The functionalization of titanium with EDTA to induce biomimetic mineralization of hydroxyapatite

Abstract

A new process is developed to functionalize an inorganic substrate with an organic polycarboxylic chelating agent to obtain a biomimetic template for mimicking biomineralization for the synthesis of films or coatings. A titanium plate is first placed in ethylenediaminetetracetic acid (EDTA) solution to effect chemisorption and self-assembly of EDTA molecules on the plate. The plate is then aged in supersaturated hydroxyapatite [(Ca₁₀(PO₄)₆(OH)₂, HA] solution to mimic biomineralization. The functionalization process is found to be very effective in creating a surface with an organized arrangement of carboxylate ions (–COO^–) with the orientation of lone pairs of electrons on O perpendicular to or radiating from the substrate surface. The coating is formed through the plate-like outgrowth of HA grains along the [001] direction under the mediation of the functionalized surface, giving rise to the coexistence of two kinds of microstructural patterns in coating. One is a parallel arrangement of the plate-like HA grains with (001) planes preferably parallel to the substrate surface, the other is a radial arrangement of the plate-like HA grains with the [001] direction radiating from one surface core and the (111) planes preferably parallel to the surface. The mineralization mechanism is discussed on the basis of the conformation of the self-assembled EDTA molecules and the interfacial molecular recognition, analogous to the biomineralization, including electrostatic interactions, hydrogen bonding, stereochemical arrangement and geometrical correspondence.

References

1. F. J. Fendler and F. C. Meldrum, Adv. Mater., 1995, 7, 607.
2. B. C. Bunker, P. C. Rieke, B. J. Tarasevich, A. H. Campbell, G. E. Fryxell, G. L. Graft, L. Song, J. Liu, J. W. Virden and G. L. McLay, Science, 1994, 264, 48.
3. Q. Huo, H. I. Margolese and G. D. Stucky, Chem. Mater., 1996, 8, 1147.
4. S. Mann and G. A. Ozin, Nature, 1996, 382, 313.
5. S. Weiner, CRC Crit. Rev. Biochem., 1986, 20, 365.
6. S. Mann, J. Mater. Chem., 1995, 5, 935.
7. S. Mann, Nature, 1988, 322, 119.
8. H. B. Lu, C. L. Ma, H. Cui, L. F. Zhou, R. Z. Wang and F. Z. Cui, J. Cryst. Growth, 1995, 155, 120.
9. A. A. Campbell, G. E. Fryxell, J. C. Linehan and G. L. Graff, J. Biomed. Mater. Res., 1996, 32, 111.
10. C. Ohtsuki, H. Iida, S. Hayakawa and A. Osaka, J. Biomed. Mater. Res., 1997, 35, 39.
11. H. B. Wen, J. B. de Wijn, Q. Liu, F. Z. Cui and K. de Groot, J. Mater. Sci. Mater. Med., 1997, 8, 765.
12. R. Pribil, Analytical Application of EDTA and Related Compounds, Pergamon Press, Oxford, 1972, pp. 1–50.
13. M. A. Blesa, E. B. Borghi, A. J. G. Maroto and A. E. Regazzoni, J. Colloid Interface Sci., 1984, 98, 295.
14. E. H. Rueda, R. L. Grassi and M. A. Blesa, J. Colloid Interface Sci., 1985, 106, 243.
15. H. C. Chang and E. Matijevic, J. Colloid Interface Sci., 1983, 92, 479.
16. J. Rubi and E. Matijevic, J. Colloid Interface Sci., 1979, 68, 408.
17. E. B. Borghi, A. E. Regazzoni, A. J. G. Maroto and M. A. Blesa, J. Colloid Interface Sci., 1989, 130, 299.
18. A. R. Browers and C. P. Huang, J. Colloid Interface Sci., 1986, 110, 575.
19. A. Ulman, Chem. Rev., 1996, 96, 1533 and references therein.
20. H. Shin, R. J. Collins, M. R. De Guire, A. H. Heuer and C. N. Sukenik, J. Mater. Res., 1995, 10, 692.
21. Y. T. Tao, J. Am. Chem. Soc., 1993, 115, 4350.
22. N. E. Schlotter, M. D. Porter, T. B. Bright and D. L. Allara, Chem. Phys. Lett., 1986, 132, 93.
23. H. Ogawa, T. Chihara and K. Taya, J. Am. Chem. Soc., 1985, 107, 1365.
24. Y. T. Tao, M. F. Lee and S. C. Chang, J. Am. Chem. Soc., 1993, 115, 9547.
25. M. T. Glimcher, Parodontologie, 1967, 1, 55.
26. M. J. Glimcher and S. M. Krane, Treatise Collagen, 1965, 2, 67.
27. M. J. Glimcher, Annu. Symp. Soc. Gen. Physiol., 1959, 6, 53.
28. M. J. Glimcher, U. A. Friberg, S. Orloff and J. Gross, J. Ultrastruct. Res., 1966, 15, 74.
29. M. J. Glimcher, B. Lefteriou and D. Kossiva, Calcif. Tissue. Int., 1979, 28, 83.
30. M. J. Glimcher, J. Bone Miner. Res., 1986, 1, 509.
31. M. J. Glimcher, D. Kossiva and D. Brickley-Parsons, J. Biol. Chem., 1984, 259, 290.
32. F. Vigliuni and F. Maroti, Clin. Ortoped., 1963, 15, 521.
33. M. Mori, M. Ito and S. Fukui, Histochemie, 1965, 5, 521.
34. D. Chapman, J. Chem. Soc., 1955, 1766.
35. R. E. Sievers and J. C. Bailar Jr., Inorg. Chem., 1962, 1, 174.
36. D. H. Bush and J. C. Bailar Jr., J. Am. Chem. Soc., 1953, 75, 4574.
37. D. H. Bush and J. C. Bailar Jr., J. Am. Chem. Soc., 1956, 78, 716.
38. K. Nakamoto, Infrared and Raman Spectra of Inorganic and Coordination Compounds, Wiley & Sons, New York, 1986, 4th edn.
39. R. G. Greenler, J. Chem. Phys., 1966, 44, 310.
40. J. Umemura, T. Kamata, T. Kawai and T. Takenaka, J. Phys. Chem., 1990, 94, 62.
41. S. Anderson, E. C. Constable, M. P. Dare-Edwards, J. B. Goodenough, A. Hamnett, K. R. Seddon and R. D. Wright, Nature, 1979, 280, 571.
42. D. L. Parfit, G. D. Russell and V. C. Farmer, J. Chem. Soc., Faraday Trans. 1, 1976, 72, 1082.
43. R. L. Parfitt, G. D. Russell, A. R. Fraser and V. C. Farmer, Nature, 1974, 248, 220.
44. A. D. Buckland, C. H. Rochester and S. A. Topham, J. Chem. Soc., Faraday Trans. 1, 1980, 76, 302.
45. V. E. Henrich and P. A. Cox, The surface science of metal oxides, Cambridge University Press, Cambridge, 1994, pp. 280–283, 332–333.
46. H. P. Boehm, Discuss. Faraday Soc., 1971, 52, 264.
47. I. Nakagawa and T. Shimanouchi, Spectrochim. Acta, 1964, 20, 429.
48. M. Tsuboi, T. Onishi, I. Nakagawa, T. Shimanouchi and S. Mizuschima, Spectrochim. Acta, 1958, 12, 253.
49. R. A. Condrate and K. Nakamoto, J. Chem. Phys., 1965, 42, 2590.
50. M. Mikami, I. Nakagawa and T. Shimanouchi, Spectrochim. Acta, 1967, 23, 1037.
51. C. D. Wagner, W. M. Riggs, L. E. Davies, J. F. Moulder and G. E. Muilenberg, Handbook of X-ray photoelectron spectroscopy, Perkin-Elmer Corporation, Eden Prairie, MN, 1979, pp. 58–70.
52. C. N. Sayer and N. R. Armstrong, Surf. Sci., 1978, 77, 301.
53. E. Bertel, R. Stockbauer and T. E. Mady, Surf. Sci., 1984, 141, 355.
54. D. E. Eastman, Solid State Commun., 1972, 10, 933.
55. K. I. Hadjiivanov and D. G. Klissurski, Chem. Soc. Rev., 1996, 25, 61.
56. T. Hanawa, M. Kon, H. Ukai, K. Murakami, Y. Miyamoto and K. Asaska, J. Biomed. Mater. Res., 1997, 34, 273.
57. G. Beamson and D. Briggs, High Resolution XPS of Organic Polymers, the Scienta ESCA300 Database, John Wiley & Sons, New York, 1992, pp. 66, 116.
58. G. M. Whitesides, J. P. Mathias and C. T. Seto, Science, 1991, 254, 1312.
59. R. J. Fessenden and J. S. Fessenden, Organic Chemistry, Brooko/Cole Publishing Company, California, 1986, 5th edn., pp. 64–65, 584–585.
60. J. A. Dean, Lange's Handbook of Chemistry, Mc-Graw-Hill Book Company, New York, 14th edn, 1992.
61. Th. Zeegers-Huyskens and P. Huyskens, Intermolecular forces, in Intermolecular forces, an Introduction to Modern Methods and Results, ed. P. L. Huyskens, W. A. P. Luck and T. Zeegers-Huyskens, Springer-Verlag, Berlin, 1991, pp. 17–29.
62. C. B. Mao, H. D. Li, F. Z. Cui, Q. L. Feng, H. Wang and C. L. Ma, J. Mater. Chem., 1998, 8, 2795.
63. M. M. Walczac, C. Chung, S. M. Stole, C. A. Nidrig and M. D. Porter, J. Am. Chem. Soc., 1991, 113, 2370.
64. J. H. Keeler, W. R. Hibbard and B. F. Decker, Trans. AIME, 1953, 197, 932.
65. M. Kukura, L. C. Bell, A. M. Posner and J. P. Quirk, J. Phys. Chem., 1972, 76, 900.
66. M. Tanahashi and T. Matsuda, J. Biomed. Mater. Res., 1997, 34, 305.
67. A. S. Posner, F. Betts and N. C. Blumenthal, Prog. Cryst. Growth Charact., 1980, 3, 49.
68. T. Hanazawa, Inorganic Phosphate Materials, Elsevier, Amsterdam, 1989, pp. 24–29, 91–92.