Abstract
Vibrational spectroscopies are extensively used for the characterization of calcium phosphates either as natural biological minerals (bone, teeth, ectopic calcifications) or as biomaterials (bioceramics, coatings, composites). The present review begins with a theoretical description of expected spectra for the main calcium phosphate phases (i.e., brushite, monetite, octacalcium phosphate, tricalcium phosphates, apatites, amorphous calcium phosphate) followed by the analysis of real spectra, line positions and assignments, and observed anomalies. In the second part, the spectra of complex well-crystallized ion-substituted apatites and other calcium phosphates, as well as solid solutions, are investigated, and the information gained regarding the substitution types and ion distributions are derived. Finally, we will examine and interpret the spectra of nanocrystalline apatites considering the ion substitution effects and the existence of a surface hydrated layer. Quantification processes and spectra treatments are briefly presented and discussed. Examples of the use of vibrational spectroscopies for biomaterials and biominerals characterization will be detailed for coating evaluations, including spectroscopic imaging, following up on mineral cement setting reactions, adsorption studies, near infrared investigations of surface water, residual strains determinations in bone, orientation of apatite crystals in biological tissues, and crystallinity and maturity of bone mineral.
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References
Bishop DM (1993) Group theory and chemistry. Dover Publications, New York
Ross SD (1972) Inorganic infrared and Raman spectra. McGraw-Hill, Maidenhead
Farmer VC (ed) (1974) The infrared spectra of minerals. Mineralogical Society, London
Santhyanarayana DN (2011) Vibrational spectroscopy. New Age International Publisher, New Delhi
Casciani F, Condrate RA Sr (1979) The vibrational spectra of brushite. CaHPO4 ·2H2O. Spectrosc Lett 12:699–713
White WB (1974) The carbonate minerals. In: Farmer VC (ed) The infrared spectra of minerals Mineralogical society monograph, 4th edn. Mineralogical Society, London
Elliott JC (1994) Structure and chemistry of the apatites and other calcium orthophosphates. Elsevier, Amsterdam
Bertoluzza A, Battaglia MA, Bonora S, Monyi P (1985) Hydrogen bonds in calcium acidic phosphates by infrared and Raman spectra. J Mol Struct 127:35–45
Trpkovska M, Soptrajanov B, Malkov P (1999) FTIR re-investigation of the spectra of synthetic brushite and its partially deuterated analogues. J Mol Struct 480–481:661–666
Posset U, Löcklin E, Thull R, Kiefer W (1998) Vibrational spectroscopic study of tetracalcium phosphate in pure polycrystalline form and as a constituent of a self-setting bone cement. Biomed Mater Res 40:640–645
Markovic M, Fowler BO, Tung MS (2004) Preparation and characterization of a comprehensive hydroxyapatite reference standard. J Res Natl Inst Stand Technol 109:553–568
Fowler BO, Moreno EC, Brown WE (1996) Infrared spectra of hydroxyapatite octacalcium phosphate and pyrolysed octacalcium phosphate. Arch Oral Biol 11:477–492
Jillavenkatesa A, Condrate RA Sr (1998) The infrared and Raman spectra of α- and β- tricalcium phosphate (Ca3(PO4)2). Spectrosc Lett 31:1619–1634
Fowler BO, Markovic M, Brown WE (1993) Octacalcium phosphate. 3. Infrared and Raman vibrational spectra. Chem Mater 5:1417–1423
Ulian G, Valdre G, Corno M, Ugliengo P (2013) The vibrational features of hydroxylapatite and type A carbonated apatite: a first principle contribution. Am Miner 98:752–759
Treboux G, Layrolle P, Kanzaki N, Onuma K, Ito A (2000) Symmetry of Posner’s cluster. J Am Chem Soc 122:8323–8324
Yin X, Stott J (2003) Biological calcium phosphates and Posner’s cluster. J Chem Phys 118:3717–3723
Petrov I, Soptrajanov B, Fuson N, Lawson JR (1967) Infrared investigation of dicalcium phosphates. Spectrochim Acta 23A:2636–2646
Penel G, Leroy G, van Landuyt P, Flautre B, Hardouin P, Lemaitre J, Leroy G (1999) Raman microspectrometry studies of brushite cement: in vivo evolution in a sheep model. Bone 25(suppl 2):81S–84S
Penel G, Leroy G, Rey C, Bres E (1998) Micro-Raman spectral study of the PO4 and CO3 vibrational modes in synthetic and biological apatites. Calcif Tissue Int 63:475–481
Walters MA, Leung YC, Blumenthal NC, LeGeros RZ, Konsker KA (1990) A Raman and infrared spectroscopic investigation of biological hydroxyapatite. J Inorg Biochem 39:193–200
Penel G, Leroy G, Rey C, Sombret B, Huvenne JP, Bres E (1997) Infrared and Raman microspectrometry study of fluor- fluor-hydroxy- and hydroxy-apatites powders. J Mater Sci Mater Med 8:271–276
Trombe JC (1973) Decomposition et réactivité d’apatites hydroxylées et carbonatée. Ann Chim Paris 8:251–269
Fowler BO (1973) Infrared studies of apatites. I. Vibrational assignments for calcium, strontium and barium hydroxyapatites utilizing isotopic substitution. Inorg Chem 13:94–207
Tsuda H, Arends J (1994) Orientation micro-Raman spectroscopy on hydroxyapatite single crystals and human enamel crystallites. J Dent Res 73:1703–1710
Herzberg G (1968) Molecular spectra and molecular structure. II Infrared and Raman spectra of polyatomic molecules. D. Van Nostrand Company, London
Rey C, Collins B, Goehl T, Glimcher MJ (1989) The carbonate environment in bone mineral. A resolution enhanced Fourier transform infrared spectroscopy study. Calcif Tissue Int 45:157–164
Kaupinnen JK, Moffatt DJ, Mantsch HH, Cameron DG (1981) Fourier self-deconvolution: a method for resolving intrinsically overlapped bands. Appl Spectrosc 35:271–276
Pleshko N, Boskey A, Mendelsohn R (1991) Novel infrared spectroscopic method for the determination of crystallinity of hydroxyapatite minerals. Biophys J 60:786–793
Galadeta SJ, Paschalis EP, Betts F, Mendelsohn R, Boskey AL (1996) Fourier transform infrared spectroscopy of the solution mediated conversion of amorphous calcium phosphate to hydroxyapatite: new correlations between X-ray diffraction and infrared data. Calcif Tissue Int 58:9–16
Morris MD, Drumm CA (1995) Microscopic Raman line–imaging with principal component analysis. Appl Spectrosc 49:1331–1337
Bigi A, Boanini E, Capuccini C, Gazzano M (2007) Strontium-substituted hydroxyapatite nanocrystals. Inorg Chim Acta 360:1009–1016
Hadrich A, Lautié A, Mhiri T (2001) Vibrational study and fluorescence bands in the FT-Raman spectra of Ca10−xPbx(PO4)6(OH)2 compounds. Spectrochim Acta Part A 57:1673–1681
de Mul FFM, Otto C, Greve J, Arends J, ten Bosch JJ (1998) Calculation of the Raman line broadening on carbonation in synthetic hydroxyapatite. J Raman Spectrosc 19:13–21
He Q, Liu X, Hu X, Li S, Wang H (2011) Solid solution between lead fluorapatite and lead fluorvanadate apatite: mixing behavior, Raman feature and thermal expansivity. Phys Chem Miner 38:741–752
Trombe JC, Montel G (1973) Sur le spectre d’absorption infrarouge des apatites dont les tunnels contiennent des ions bivalents et des lacunes. CR Acad Sci Paris 276:1271–1274
Barroug A, Rey C, Trombe JC (1994) Precipitation and formation mechanism of type AB carbonate apatite analogous to dental enamel. Adv Mater Res 1–2:147–153
Fleet ME, Liu X (2007) Coupled substitution of type A and B carbonate in sodium bearing apatites. Biomaterials 28:916–926
Legeros RZ, LeGeros JP (1996) Carbonate apatite: formation and properties. Bioceramics 9:161–164
Quillard S, Paris M, Deniard P, Gildenhaar R, Berger G, Obadia L, Bouler JM (2011) Structural and spectroscopic characterization of a series of potassium and/or sodium-substituted β-tricalcium phosphate. Acta Biomater 7:1844–1852
Eichert D, Drouet C, Sfihi H, Rey C, Combes C (2007) Nanocrystalline apatite-based biomaterials: synthesis, processing and characterization. In: Kendal JB (ed) Biomaterials research advances. Nova Science, New York, pp 93–143
Jäger C, Welzel T, Meyer-Zaika W, Epple M (2006) A solid-state NMR investigation of the structure of nanocrystalline hydroxyapatite. Magn Reson Chem 44:573–580
Eichert D, Combes C, Drouet C, Rey C (2005) Formation and evolution of hydrated surface layers of apatites. Key Eng Mater 284–286:3–6
Brown WE, Mathew M, Chow LC (1984) Roles of octacalcium phosphate in surface chemistry of apatites. In: Misra DN (ed) Adsorption and surface chemistry of hydroxyapatite. Plenum Press, New York, pp 13–28
Rey C, Combes C, Drouet C, Sfihi H, Barroug A (2007) Physico-chemical properties of nanocrystalline apatites: implications for biomaterials and biominerals. Mater Sci Eng C 27:198–205
Leeuwenburgh SCG, Wolke JGC, de Jansen JA, Groot K (2008) Calcium phosphate coatings. In: Kokubo T (ed) Bioceramics and their clinical applications. Woodhead Publishing Limited, Cambridge, pp 464–484
Sun L, Berndt CC, Gross KA, Kucuk A (2001) Material fundamentals and clinical performance of plasma sprayed hydroxyapatite coatings: a review. J Biomed Mater Res 58:570–592
Gross KA, Berndt C, Herman H (1998) Amorphous phase formation in plasma-sprayed hydroxyapatite coatings. J Biomed Mater Res Part A 39:407–414
Carayon M, Lacout J-L (2003) Study of the Ca/P atomic ratio of the amorphous phase in plasma-sprayed hydroxyapatite coatings. J Solid State Chem 172:339–350
Demnati I, Grossin D, Combes C, Rey C (2013) Plasma sprayed apatite coatings: review of physical-chemical aspects and their biological consequences. J Med Biol Eng 34:1–7. doi:10.5405/jmbe.1459
Yan L, Leng Y, Weng L-T (2003) Characterization of chemical inhomogeneity in plasma-sprayed hydroxyapatite coatings. Biomaterials 24:2585–2592
Podlesak H, Pawlowski L, d’Haese R, Laureyns J, Lampke T, Bellayer S (2010) Advanced microstructural study of suspension plasma sprayed hydroxyapatite coatings. J Therm Spray Technol 19:657–664
Weinlaender M, Beumer J, Kenney EB, Moy PK (1992) Raman microprobe investigation of the calcium phosphate phases of three commercially available plasma-flame-sprayed hydroxyapatite-coated dental implants. J Mater Sci Mater Med 3:397–401
Demnati I, Parco M, Grossin D, Fagoaga I, Drouet C, Barykin G, Combes C, Braceras I, Goncalves S, Rey C (2012) Hydroxyapatite coating on titanium by a low energy plasma spraying mini-gun. Surf Coat Technol 206:2342–2353
Demnati I (2011) Développement et caractérisation de revêtements bioactifs d’apatite obtenus par projection plasma à basse énergie: application aux implants biomédicaux. PhD thesis, Institut National Polytechnique de Toulouse
Tadier S (2009) Etude des propriétés physico-chimiques et biologiques de ciments biomédicaux à base de carbonate de calcium: apport du procédé de co-broyage. PhD thesis, Institut National Polytechnique de Toulouse
Tadier S, Le Bolay N, Rey C, Combes C (2011) Co-grinding significance for calcium carbonate-calcium phosphate mixed cement. Part I: effect of particle size and mixing on solid phase reactivity. Acta Biomater 7:1817–1826
Cummings LJ, Snyder MA, Brisack K (2009) Protein chromatography on hydroxyapatite columns. Methods Enzymol 463:387–404
Tamerler C, Sarikaya M (2009) Molecular biomimetics: nanotechnology and bionanotechnology using genetically engineered peptides. Philos Trans A Math Phys Eng Sci 367:1705–1726
Goldberg HA, Warner KJ, Hunter GK (2001) Binding of bone sialo-protein osteopontin and synthetic polypeptides to hydroxyapatite. Connect. Tissue Res 42:25–37
Al-Kattan A, Errassifi F, Sautereau AM, Sarda S, Dufour P, Barroug A, Dos Santos I, Combes C, Grossin D, Rey C, Drouet C (2010) Medical potentialities of biomimetic apatites through adsorption, ionic substitution, and mineral/organic associations: three illustrative examples. Adv Eng Mater 12:B224–B233
Juillard A, Falgayrac G, Cortet B, Vieillard MH, Azaroual N, Hornez JC, Penel G (2010) Molecular interactions between zoledronic acid and bone: an in vitro Raman microspectroscopic study. Bone 47:895–904
Cukrowski I, Popovic L, Barnard W, Paul SO, van Roovyen PH, Liles DC (2007) Modeling and spectroscopic studies of bisphosphonates-bone interactions. The Raman, NMR and crystallographic investigations of Ca-HEDP complexes. Bone 41:668–678
Xie HN, Stevenson R, Stone N, Hernandez-Santana A, Faulds K, Graham D (2012) Tracking bisphosphonates through a 20 mm thick porcine tissue by using surface-enhanced spatially offset Raman spectroscopy. Angew Chem Int Ed Engl 51:8509–8511
Rodan GA, Fleisch HA (1996) Bisphosphonates: mechanisms of action. J Clin Invest 97:2692–2696
Pascaud P, Gras P, Coppel Y, Rey C, Sarda S (2013) Interaction between a bisphosphonate, tiludronate, and biomimetic nanocrystalline apatites. Langmuir 29:2224–2232
Pascaud P (2012) Apatite nanocrystallines biomimétiques comme modèles de la réactivité osseuse: étude des propriétés d’adsorption et de l’activité cellulaire d’un bisphosphonate, le tiludronate. Thesis INPT, University of Toulouse
Burneau A, Barres O, Gallas JP, Lavalley JC (1990) Comparative study of the surface hydroxyl groups of fumed and precipitated silicas. 2 Characterization by infrared spectroscopy of the interactions with water. Langmuir 6:1364–1372
Bertinetti L, Drouet C, Combes C, Rey C, Tampieri A, Coluccia S, Martra G (2009) Surface characteristics of nanocrystalline apatites: effect of Mg surface enrichment on morphology, surface hydration species, and cationic environments. Langmuir 25:5647–5654
Takeuchi M, Bertinetti L, Martra G, Coluccia S, Anpo M (2009) States of H2O adsorbed on oxides: an investigation by near and mid infrared spectroscopy. Appl Catal A Gen 307:13–20
Ishikawa T, Wakamura M, Kondo S (1989) Surface characterization of calcium hydroxylapatite by Fourier transform infrared spectroscopy. Langmuir 5:140–144
Williams Q, Kettle E (1996) Infrared and Raman spectra of Ca5(PO4)6F2-fluorapatite at high pressures: compression-induced changes in phosphate site and Davydov splitting. J Phys Chem Solids 57:417–422
Xu J, Butler IS, Gilson DFR (1999) FT-Raman and high-pressure infrared spectroscopic studies of dicalcium phosphate dihydrate (CaHPO4 ·2H2O) and anhydrous dicalcium phosphate (CaHPO4). Spectrochem Acta Part A 55:2801–2809
Xu J, Gilson DFR, Butler IS, Stangel I (1996) Effect of high external pressures on the vibrational spectra of biomedical material: calcium hydroxyapatite and calcium fluorapatite. J Biomed Mater Res 30:239–244
de Carmejane O, Morris MD, Davis MK, Stixrude L, Tecklenburg M, Rajachar RM, Kohn DH (2005) Bone chemical structure response to mechanical stress studied by high pressure Raman spectroscopy. Calcif Tissue Int 76:207–213
Fleet ME, Liu X, Liu X (2011) Orientation of channel carbonate ions in apatite: effect of pressure and composition. Am Miner 96:1148–1157
Carden A, Rajachar RM, Morris MD, Kohn DH (2003) Ultrastructural changes accompanying the mechanical deformation of bone tissue: a Raman imaging study. Calcif Tissue Int 72:166–175
Timlin JA, Carden A, Morris MD (2000) Raman spectroscopic imaging markers for fatigue-related microdamage in bovine bone. Anal Chem 72:2229–2236
Tsuda H, Arends J (1997) Raman spectroscopy in dental Research: a short review of recent studies. Adv Dent Res 11:539–547
Falgayrac G, Facq S, Leroy G, Cortet B, Penel G (2010) New method for Raman investigation of the orientation of collagen fibrils and crystallites in the Haversian system of bone. Appl Spectrosc 64:775–780
Rey C, Combes C, Drouet C, Glimcher MJ (2009) Bone mineral: update on chemical composition and structure. Osteoporos Int 20:1013–1021
Bonar LC, Roufosse AH, Sabine WK, Grynpas MD, Glimcher MJ (1983) X-ray diffraction studies of the crystallinity of bone mineral in newly synthesized and density fractionated bone. Calcif Tissue Int 35:202–209
Farlay D, Panczer G, Rey C, Delmas PD, Boivin G (2010) Mineral maturity and crystallinity index are distinct characteristics of bone mineral. J Bone Miner Metab 28:433–445
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Rey, C., Marsan, O., Combes, C., Drouet, C., Grossin, D., Sarda, S. (2014). Characterization of Calcium Phosphates Using Vibrational Spectroscopies. In: Ben-Nissan, B. (eds) Advances in Calcium Phosphate Biomaterials. Springer Series in Biomaterials Science and Engineering, vol 2. Springer, Berlin, Heidelberg. https://doi.org/10.1007/978-3-642-53980-0_8
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