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Probing the calcium and sodium local environment in bones and teeth using multinuclear solid state NMR and X-ray absorption spectroscopy

Laurencin, D., Wong, A., Chrzanowski, W., Knowles, J.C., Qiu, D., Pickup, D.M., Newport, Robert J., Gan, Z., Duer, M.J., Smith, M.E. and others. (2010) Probing the calcium and sodium local environment in bones and teeth using multinuclear solid state NMR and X-ray absorption spectroscopy. Physical Chemistry Chemical Physics, 12 (5). pp. 1081-1091. ISSN 1463-9076. (doi:10.1039/b915708e) (KAR id:46968)


Despite the numerous studies of bone mineral, there are still many questions regarding the exact structure and composition of the mineral phase, and how the mineral crystals become organised with respect to each other and the collagen matrix. Bone mineral is commonly formulated as hydroxyapatite, albeit with numerous substitutions, and has previously been studied by 31P and 1H NMR, which has given considerable insight into the complexity of the mineral structure. However, to date, there has been no report of an NMR investigation of the other major component of bone mineral, calcium, nor of common minority cations like sodium. Here, direct analysis of the local environment of calcium in two biological apatites, equine bone (HB) and bovine tooth (CT), was carried out using both 43Ca solid state NMR and Ca K-edge X-ray absorption spectroscopy, revealing important structural information about the calcium coordination shell. The 43Ca δiso in HB and CT is found to correlate with the average Ca-O bond distance measured by Ca K-edge EXAFS, and the 43Ca NMR linewidths show that there is a greater distribution in chemical bonding around calcium in HB and CT, compared to synthetic apatites. In the case of sodium, 23Na MAS NMR, high resolution 3Q-MAS NMR, as well as 23Na{31P} REDOR and 1H{23Na} R3-HMQC correlation experiments give the first direct evidence that some sodium is located inside the apatite phase in HB and CT, but with a greater distribution of environments compared to a synthetic sodium substituted apatite (Na-HA).

Item Type: Article
DOI/Identification number: 10.1039/b915708e
Additional information: Unmapped bibliographic data: LA - English [Field not mapped to EPrints] J2 - Phys. Chem. Chem. Phys. [Field not mapped to EPrints] C2 - 20094673 [Field not mapped to EPrints] AD - Department of Physics, University of Warwick, Coventry, CV4 7AL, United Kingdom [Field not mapped to EPrints] AD - Eastman Dental Institute, University College London, 256 Gray's Inn Road, London, WC1X 8LD, United Kingdom [Field not mapped to EPrints] AD - School of Physical Sciences, Ingram Building, University of Kent, Canterbury, CT2 7NR, United Kingdom [Field not mapped to EPrints] AD - Center of Interdisciplinary Magnetic Resonance, National High Magnetic Field Laboratory, Tallahassee, FL 32310, United States [Field not mapped to EPrints] AD - Department of Chemistry, University of Cambridge, Lensfield Road, Cambridge, CB2 1EW, United Kingdom [Field not mapped to EPrints] DB - Scopus [Field not mapped to EPrints]
Uncontrolled keywords: calcium, sodium, animal, article, bone, cattle, chemistry, nuclear magnetic resonance spectroscopy, tooth, X ray absorption spectroscopy, Animals, Bone and Bones, Calcium, Cattle, Magnetic Resonance Spectroscopy, Sodium, Tooth, X-Ray Absorption Spectroscopy
Subjects: Q Science > QC Physics > QC173.45 Condensed Matter
Q Science > QD Chemistry > QD478 Solid State Chemistry
Divisions: Divisions > Division of Natural Sciences > Physics and Astronomy
Depositing User: Giles Tarver
Date Deposited: 11 Feb 2015 13:50 UTC
Last Modified: 16 Nov 2021 10:19 UTC
Resource URI: (The current URI for this page, for reference purposes)

University of Kent Author Information

Pickup, D.M..

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Newport, Robert J..

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