Fourier transform infrared spectroscopic study of the carbonate ions in bone mineral during aging

SummaryThe environment of CO32− ions in the bone mineral of chickens of different ages and in bone fractions of different density have been investigated by resolution-enhanced Fourier Transform Infrared (FTIR) Spectroscopy. Three carbonate bands appear in thev2 CO3 domain at 878, 871, and 866 cm−1, which may be assigned to three different locations of the ion in the mineral: in monovalent anionic sites of the apatitic structure (878 cm−1), in trivalent anionic sites (871 cm−1), and in unstable location (866 cm−1) probably in perturbed regions of the crystals. The distribution of the carbonate ions among these locations was estimated by comparing the intensities of the corresponding FTIR spectral bands. The intensity ratio of the 878 and 871 cm−1 bands remains remarkably constant in whole bone as well as in the fractions obtained by density centrifugation. On the contrary, the intensity ratio of the 866 cm−1 to the 871 cm−1 band was found to vary directly and decreased with the age of the animal. In bone of the same age, the relative content of the unstable carbonate ion was found to be highest in the most abundant density centrifugation fraction. A resolution factor of the CO32− band (CO3 RF) was calculated from the FTIR spectra which was shown to be very sensitive to the degree of crystallinity of the mineral. The crystallinity was found to improve rapidly with the age of the animal. The CO3 RF in the bone samples obtained by density centrifugation from bone of the same animal was found to be essentially constant. This indicates a fairly homogeneous, crystalline state of the mineral phase. A comparison of the maturation characteristics of synthetic carbonated apatites with bone mineral indicates that a simple, passive, physicochemical maturation process cannot explain the changes observed in the mineral phase of whole bone tissue or in the density centrifugation fractions of bone during aging and maturation.

[1]  W. H. Emerson,et al.  The infra-red absorption spectra of carbonate in calcified tissues , 1962 .

[2]  R. Heaney,et al.  Effect of Growth Hormone on Skeletal Mass in Adult Dogs , 1969, Nature.

[3]  V. Farmer The Infrared spectra of minerals , 1974 .

[4]  E. Eanes,et al.  Phosphoprotein modulation of apatite crystallization , 2006, Calcified Tissue International.

[5]  M. Glimcher,et al.  X-ray diffraction studies of the crystallinity of bone mineral in newly synthesized and density fractionated bone , 2006, Calcified Tissue International.

[6]  W. Neuman,et al.  Synthetic hydroxyapatite crystals , 1967, Calcified Tissue Research.

[7]  J. Burnell,et al.  Normal maturational changes in bone matrix, mineral, and crystal size in the rat , 2006, Calcified Tissue International.

[8]  W. Harris,et al.  Skeletal renewal and metabolic bone disease. , 1969, The New England journal of medicine.

[9]  M. Glimcher Recent studies of the mineral phase in bone and its possible linkage to the organic matrix by protein-bound phosphate bonds. , 1984, Philosophical transactions of the Royal Society of London. Series B, Biological sciences.

[10]  L. Rosenberg,et al.  Effect of proteoglycans on in vitro hydroxyapatite formation , 1979, Calcified Tissue International.

[11]  J. P. LeGeros,et al.  Two types of carbonate substitution in the apatite structure , 1969, Experientia.

[12]  M. Glimcher,et al.  Recent studies of bone mineral: Is the amorphous calcium phosphate theory valid? , 1981 .

[13]  G. Daculsi,et al.  In vitro Caries-like Lesion Formation in F-containing Tooth Enamel , 1983, Journal of dental research.

[14]  W. Armstrong,et al.  The hydroxyl content of calcified tissue mineral , 1971, Calcified Tissue Research.

[15]  J. Termine,et al.  Hydroxide and carbonate in rat bone mineral and its synthetic analogues , 2005, Calcified Tissue Research.

[16]  J. C. Elliott,et al.  The crystallographic structure of dental enamel and related apatites , 1964 .

[17]  A. Boskey,et al.  Mineral and matrix alterations in the bones of incisors-absent (ia/ia) osteopetrotic rats , 1985, Calcified Tissue International.

[18]  E. Pellegrino,et al.  Mineralization in the chick embryo , 1972, Calcified Tissue Research.

[19]  T. Y. Toribara,et al.  The Surface Chemistry of Bone. IX. Carbonate: Phosphate Exchange1 , 1956 .

[20]  M. Okazaki,et al.  Diffuse X-ray scattering from apatite crystals and its relation to amorphous bone mineral. , 1980, The Journal of Osaka University Dental School.

[21]  W. Neuman,et al.  in Surface , 2003 .

[22]  E. Pellegrino,et al.  The physical state of bone carbonate. A comparative infra-red study in several mineralized tissues. , 1966, The Yale journal of biology and medicine.

[23]  A. Boskey,et al.  The effect of osteocalcin onIn vitro lipid-induced hydroxyapatite formation and seeded hydroxyapatite growth , 2007, Calcified Tissue International.

[24]  M. Glimcher,et al.  Identification of brushite in newly deposited bone mineral from embryonic chicks. , 1979, Journal of ultrastructure research.

[25]  R. Legros,et al.  Structure and composition of the mineral phase of periosteal bone , 1986 .

[26]  P. Bodson,et al.  Le calcium échangeable de la substance minérale de l'os étudié à l'aide de 45Ca , 1955 .

[27]  E. Pellegrino,et al.  THE COMPOSITION OF HUMAN BONE IN UREMIA: Observations on the Reservoir Functions of Bone and Demonstration of a Labile Fraction of Bone Carbonate , 1965, Medicine.

[28]  A. S. Posner,et al.  Infra-Red Determination of the Percentage of Crystallinity in Apatitic Calcium Phosphates , 1966, Nature.

[29]  J. Lian,et al.  Non-apatitic environments in bone mineral: FT-IR detection, biological properties and changes in several disease states. , 1989, Connective tissue research.

[30]  J. Featherstone,et al.  An infrared method for quantification of carbonate in carbonated apatites. , 1984, Caries research.

[31]  A. S. Posner,et al.  Amorphous/crystalline interrelationships in bone mineral , 2005, Calcified Tissue Research.

[32]  M. Francis,et al.  Hydroxyapatite formation from a hydrated calcium monohydrogen phosphate precursor , 1970, Calcified Tissue Research.

[33]  D. W. Holcomb,et al.  Infrared determination of the degree of substitution of hydroxyl by carbonate ions in human dental enamel , 1985, Calcified Tissue International.

[34]  C. Rey,et al.  The carbonate environment in bone mineral: A resolution-enhanced fourier transform infrared spectroscopy study , 1989, Calcified Tissue International.

[35]  W. E. Brown,et al.  Crystal Growth of Bone Mineral , 1966, Clinical orthopaedics and related research.

[36]  Douglas J. Moffatt,et al.  Fourier Self-Deconvolution: A Method for Resolving Intrinsically Overlapped Bands , 1981 .

[37]  A. S. Posner,et al.  Effect of carbonate and biological macromolecules on formation and properties of hydroxyapatite , 1975, Calcified Tissue Research.

[38]  E. Pellegrino,et al.  Glutamine metabolism in bone. , 1983, Mineral and electrolyte metabolism.