Summary
By modelling a hydroxyapatite crystal lattice as a finite cluster of atoms surrounded by an array of point ions, molecular orbital MS-Xα calculations point to differences in fluoride and hydroxyl migration energies. Despite the fluoride ion being more tightly bound to the lattice, it is in fact more mobile. Color center optical absorption is predicted to be in the infrared region of the spectrum for hydroxyapatite, whereas for fluorapatite the absorption peak of a vacancy is predicted to within 2% of the observed peak in the optical region. This result is discussed in terms of experimental studies of bonding between the calcified and organic phases of bone.
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References
Johnson, K.H.: Scattered wave theory of the chemical bond. In P.O. Lowdin (ed.): Advances in Quantum Chemistry, pp. 143–185. Academic Press, New York, 1973
Slater, J.C.: In P.O. Lowdin (ed.): Advances in Quantum Chemistry, vol. 6, p. 1. Academic Press, New York, 1973
Messmer, R.P.: Cluster model theory and its application to metal surface-adsorbate systems. In G. Ertland, T.N. Rhodin (eds.): The Nature of the Surface Chemical Bond. North-Holland Press, Amsterdam, 1978
Tse, C., Welch, D.O., Royce, B.S.H.: The migration of F−, OH−, and O2− ions in apatite, Calcif. Tissue Res.13:47–52, 1973
Messmer, R.P., Watkins, G.D.: Molecular orbital treatment for deep levels in semiconductors: substitutional nitrogen and the lattice vacancy in diamond, Physiol. Rev. B7:2568–2590, 1973
Herman, F., Salahub, D.R., Messmer, R.P.: Xα scatteredwave calculations for dimers and trimers of tetrathiafulvalene (TTF) and tetracyanoquinodimethane (TCNQ), Physiol. Rev. B16:2453–2465, 1977
Johnson, K.H., Smith, F.C.: Chemical bonding of a molecular transition-metal ion in a crystalline environment, Physiol. Rev. B5:831–843, 1972
Michels, H.H., Hobbs, R.H., Wright, L.A., Connolly, J.W.D.: Electronic structure of excimer molecular lasers, Int. J. Quant. Chem.13:169–187, 1978
Yu, H., DeSeqeira, M.L., Connolly, J.W.D.: Calculation of the electronic structure of color centers by the multiple scattering method, Physiol. Rev. B14:772–779, 1976
Norman, J.G.: SCF-Xα calculations on PH3 using a non-empirical scheme for choosing overlapping sphere radii, J. Chem. Phys.61:4630–4635, 1974
Norman, J.G.: Non-empirical versus empirical choices for overlapping sphere radii ratios in SCF-Xα-SW calculations on ClO4 and SO2, Mol. Phys.31:1191–1197, 1976
Lamson, S.H.: Ph.D. Thesis, Rensselaer Polytechnic Institute, Troy, N.Y., 1978
Piper, W.W., Kravitz, L.C., Swank, R.K.: Axially symmetric paramagnetic color centers in fluorapatite, Physiol. Rev.138:A1802-A1814, 1965
Swank, R.K.: Color centers in x-irradiated halophosphate crystals, Physiol. Rev.135:A266-A275, 1965
Warren, R.W.: Defect centers in calcium fluorophosphate, Physiol. Rev. B6:4679–4689, 1972
Sudarsanan, K., Mackie, P.E., Young, R.A.: Comparison of synthetic and mineral fluorapatite, Ca5(PO4)3F in crystallographic detail, Mat. Res. Bull.7:1331–1338, 1972
Sudarsanan, K., Young, R.A.: Significant precision in crystal structure details: Holly Springs hydroxyapatite, Acta Cryst.B25:1534–1543, 1969
Fowler, B.O.: International Symposium on Structural Properties of Hydroxyapatite and Related Compounds, National Bureau of Standards, Gaithersburg, Maryland 1968
Young, R.A., Van der Lugt, W., Elliott, J.C.: Mechanism for fluorine inhibition of diffussion in hydroxyapatite, Nature223:729–730, 1969
Koberle, G., Terrile, C., Panepucci, H.C., Mascarenhas, S.: On the paramagnetism of bone irradiated in vivo, An. Acad. Brasil. Cienc.45:157–160, 1973
Panepucci, H., Mascarenhas, S., Terrile, C.: Bone as a dosimeter. In S. Watanabe (ed.): Proc. 1st Latin American Cong. Phys. Med., Univ. Sao Paulo, Brazil, 1972
Panepucci, H., Farach, H.A.: ESR spectra of quasi randomly oriented centers: application to radiation damage centers in bone, Med. Phys.4:46–48, 1977
Behari, J., Guha, S.K., Agarwal, P.N.: Absorption spectra of bone, Calcif. Tissue Res.23:113–114, 1977
Peckauskas, R.A., Termine, J.D., Pullman, I: ESR investigation of the binding of acidic biopolymers to synthetic apatite, Biopolymers15:569–581, 1976
Termine, J.D.: Ph.D. thesis, Cornell University, Ithaca, N.Y., 1966
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Lamson, S.H., Harper, R.A. & Katz, J.L. Ion migration energies and color center absorption in hydroxyapatite. Calcif Tissue Int 30, 21–25 (1980). https://doi.org/10.1007/BF02408602
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DOI: https://doi.org/10.1007/BF02408602