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Mineralogical characterization of calcification in cardiovascular aortic atherosclerotic plaque: A case study

  • Yan Li (a1), Xin Wang (a1), Meiqian Zhu (a1), Chong-Qing Yang (a2), Anhuai Lu (a1), Kang Li (a3), Fanlu Meng (a1) and Changqiu Wang (a1)...


Calcification in cardiovascular aortic atherosclerotic plaque contains Ca-phosphate minerals. However, most research on cardiovascular calcification has focused on its physiological properties rather than its mineralogical features. In this present study, cardiovascular calcification was characterized by collecting samples from patients’ tissues and applying mineralogical techniques. Synchrotron radiation-based micro-X-ray diffraction showed the calcification had a similar structure to hydroxylapatite (HAp). Transmission electron microscopy showed some structurally HAp-like spherical particles with a diameter of ∼200 nm and acicular crystals ∼100 nm × ∼20 nm in size. Selected-area electron diffraction indicated that these mineral particles belonged to the hexagonal crystal system. Fourier-transform infrared (FTIR) spectroscopy showed three typical peaks at 1469 cm−1, 1455 cm−1 and 1413 cm−1, indicating that the carbonate group in the calcification plaque substituted for a hydroxyl group to form B-type CHAp (Ca10(PO4,CO3) x (OH) y ). The FTIR mapping results illustrated the intergrowth of calcification and organic tissues and the inhomogeneous substitution of phosphate by carbonate in the calcification area. X-ray absorption near-edge structure analysis affirmed that the chemical environments of Ca in the calcification were close to those in HAp. Based on these mineralogical characteristics, the calcification in plaque is identified as a mixture phase of HAp and B-type carbonate HAp, which is similar to the composition of bones.


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§ The first two authors contributed equally to this work.


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Abedin, M., Tintut, Y. and Demer, L.L. (2004) Vascular calcification – mechanisms and clinical ramifications. Arteriosclerosis Thrombosis and Vascular Biology, 24, 11611170.
Avwioro, G. (2011) Histochemical uses of haematoxylin – a review. Journal of Pharmacy and Clinical Sciences, 1, 2434.
Barinov, S., Rau, J., Cesaro, S., Ďurišin, J., Fadeeva, I., Ferro, D., Medvecky, L. and Trionfetti, G. (2006) Carbonate release from carbonated hydroxyapatite in the wide temperature rage. Journal of Materials Science: Materials in Medicine, 17, 597604.
Barralet, J., Best, S. and Bonfield, W. (1998) Carbonate substitution in precipitated hydroxyapatite: An investigation into the effects of reaction temperature and bicarbonate ion concentration. Journal of Biomedical Materials Research, 41, 7986.
Bild, D.E., Detrano, R., Peterson, D., Guerci, A., Liu, K., Shahar, E., Ouyang, P., Jackson, S. and Saad, M.F. (2005) Ethnic differences in coronary calcification – the multiethnic study of atherosclerosis (mesa). Circulation, 111, 13131320.
Bobryshev, Y.V. (2005) Calcification of elastic fibers in human atherosclerotic plaque. Atherosclerosis, 180, 293303.
Boström, K. (2005) Proinflammatory vascular calcification. Circulation Research, 96, 12191220.
Boström, K., Watson, K.E., Horn, S., Wortham, C., Herman, I.M. and Demer, L.L. (1993). Bone morphogenetic protein expression in human atherosclerotic lesions. Journal of Clinical Investigation, 91(4), 18001809.
Brown, W.E., Eidelman, N. and Tomazic, B. (1987) Octacalcium phosphate as a precursor in biomineral formation. Advances in Dental Research, 1, 306313.
Camacho, N.P., West, P., Torzilli, P.A. and Mendelsohn, R. (2001) FTIR microscopic imaging of collagen and proteoglycan in bovine cartilage. Biopolymers, 62, 18.
Carpentier, X., Bazin, D., Jungers, P., Reguer, S., Thiaudiere, D. and Daudon, M. (2010) The pathogenesis of Randall’s plaque: a papilla cartography of Ca compounds through an ex vivo investigation based on XANES spectroscopy. Synchrotron Radiation, 17, 374379.
Chaboy, J. and Quartieri, S. (1995) X-ray absorption at the Ca K-edge in natural-garnet solid solutions: A full-multiple-scattering investigation. Physical Review B, 52, 63496357.
Dekker, R.J., de Bruijn, J.D., Stigter, M., Barrere, F., Layrolle, P. and van Blitterswijk, C.A. (2005) Bone tissue engineering on amorphous carbonated apatite and crystalline octacalcium phosphate-coated titanium discs. Biomaterials, 26, 52315239.
Dhore, C.R., Cleutjens, J.P.M., Lutgens, E., Cleutjens, K.B.J.M., Geusens, P.P.M., Kistslaar, P.J.E.H.M., Tordoir, J.H.M., Spronk, H.M.H., Vermeer, C. and Daemen, M.J.A.P. (2001) Differential expression of bone matrix regulatory proteins in human atherosclerotic plaques. Arteriosclerosis, Thrombosis, and Vascular Biology, 21, 19982003.
Eichert, D., Salome, M., Banu, M., Susini, J. and Rey, C. (2005) Preliminary characterization of calcium chemical environment in apatitic and non-apatitic calcium phosphates of biological interest by X-ray absorption spectroscopy. Spectrochimica Acta Part B: Atomic Spectroscopy, 60, 850858.
Gibson, I.R. and Bonfield, W. (2002) Novel synthesis and characterization of an AB-type carbonatesubstituted hydroxyapatite. Journal of Biomedical Materials Research, 59, 697708.
Hamm, P., Lim, M.H. and Hochstrasser, R.M. (1998) Structure of the amide I band of peptides measured by femtosecond nonlinear-infrared spectroscopy. Journal of Physical Chemistry B, 102, 61236138.
Iyemere, V.P., Proudfoot, D., Weissberg, P.L. and Shanahan, C.M. (2006) Vascular smooth muscle cell phenotypic plasticity and the regulation of vascular calcification. Journal of Internal Medicine, 260, 192210.
Jackson, M., Choo, L.-Pi., Watson, P.H., Halliday, W.C. and Mantsch, H.H. (1995) Beware of connective tissue proteins: Assignment and implications of collagen absorptions in infrared spectra of human tissues. Biochimica et Biophysica Acta (BBA) - Molecular Basis of Disease, 1270, 16.
Jeziorska, M., McCollum, C. and Woolley, D.E. (1998) Calcification in atherosclerotic plaque of human carotid arteries: Associations with mast cells and macrophages. Journal of Pathology, 185, 1017.
Johnsson, M.S.A. and Nancollas, G.H. (1992) The role of brushite and octacalcium phosphate in apatite formation. Critical Reviews in Oral Biology & Medicine, 3, 6182.
Kips, J.G., Segers, P. and Van Bortel, L.M. (2008) Identifying the vulnerable plaque: A review of invasive and non-invasive imaging modalities. Artery Research, 2, 2134.
Landi, E., Celotti, G., Logroscino, G. and Tampieri, A. (2003) Carbonated hydroxyapatite as bone substitute. Journal of the European Ceramic Society, 23, 29312937.
LeGeros, R.Z., Daculsi, G., Orly, I., Abergas, T. and Torres, W. (1989). Solution-mediated transformation of octacalcium phosphate (OCP) to apatite. Scanning Microscopy, 3, 129137.
Milev, A., Kannangara, G.S.K. and Ben-Nissan, B. (2003) Morphological stability of hydroxyapatite precursor. Materials Letters, 57, 19601965.
Mohler, E.R. III, Gannon, F., Reynolds, C., Zimmerman, R., Keane, M.G. and Kaplan, F.S. (2001) Bone formation and inflammation in cardiac valves. Circulation, 103, 15221528.
Movasaghi, Z., Rehman, S. and Rehman, I. (2008) Fourier transform infrared (FTIR) spectroscopy of biological tissues. Applied Spectroscopy Reviews, 43, 134179.
Myneni, S.C., Traina, S.J., Waychunas, G.A. and Logan, T.J. (1998) Experimental and theoretical vibrational spectroscopic evaluation of arsenate coordination in aqueous solutions, solids, and at mineral-water interfaces. Geochimica et Cosmochimica Acta, 62(19), 32853300.
Neogi, T., Ellison, R.C., Hunt, S., Terkeltaub, R., Felson, D.T. and Zhang, Y. (2009) Serum uric acid is associated with carotid plaques: the National Heart, Lung, and Blood Institute Family Heart Study. The Journal of Rheumatology, 36(2), 378384.
Pham, P.H., Rao, D.S., Vasunilashorn, F., Fishbein, M.C. and Goldin, J.G. (2006) Computed tomography calcium quantification as a measure of atherosclerotic plaque morphology and stability. Investigative Radiology, 41, 674680.
Richardson, P.D., Davies, M.J. and Born, G.V.R. (1989) Influence of plaque configuration and stress-distribution on fissuring of coronary atherosclerotic plaques. The Lancet, 2, 941944.
Roggli, V.L., Pratt, P.C. and Brody, A.R. (1986) Asbestos content of lung tissue in asbestos associated diseases: a study of 110 cases. British Journal of Industrial Medicine, 43, 1828.
Sauer, G.R. and Wuthier, R.E. (1988) Fourier transform infrared characterization of mineral phases formed during induction of mineralization by collagenasereleased matrix vesicles in vitro. Journal of Biological Chemistry, 263, 1371813724.
Scatena, L.F., Brown, M.G. and Richmond, G.L. (2001) Water at hydrophobic surfaces: weak hydrogen bonding and strong orientation effects. Science, 292(5518), 908912.
Severinghaus, J.W. (1958) Oxyhemoglobin dissociation curve correction for temperature and pH variation in human blood. Journal of Applied Physiology, 12(3), 485–486.
Shah, P.K. (2003) Mechanisms of plaque vulnerability and rupture. Journal of the American College of Cardiology, 41, 15S22S.
Shioi, A., Mori, K., Jono, S., Wakikawa, T., Hiura, Y., Koyama, H., Okuno, Y., Nishizawa, Y. and Morii, H. (2000) Mechanism of atherosclerotic calcification. Zeitschrift für Kardiologie, 89, 7579.
Sofia, S., McCarthy, M.B., Gronowicz, G. and Kaplan, D.L. (2001) Functionalized silk-based biomaterials for bone formation. Journal of Biomedical Materials Research, 54, 139148.
Trommer, R.M., Santos, L.A. and Bergmann, C.P. (2009) Nanostructured hydroxyapatite powders produced by a flame-based technique. Materials Science and Engineering: C, 29, 17701775.
Wang, A.Y.M., Ho, S.S.Y., Wang, M., Liu, E.K.H., Ho, S., Li, P.K.T., Lui, S.F. and Sanderson, J.E. (2005) Cardiac valvular calcification as a marker of atherosclerosis and arterial calcification in end-stage renal disease. Archives of Internal Medicine, 165, 327332.
Xin, R.L., Leng, Y. and Wang, N. (2006) In situ TEM examinations of octacalcium phosphate to hydroxyapatite transformation. Journal of Crystal Growth, 289, 339344.



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