Probing the calcium and sodium local environment in bones and teeth using multinuclear solid state NMR and X-ray absorption spectroscopy.
Abstract: 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 (31)P and (1)H 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 (43)Ca solid state NMR and Ca K-edge X-ray absorption spectroscopy, revealing important structural information about the calcium coordination shell. The (43)Ca delta(iso) in HB and CT is found to correlate with the average Ca-O bond distance measured by Ca K-edge EXAFS, and the (43)Ca 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, (23)Na MAS NMR, high resolution 3Q-MAS NMR, as well as (23)Na{(31)P} REDOR and (1)H{(23)Na} R(3)-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).
Publication Date: 2009-11-07 PubMed ID: 20094673DOI: 10.1039/b915708eGoogle Scholar: Lookup
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- Journal Article
- Research Support
- Non-U.S. Gov't
Summary
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This research delves into the structure and composition of bone mineral, specifically focusing on calcium and sodium components. Using advanced scientific techniques, the study explores how these minerals are arranged within the complex structure of bone and teeth.
Understanding the Bone Mineral Structure
- The study addresses the unresolved questions about bone mineral composition and structure. While the bone mineral is generally composed of hydroxyapatite with various replacements, its organization and relationship with the collagen matrix remains complex and poorly understood.
- Previous researches predominantly used phosphorus ((31)P) and hydrogen ((1)H) NMR to study bone mineral, providing meaningful insights into its intricate structure.
- However, former research has not thoroughly investigated significant bone mineral elements, such as calcium and lesser-known cations like sodium. This study aims to fill this research gap.
Exploration of Calcium in Biological Apatites
- The research analyses the local environment of calcium in equine bone (HB) and bovine tooth (CT) using multitechnique approach – solid state NMR (43Ca) and Ca K-edge X-ray absorption spectroscopy.
- This approach provided valuable data about the calcium coordination shell’s structure.
- Findings suggest a higher distribution in chemical bonding around calcium in HB and CT, indicating more complexity compared to synthetic apatites.
Investigation of Sodium in Biological Apatites
- The study additionally used high resolution 3Q-MAS NMR, (23)Na{(31)P} REDOR, and (1)H{(23)Na} R(3)-HMQC correlation experiments to probe sodium’s presence in HB and CT.
- Results revealed the first direct evidence of some sodium located inside the apatite phase of HB and CT, implying a varied distribution of environments than a synthetic sodium substituted apatite (Na-HA).
Significance of the Study
- This study is groundbreaking as it uses state-of-the-art techniques to explore the under-researched areas of bone structure and composition, yielding new insights about calcium and sodium’s localization and distribution in bone and teeth.
- The results could fundamentally enhance the existing understanding of the bone’s complex organization, composition, and bonding properties, potentially guiding future research on bone health and diseases.
Cite This Article
APA
Laurencin D, Wong A, Chrzanowski W, Knowles JC, Qiu D, Pickup DM, Newport RJ, Gan Z, Duer MJ, Smith ME.
(2009).
Probing the calcium and sodium local environment in bones and teeth using multinuclear solid state NMR and X-ray absorption spectroscopy.
Phys Chem Chem Phys, 12(5), 1081-1091.
https://doi.org/10.1039/b915708e Publication
Researcher Affiliations
- Department of Physics, University of Warwick, Coventry, UKCV4 7AL. danielle.laurencin@univ-montp2.fr
MeSH Terms
- Animals
- Bone and Bones / chemistry
- Calcium / analysis
- Calcium / chemistry
- Cattle
- Magnetic Resonance Spectroscopy
- Sodium / analysis
- Sodium / chemistry
- Tooth / chemistry
- X-Ray Absorption Spectroscopy
Grant Funding
- Biotechnology and Biological Sciences Research Council
Citations
This article has been cited 8 times.- Shen S, Liu Z, Wang J, Fan L, Ji F, Tao J. Machine learning assisted Cameriere method for dental age estimation.. BMC Oral Health 2021 Dec 15;21(1):641.
- Zuo W, Liu X, Qiu J, Zhang D, Xiao Z, Xie J, Ren F, Wang J, Li Y, Ortiz GF, Wen W, Wu S, Wang MS, Fu R, Yang Y. Engineering Na(+)-layer spacings to stabilize Mn-based layered cathodes for sodium-ion batteries.. Nat Commun 2021 Aug 12;12(1):4903.
- Mathe Z, Pantazis DA, Lee HB, Gnewkow R, Van Kuiken BE, Agapie T, DeBeer S. Calcium Valence-to-Core X-ray Emission Spectroscopy: A Sensitive Probe of Oxo Protonation in Structural Models of the Oxygen-Evolving Complex.. Inorg Chem 2019 Dec 2;58(23):16292-16301.
- Quinn CM, Wang M, Polenova T. NMR of Macromolecular Assemblies and Machines at 1 GHz and Beyond: New Transformative Opportunities for Molecular Structural Biology.. Methods Mol Biol 2018;1688:1-35.
- Lee D, Leroy C, Crevant C, Bonhomme-Coury L, Babonneau F, Laurencin D, Bonhomme C, De Paëpe G. Interfacial Ca(2+) environments in nanocrystalline apatites revealed by dynamic nuclear polarization enhanced (43)Ca NMR spectroscopy.. Nat Commun 2017 Jan 27;8:14104.
- Sun Y, Brauckmann O, Nixdorf DR, Kentgens A, Garwood M, Idiyatullin D, Heerschap A. Imaging human teeth by phosphorus magnetic resonance with nuclear Overhauser enhancement.. Sci Rep 2016 Aug 8;6:30756.
- Mroue KH, Xu J, Zhu P, Morris MD, Ramamoorthy A. Selective detection and complete identification of triglycerides in cortical bone by high-resolution (1)H MAS NMR spectroscopy.. Phys Chem Chem Phys 2016 Jul 28;18(28):18687-91.
- Mathew R, Gunawidjaja PN, Izquierdo-Barba I, Jansson K, García A, Arcos D, Vallet-Regí M, Edén M. Solid-State P and H NMR Investigations of Amorphous and Crystalline Calcium Phosphates Grown Biomimetically From a Mesoporous Bioactive Glass.. J Phys Chem C Nanomater Interfaces 2011 Oct 27;115(42):20572-20582.
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