallinity over the 0.3-10.3 wt% CO3 2- range investigated. Comparison with bone powder crystallinities showed agreement with values predicted by NMR and Raman calibration curves. Carbonate content was divided into two domains by the 31P NMR chemical shift frequency and the Raman phosphate ν1 band position. These parameters remain stable except for an abrupt transition at 6.5 wt% carbonate, a composition which corresponds to an average of one carbonate per unit cell. This near-binary distribution of spectroscopic properties was also found in AFM-measured particle sizes and Ca/P molar ratios by elemental analysis. We propose that this transition differentiates between two charge-balancing ion-loss mechanisms as measured by Ca/P ratios. These results define a criterion for spectroscopic characterization of B-type carbonate substitution in apatitic minerals.

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KW - Bone mineral

KW - Carbonated apatite

KW - Crystallinity

KW - MAS

KW - NMR

KW - Raman spectroscopy

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