Skip to content
Licensed Unlicensed Requires Authentication Published by De Gruyter January 3, 2017

Infrared spectra of carbonate apatites: Evidence for a connection between bone mineral and body fluids

  • Michael E. Fleet EMAIL logo
From the journal American Mineralogist

Abstract

The complex asymmetric stretch (ν3) region infrared (IR) spectrum of synthetic sodium- and carbonate-bearing hydroxylapatites (CHAP) has been interpreted using overlapped Gaussian distributions for individual carbonate ion species. There is now good agreement for the distribution of carbonate ions between phosphate (type B) and c-axis channel (type A) positions using three independent methods: X-ray structure site occupancies, out-of-plane bend (ν2) band areas, and asymmetric stretch (ν3) band areas; B/A ratios for a well-crystallized CHAP sample being 0.77, 0.78, and 0.75, respectively. The reported dominance of type B carbonate ions in bone mineral and dental enamel is attributed to the anomalous shift of type A band frequencies into the spectral region of type B, resulting from the substitution of Ca2+ by Na+ in the nearest-neighbor cation shell of the channel carbonate ions. The infrared spectra show that the hydrogencarbonate (bicarbonate) ion in apatite crystals is a channel species, as are its room-temperature decomposition products, type A carbonate and labile (type L) carbonate. The research suggests that bone mineral crystals may actively communicate with body fluids through the apatite channel, pointing to a possible role for the apatite channel in mediating acid-base reactions in the body.

Acknowledgements

I thank Xi Liu for crystal synthesis and FTIR measurements, Chris Tacker and a second unnamed reviewer for helpful comments, and the Natural Sciences and Engineering Research Council of Canada for financial support.

References cited

Arends, J., and Davidson, C.L. (1975) HPO42 content in enamel and artificial carious lesions. Calcified Tissue Research, 18, 65–79.10.1007/BF02546227Search in Google Scholar

Baxter, J.D., Biltz, R.M., and Pellegrino, E.D. (1966) The physical state of bone carbonate: A comparative infra-red study in several mineralized tissues. The Yale Journal of Biology and Medicine, 38, 456–470.Search in Google Scholar

Bettice, J.A. (1984) Skeletal carbon dioxide stores during metabolic acidosis. American Journal of Physiology, 247, F326–F330.10.1152/ajprenal.1984.247.2.F326Search in Google Scholar

Bonel, G. (1972) Contribution à l’ étude de la carbonatation des apatites. I.—Synthèse et étude des propriétés physico-chimiques des apatites carbon atées du type A. Annales de Chimie, (Paris, France), 7, 65–88.Search in Google Scholar

Brudevold, F., Gardner, D.E., and Smith, F.A. (1956) Distribution of fluorine in human enamel. Journal of Dental Research, 35, 420–429.10.1177/00220345560350031301Search in Google Scholar

Bushinsky, D.A., Smith, S.B., Gavrilov, K.L., Gavrilov, L.F., Li, J., and Levi-Setti, R. (2002) Acute acidosis-induced alteration in bone bicarbonate and phosphate. American Journal of Physiology–Renal Physiology, 283, F1091–F1097.10.1152/ajprenal.00155.2002Search in Google Scholar

Carlström, D. (1968) Mineralogical carbonate-containing apatites. In W. E. Brown and R.A. Young, Eds., Proceedings of International Symposium on Structural Properties of Hydroxyapatite and Related Compounds, Gaithersburg, Maryland, Chap. 10.Search in Google Scholar

Driessens, F.C.M., Verbeeck, R.M.H., and Heijligers, H.J.M. (1983) Some physical properties of Na- and CO3-containing apatites synthesized at high temperatures. Inorganica Chimica Acta, 80, 19–23.10.1016/S0020-1693(00)91256-8Search in Google Scholar

Elliott, J.C. (1964) The interpretation of the infra-red absorption spectra of some carbonate-containing apatites. In R.W. Fearnhead and M.V. Stack, Eds., Tooth Enamel: Its Composition, Properties, and Fundamental Structure, pp. 20-22. John Wright & Sons Bristol, U.K.Search in Google Scholar

——— (1994) Structure and Chemistry of the Apatites and Other Calcium Orthophosphates, 389 p. Elsevier, Amsterdam.Search in Google Scholar

——— (2002) Calcium phosphate biominerals. In M.J. Kohn, J. Rakovan, and J.M. Hughes, Eds., Phosphates, pp. 427–453. Reviews in Mineralogy and Geochemistry, 48, Mineralogical Society of America, Chantilly, Virginia.10.1515/9781501509636Search in Google Scholar

Farlay, D., Panzcer, G., Rey, C., Delmas, P.D., and Boivin, G. (2010) Mineral maturity and crystallinity index are distinct characteristics of bone mineral. Journal of Bone and Mineral Metabolism, 28, 433–445.10.1007/s00774-009-0146-7Search in Google Scholar

Fleet, M.E. (2009) Infrared spectra of carbonate apatites: ν2-region bands. Biomaterials, 30, 1473–1481.10.1016/j.biomaterials.2008.12.007Search in Google Scholar

——— (2012) The carbonate ion in hydroxyapatite and biological apatite. In R.B. Heimann, Ed., Calcium Phosphate: Structure, Synthesis, Properties, and Applications, pp. 41–61, Nova Science Publishers, New York.Search in Google Scholar

——— (2014a) Distribution of carbonate ions in biological apatite and excess fluorine in francolite. In M. Iafisco and J.M. Delgado-López, Eds., Apatite: Synthesis, Structural Characterization and Biomedical Applications, pp. 103–122, Nova Science Publishers, New York.Search in Google Scholar

——— (2014b) Carbonated Hydroxyapatite: Materials, Synthesis, and Applications, 268 p, Pan Stanford Publishing, Singapore.Search in Google Scholar

Fleet, M.E., and Liu, X. (2003) Carbonate apatite type A synthesized at high pressure: new space group (P3¯) and orientation of channel carbonate ion. Journal of Solid State Chemistry, 174, 412–417.10.1016/S0022-4596(03)00281-0Search in Google Scholar

——— (2004) Location of type B carbonate ion in type A-B carbonate apatite synthesized at high pressure. Journal of Solid State Chemistry, 177, 3174–3182.10.1016/j.jssc.2004.04.002Search in Google Scholar

——— (2005) Local structure of channel ions in carbonate apatite. Biomaterials, 26, 7548–7554.10.1016/j.biomaterials.2005.05.025Search in Google Scholar PubMed

——— (2007a) Coupled substitution of type A and B carbonate in sodium-bearing apatite. Biomaterials, 28, 916–926.10.1016/j.biomaterials.2006.11.003Search in Google Scholar PubMed

——— (2007b) Hydrogen-carbonate ion in synthetic high-pressure apatite. American Mineralogist, 92, 1764–1767.10.2138/am.2007.2716Search in Google Scholar

——— (2008a) Accommodation of the carbonate ion in fluorapatite synthesized at high pressure. American Mineralogist, 93, 1460–1469.10.2138/am.2008.2786Search in Google Scholar

——— (2008b) Type A-B carbonate chlorapatite synthesized at high pressure. Journal of Solid State Chemistry, 181, 2494–2500.10.1016/j.jssc.2008.06.016Search in Google Scholar

Fleet, M.E., Liu, X., and King, P.L. (2004) Accommodation of the carbonate ion in apatite: An FTIR and X-ray structure study of crystals synthesized at 2–4 GPa. American Mineralogist, 89, 1422–1432.10.2138/am-2004-1009Search in Google Scholar

Fleet, M.E., Liu, X., and Liu, Xi (2011) Orientation of channel carbonate ions in apatite: Effect of pressure and composition. American Mineralogist, 96, 1148–1157.10.2138/am.2011.3683Search in Google Scholar

Green, J., and Kleeman, C.R. (1991) Role of bone in regulation of systemic acid- base balance. Kidney International, 39, 9–26.10.1159/000420160Search in Google Scholar PubMed

LeGeros, R.Z. (1991) Calcium Phosphates in Oral Biology and Medicine, 201 p., Karger, Basel.Search in Google Scholar

LeGeros, R.Z., Trautz, O.R., Klein, E., and LeGeros, J.P. (1969) Two types of carbonate substitution in the apatite structure. Experimentia, 25, 5–7.10.1007/BF01903856Search in Google Scholar PubMed

Libowitzky, E., and Rossman, G.R. (1996) Principles of quantitative absorbance measurements in anisotropic cystals. Physics and Chemistry of Minerals, 23, 319–327.10.1007/BF00199497Search in Google Scholar

Liu, X., Shieh, S.R., Fleet, M.E., Zhang, L., and He, Q. (2011) Equation of state of carbonated hydroxylapatite at ambient temperature up to 10 GPa: Significance of carbonate. American Mineralogist, 96, 74–80.10.2138/am.2011.3535Search in Google Scholar

Madix, R.J., Solomon, J.L., and Stöhr, J. (1988) The orientation of the carbonate anion on Ag(110). Surface Science, 197, L253–L259.10.1016/0039-6028(88)90624-3Search in Google Scholar

McClellan, G.H., and Lehr, J.R. (1969) Crystal chemical investigation of natural apatites. American Mineralogist, 54, 1374–1391.Search in Google Scholar

Mehmel, M. (1930) Über die Struktur des Apatits. Zietschrift für Kristallographie, 75, 323–331.10.1515/zkri-1930-0122Search in Google Scholar

Nakamoto, K. (1997) Infrared and Raman Spectra of Inorganic and Coordination compounds. Part A: Theory and Applications in Inorganic Chemistry, 387 p., 5th ed. Wiley, New York.Search in Google Scholar

Náray-Szabó, S. (1930) The structure of apatite (CaF)Ca4(PO4)3. Zietschrift für Kristallographie, 75, 387–398.Search in Google Scholar

Nelson, D.G.A., and Featherstone, J.D.B. (1982) Preparation, analysis, and characterization of carbonated apatites. Calcified Tissue International, 34, S69–S81.Search in Google Scholar

Neuman, W.F., and Mulryan, B.J. (1967) Synthetic hydroxyapatite crystals. III. The carbonate system. Calcified Tissue Research, 1, 94–104.10.1007/BF02008079Search in Google Scholar

Neuman, W.F., Terepka, A.R., and Triffitt, J.T. (1968) Cycling concept of exchange in bone. Calcified Tissue Research, 2, 262–270.10.1007/BF02279214Search in Google Scholar

Palmer, L.C., Newcomb, C.J., Kaltz, S.R., Spoerke, E.D., and Stupp, S.I. (2008) Biomimetic systems for hydroxyapatite mineralization inspired by bone and enamel. Chemical Reviews, 108, 4754–4783.10.1021/cr8004422Search in Google Scholar

Paschalis, E.P., DiCarlo, E., Betts, F., Sherman, P., Mendelsohn, R., and Boskey, A.L. (1996) FTIR microspectroscopic analysis of human osteonal bone. Calcified Tissue International, 59, 480–487.10.1007/BF00369214Search in Google Scholar

Poyart, C.F., Bursaux, E., and Fréminet, A. (1975a) The bone CO2 compartment: evidence for a bicarbonate pool. Respiration Physiology, 25, 89–99.10.1016/0034-5687(75)90053-5Search in Google Scholar

Poyart, C.F., Fréminet, A., and Bursaux, E. (1975b) The exchange of bone CO2in vivo. Respiration Physiology, 25, 101–107.10.1016/0034-5687(75)90054-7Search in Google Scholar

Rey, C., Collins, B., Goehl, T., Dickson, I.R., and Glimcher, M.J. (1989) The carbonate environment in bone mineral: A resolution-enhanced Fourier transform infrared study. Calcified Tissue International, 45, 157–164.10.1007/BF02556059Search in Google Scholar PubMed

Rey, C., Renugopalakrishnan, V., Shimizu, M., Collins, B., and Glimcher, M.J. (1991) A resolution-enhanced Fourier transform infrared spectroscopic study of the environment of the CO32– ion in the mineral phase of enamel during its formation and maturation. Calcified Tissue International, 49, 259–268.10.1007/BF02556215Search in Google Scholar PubMed

Rey, C., Combes, C., Drouet, C., and Glimcher, M.J. (2009) Bone mineral: Update on chemical composition and structure. Osteoporosis International, 20, 1013–1021.10.1007/s00198-009-0860-ySearch in Google Scholar PubMed PubMed Central

Shimoda, S., Aoba, T., Moreno, E.C., and Miake, Y. (1990) Effect of solution composition on morphological and structural features of carbonated calcium apatites. Journal of Dental Research, 69, 1731–1740.10.1177/00220345900690110501Search in Google Scholar PubMed

Suetsugu, Y., Shimoya, I., and Tanaka, J. (1998) Configuration of carbonate ions in apatite structure determined by polarized infrared spectroscopy. Journal of the American Ceramic Society, 81, 746–748.10.1111/j.1151-2916.1998.tb02403.xSearch in Google Scholar

Tacker, R.C. (2008) Carbonate in igneous and metamorphic fluorapatite: Two type A and two type B substitutions. American Mineralogist, 93, 168–176.10.2138/am.2008.2551Search in Google Scholar

Tyliszcak, T. (1992) BGAUSS Data Analysis Program. McMaster University.Search in Google Scholar

Verbeeck, R.M.H., De Maeyer, E.A.P., and Driessens, F.C.M. (1995) Stoichiometry of potassium- and carbonate-containing apatites synthesized by solid state reactions. Inorganic Chemistry, 34, 2084–2088.10.1021/ic00112a021Search in Google Scholar

Verdelis, K., Lukashova, L., Wright, J.T., Mendelsohn, R., Peterson, M.G.E., Doty, S., and Boskey, A.L. (2007) Maturational changes in dentin mineral properties. Bone, 40, 1399–1407.10.1016/j.bone.2006.12.061Search in Google Scholar PubMed PubMed Central

Vignoles, C. (1973) Contribution à l’étude de l’influence des ions alcalins sur la carbonatation dans les sites de type B des apatites phosphor-calciques, thèse, L’université de Paul Sabatier, Toulouse, France.Search in Google Scholar

Wilson, R.M., Elliott, J.C., Dowker, S.E.P., and Smith, R.I. (2004) Rietveld structure refinement of precipitated carbonate apatite using neutron diffraction data. Biomaterials, 25, 2205–2213.10.1016/j.biomaterials.2003.08.057Search in Google Scholar PubMed

Yi, H., Balan, E., Gervais, C., Ségalen, L., Blanchard, M., and Lazzeri, M. (2014) Theoretical study of the local charge compensation and spectroscopic properties of B-type carbonate defects in apatite. Physics and Chemistry of Minerals, 41, 347–359.10.1007/s00269-013-0654-9Search in Google Scholar

Received: 2016-2-1
Accepted: 2016-8-25
Published Online: 2017-1-3
Published in Print: 2017-1-1

© 2017 by Walter de Gruyter Berlin/Boston

Downloaded on 28.3.2024 from https://www.degruyter.com/document/doi/10.2138/am-2017-5704/html
Scroll to top button