Top

Published in:

01-10-2003 | Laboratory Investigations

¹H MAS and ¹H → ³¹P CP/MAS NMR Study of Human Bone Mineral

Authors: A. Kaflak-Hachulska, A. Samoson, W. Kolodziejski

Published in: Calcified Tissue International | Issue 5/2003

Abstract

Chemical structure of human bone mineral was studied by solid-state nuclear magnetic resonance (NMR) with magic-angle spinning (MAS). Trabecular and cortical bone samples from adult subjects were compared with mineral standards: hydroxyapatite (HA), hydrated and calcined, carbonatoapatite of type B with 9 wt% of CO ₃ ²⁻ (CHA-B), brushite (BRU) and mixtures of HA with BRU. Proton spectra were acquired with excellent spectral resolution provided by ultra-high speed MAS at 40 kHz. 2D ¹H-³¹P NMR heteronuclear correlation was achieved by cross-polarization (CP) under fast MAS at 12 kHz. ³¹P NMR was applied with CP from protons under slow MAS at 1 kHz. Appearance of ³¹P rotational sidebands together with their CP kinetics were analyzed. It was suggested that the sidebands of CP spectra are particularly suitable for monitoring the state of apatite crystal surfaces. The bone samples appeared to be deficient in structural hydroxyl groups analogous to those in HA. We found no direct evidence that the HPO ₄ ²⁻ brushite-like ions are present in bone mineral. The latter problem is extensively discussed in the literature. The study proves there is a similarity between CHA-B and bone mineral expressed by their similar NMR behavior.

Fyfe, CA 1983Solid state NMR for chemists.CFC PressGuelph

Stejskal, EO, Memory, JD 1994High resolution NMR in the solid state. Fundamentals of CP/MAS.Oxford University PressOxford

Andrew, ER 1971The narrowing of NMR spectra of solids by high-speed specimen rotation and the resolution of chemical shift and spin multiplet structures of solids.Prog NMR Spectrosc8139CrossRef

Maricq, MM, Waugh, JS 1979NMR in rotating solids.J Chem Phys7033003316CrossRef

Samoson, A 2002Extended magic-angle spinning.Grant, DMHarris, RK eds. Encyclopedia of nuclear magnetic resonance, Vol. 9, Advances in NMR.J. Wiley & Sons, LtdNew York5964

Pines, A, Gibby, MG, Waugh, JS 1973Proton-enhanced NMR of dilute spins in solids.J Chem Phys59569590

Samoson, A, Tuherm, T, Past, J 2001Ramped-speed cross polarization MAS NMR.J Magn Reson149264267CrossRefPubMed

Mehring, M 1983Principles of high resolution NMR in solids.SpringerBerlin

Kolodziejski, W, Klinowski, J 2002Kinetics of cross-polarization in solid-state NMR. A guide for chemists.Chem Rev102613628CrossRefPubMed

10.

Aue, WP, Roufosse, AH, Glimcher, MJ, Griffin, RG 1984Solid-state phosphorus-31 nuclear magnetic resonance studies of synthetic solid phases of calcium phosphate: potential models of bone mineral.Biochemistry2361106114PubMed

11.

Roufosse, AH, Aue, WP, Roberts, JE, Glimcher, MJ, Grffin, RG 1984Investigation of the mineral phases of bone by solid-state phosphorus-31 magic angle sample spinning nuclear magnetic resonance.Biochemistry2361156120PubMed

12.

Dejong, WF 1926La substance minerale dans les os.Res Trav Chim45445448

13.

Sudarsanan, K, Young, RA 1969Significant precision in crystal structural details: Holly Springs hydroxyapatite.Acta Crystallogr B2515341543CrossRef

14.

Elliott, JC 1994Studies in inorganic chemistry 18. Structure and chemistry of the apatites and other calcium orthophosphates.ElsevierAmsterdam112117

15.

Yesinowski, JP, Eckert, H 1987Hydrogen environments in calcium phosphates: ¹H MAS NMR at high spinning speeds.J Am Chem Soc10962746282

16.

Rey, C, Miquel, JL, Facchini, L, Legrand, AP, Glimcher, MJ 1995Hydroxyl groups in bone mineral.Bone16583586CrossRefPubMed

17.

Kaflak-Hachulska, A, Zlotkowska, A, Kolodziejski, W 1999Infrared study of hydroxylic groups in human bone and bone components.Materials of Vth International Conference on Molecular Spectroscopy from Molecules to Molecular Biological Systems and Molecular Materials: Role of Molecular Interactions and Recognition.Wroclaw-Ladek ZdrójPoland

18.

Kolodziejski, W, Kaflak-Hachulska, A 1999Proton MAS NMR studies of human bone and bone components.Emsley, L eds. Materials of the Alpine Conference on Solid-State NMR.Chamonix-Mont BlancFrance

19.

Loong, C-K, Rey, C, Kuhn, LT, Combes, C, Wu, Y, Chen, S-H, Glimcher, MJ 2000Evidence of hydroxyl-ion deficiency in bone apatites: an inelastic neutron-scattering study.Bone26599602CrossRefPubMed

20.

LeGeros, RZ 1994Biological and synthetic apatites.Brown, PWConstanz, B eds. Hydroxyapatite and related materials.CRC PressBoca Raton328

21.

LeGeros, RZ 1967Crystallographic studies of the carbonate substitution in the apatite structure. Ph.D. thesis.New York UniversityNew York

22.

LeGeros, RZ 1981Apatites in biological systems.Prog Crystal Growth Charact4145CrossRef

23.

LeGeros, RZ 1991Monographs in oral science 15. Calcium phosphates in oral biology and medicine.S. KargerBasel

24.

Featherstone, JDB, Mayer, I, Driessens, FC, Verbeeck, RMH, Heijligers, HJM 1983Synthetic apatites containing Na, Mg and CO₃ and their comparison with tooth enamel mineral.Calcif Tissue Int35169171PubMed

25.

Kaflak-Hachulska, A, Chmielewski, D, Górecki, A, Kolodziejski, W 2001Phosphorus-31 CP/NMR study of bone mineral.Materials of the 2^nd Alpine Conference on Solid-State NMR.Chamonix-Mont BlancFrance

26.

Kolodziejski, W, Kaflak-Hachulska, A 2001Kinetics of the ¹H to ³¹P NMR cross-polarization in minerals.Materials of the ISMAR 2001 Conference.RhodesGreece

27.

Legros, R, Balmain, N, Bonel, G 1986Structure and composition of the mineral phase of periosteal bone.J Chem ResS89

28.

Aoki, H 1991Science and medical applications of hydroxyapatite.Takayama PressTokyo

29.

Driessens, FC 1980Probable phase composition of the mineral in bone.Z Naturforsch (C)35357362

30.

Emerson, WH, Fisher, EE 1962The infrared spectra of carbonate in calcified tissues.Arch Oral Biol7671683

31.

Elliott, JC 1965The interpretation of the infrared absorption spectra of some carbonate-containing apatites.Slack, MVFearnhead, RW eds. Tooth enamel.J. Wright & SonsBristol2022

32.

LeGeros, RZ, Trautz, OR, LeGeros, JP, Klein, E 1968Carbonate substitution in the apatitic structure.Bull Soc Chim Fr417121718

33.

LeGeros, RZ, Trautz, OR, Klein, E, LeGeros, JP 1969Two types of carbonate substitution in the apatite structure.Experientia2557PubMed

34.

Bonel, G 1972Contribution a l’étude de la carbonation des apatites.Ann Chim7127144

35.

Labarthe, J-C, Bonel, G, Montel, G 1973Sur la structure et les propriétés des apatites carbonatées de type B phospho-calciques.Ann Chim8289301

36.

Blitz, RM, Pellegrino, ED 1977The nature of bone carbonate.Clin Orthop129279292PubMed

37.

Santos, M, González-Diaz, PF 1977A model for B carbonate apatite.Inorg Chem1621312134

38.

Featherstone, JD, Pearson, S, LeGeros, RZ 1984An infrared method for quantification of carbonate in carbonated apatites.Caries Res186366PubMed

39.

Vignoles, M, Bonel, G, Holcomb, DW 1989Influence of preparation conditions on the composition of type B carbonated hydroxyapatites and on the localization of carbonate ions.Calcif Tissue Int45157164PubMed

40.

Rey, C, Collins, B, Goehl, T, Dickson, IR, Glimcher, MJ 1989The carbonate environment in bone mineral: a resolution-enhanced Fourier transform infrared spectroscopy study.Calcif Tissue Int45157164PubMed

41.

Rey, C, Renugopalakrishnan, V, Shimuzu, M, Collins, B, Glimcher, MJ 1991A resolution-enhanced Fourier transform infrared study of the environment of the CO₃ ion in the mineral phase of enamel during its formation find maturation.Calcif Tissue Int49259268PubMed

42.

Roufosse, AH, Landis, WJ, Sabine, WK, Glimcher, MJ 1979Identification of brushite in newly deposited bone mineral from embryonic chicks.J Ultrastruct Res68235255PubMed

43.

Roberts, JE, Bonar, LC, Griffin, RG, Glimcher, MJ 1992Characterization of the very young mineral phases of bone by solid state ³¹P magic angle spinning nuclear magnetic resonance and X-ray diffraction.Calcif Tissue Int504248PubMed

44.

Rey, C, Shimizu, M, Collins, B, Glimcher, MJ 1990Resolution-enhanced Fourier transform infrared spectroscopy study of the environment of phosphate ion in the early deposits of a solid phase of calcium phosphate in bone and enamel and their evolution with age: I. Investigations in the v ₄-PO ₄ ³⁻ domain.Calcif Tissue Int46384394PubMed

45.

Rey, C, Shimizu, M, Collins, B, Glimcher, MJ 1991Resolution-enhanced Fourier transform infrared spectroscopy study of the environment of phosphate ion in the early deposits of a solid phase of calcium phosphate in bone and enamel and their evolution with age: II. Investigations in the v ₃-PO ₄ ³⁻ domain.Calcif Tissue Int49383388PubMed

46.

Wu, Y, Glimcher, MJ, Rey, C, Ackerman, JL 1994A unique protonated phosphate group in bone mineral not present in synthetic calcium phosphates.J Mol Biol244423435CrossRefPubMed

47.

Lovenstam, H, Weiner, S 1989On biomineralization.Oxford University PressOxford

48.

Wu, LNY, Genge, BR, Dunkelberger, DG, LeGeros, RZ, Concannon, B, Wuthier, RE 1997Physicochemical characterization of the nucleation core of matrix vesicles.J Biol Chem27244044411PubMed

49.

Dawson, KL, Farnan, IE, Constantz, BR, Young, SW 1991Solid-state phosphorus-31 nuclear magnetic resonance differentiation of bone mineral and synthetic apatite used to fill bone defects.Invest Radiol26946950PubMed

50.

Kaflak, A, Chmielewski, D, Górecki, A, Kolodziejski, W 1998Kinetics of ¹H → ³¹P cross-polarization in human trabecular bone.Solid State NMR10191196CrossRef

51.

Rothwell, WP, Waugh, JS, Yesinowski, JP 1980High-resolution variable-temperature ³¹P NMR of solid calcium phosphates.J Am Chem Soc10226372643

52.

Ramanathan, C, Wu, Y, Pfleiderer, B, Lizak, MJ, Garrido, L, Ackerman, JL 1996ADRF-CP surface-coil spectroscopy of synthetic calcium phosphates and bone mineral.J Magn ResonA121127138

53.

Ramanathan, C, Ackerman, JL 1997ADRF differential cross polarization spectroscopy of synthetic calcium phosphates and bone mineral.J Magn Reson1272635CrossRefPubMed

54.

Wu, Y, Ackerman, JL, Kim, H-M, Rey, C, Barroug, A, Glimcher, MJ 2002Nuclear magnetic resonance spin-spin relaxation of the crystals of bone, dental enamel and synthetic hydroxyapatites.J Bone Miner Res17472480PubMed

55.

Santos, AR, Wind, RA, Bronnimann, CE 1994 ¹H CRAMPS and ¹H-³¹P HetCor experiments on bone, bone mineral, and model calcium phosphate phases.J Magn Reson B105183187CrossRefPubMed

56.

Slósarczyk, A, Stobierska, E, Paszkiewicz, Z, Gawlicki, M 1996Calcium phosphate materials prepared from precipitates with various Ca/P molar ratios.J Am Ceram Soc7925392544

57.

Merry, JC, Gibson, IR, Best, SM, Bonfield, W 1998Synthesis and characterization of carbonate hydroxyapatite.J Mater Sci Mater Med9779783CrossRef

58.

KaleidaGraph computer program, version 3.02 for Macintosh, Abelbeck Software

59.

Vega, AJ 1988Heteronuclear chemical-shift correlations of silanol groups studied by two-dimensional cross-polarization/magic angle spinning NMR.J Am Chem Soc11010491054

60.

Kolodziejski, W, Rocha, J, He, H, Klinowski, J 1991High resolution solid state ¹H nuclear magnetic resonance spectra of organic template in hydrated aluminophoshate VPI-5.Appl Catal77L1L8CrossRef

61.

Curry, NA, Jones, DW 1971Crystal structure of brushite, calcium hydrogen ortophosphate dihydrate: a neutron-diffraction investigation.J Chem Soc A: Inorg Phys Theor3725–3729

62.

Schick, F 1996Bone marrow NMR in vivo.Prog NMR Spectrosc29169227CrossRef

63.

Miquel, JL, Facchini, L, Legrand, AP, Marchandise, X, Lecouffe, P, Chanavaz, M, Rey, C, Lemaitre, J 1990Characterisation and conversion study into natural living bone of calcium phosphate bioceramics by solid state NMR spectroscopy.Clin Mater5115125

64.

Miquel, JL, Facchini, L, Legrand, AP, Rey, C, Lemaitre, J 1990Solid state NMR to study calcium phosphate ceramics.Colloids Surfaces45427433CrossRef

65.

Kaflak-Hachulska, A, Kolodziejski, W 1999Preliminary results on IR microscopy of human bone.J Molec Struct511-512217221CrossRef

66.

Kaflak-Hachulska, A, Slósarczyk, A, Kolodziejski, W 2000Kinetics of NMR cross-polarization from protons to phosphorus-31 in natural brushite Solid State.NMR15237238CrossRef

Title: 1H MAS and 1H → 31P CP/MAS NMR Study of Human Bone Mineral
Authors: A. Kaflak-Hachulska
A. Samoson
W. Kolodziejski
Publication date: 01-10-2003
Publisher: Springer-Verlag
Published in: Calcified Tissue International / Issue 5/2003
Print ISSN: 0171-967X
Electronic ISSN: 1432-0827
DOI: https://doi.org/10.1007/s00223-002-2111-5

ACC 2024 Congress Coverage

Heart Failure Video

At a glance: The ONWARDS insulin icodec trials

Springer Medicine

¹H MAS and ¹H → ³¹P CP/MAS NMR Study of Human Bone Mineral

Abstract

ACC 2024 Congress Coverage

Year in Review: Heart failure and cardiomyopathies

Semaglutide benefits people with type 2 diabetes and obesity-related heart failure

Incentivised to exercise

New intervention for STEMI-related cardiogenic shock

» View more highlights on the ACC 2024 congress hub page

At a glance: The ONWARDS insulin icodec trials

Springer Medicine

Abstract

Please log in to get access to this content

Other articles of this Issue 5/2003

FGF-2 Regulates Enamel and Dentine Formation in Mouse Tooth Germ

Semiquantitative mRNA Measurements of Osteoinductive Growth Factors in Human Iliac-Crest Bone: Expression of LMP Splice Variants in Human Bone

The Interaction Between Sillence Type and BMD in Osteogenesis Imperfecta

A Poly Adenosine Repeat in the Human Vitamin D Receptor Gene is Associated with Bone Mineral Density in Young Swedish Women

The Small Bovine Amelogenin LRAP Fails to Rescue the Amelogenin Null Phenotype

The Influence of Fluoride Exposure on Dentin Mineralization Using an in Vitro Organ Culture Model

ACC 2024 Congress Coverage

Year in Review: Heart failure and cardiomyopathies

Semaglutide benefits people with type 2 diabetes and obesity-related heart failure

Incentivised to exercise

New intervention for STEMI-related cardiogenic shock

» View more highlights on the ACC 2024 congress hub page