Abstract
We have earlier shown that linear poly(ethylene imine) (LPEI) is an efficient growth modifier for calcium phosphate mineralization from aqueous solution (Shkilnyy et al., Langmuir, 2008, 24 (5), 2102). The current study addresses the growth process and the reason why LPEI is such an effective additive. To that end, the solution pH and the calcium and phosphate concentrations were monitored vs. reaction time using potentiometric, complexometric, and photometric methods. The phase transformations in the precipitates and particle morphogenesis were analyzed by X-ray diffraction and transmission electron microscopy, respectively. All measurements reveal steep decreases of the pH, calcium, and phosphate concentrations along with a rapid precipitation of brushite nanoparticles early on in the reaction. Brushite transforms into hydroxyapatite (HAP) within the first 2 h, which is much faster than what is reported, for example, for calcium phosphate precipitated with poly(acrylic acid). We propose that poly(ethylene imine) acts as a proton acceptor (weak buffer), which accelerates the transformation from brushite to HAP by taking up the protons that are released from the calcium phosphate precipitate during the phase transformation.
Similar content being viewed by others
References
Nancollas, G. H. Biological Mineralization and Demineralization; Springer, 1982.
Calcium Phosphates in Biological and Industrial Systems; Kluwer Academic Publishers: Norwell-Dordrecht, 1998.
Bohner M (2000) Injury 31:37
Schweizer S, Taubert A (2007) Macromol Biosci 7:1085
Bertoni E, Bigi A, Falini G, Panzavolta S, Roveri N (1999) J Mater Chem 9:779
Bigi A, Boanini E, Cojazzi G, Falini G, Panzavolta S (2001) Cryst Growth Des 1:239
Bigi A, Boanini E, Walsh D, Mann S (2002) Angew Chem Int Ed Engl 41:2163
Bigi A, Boanini E, Bracci B, Falini G, Rubini K (2003) J Inorg Biochem 95:291
Bigi A, Boanini E, Falini G, Panzavolta S, Roveri N (2000) J Inorg Biochem 78:227
Bigi A, Boanini E, Borghi M, Cojazzi G, Panzavolta S, Roveri N (1999) J Inorg Biochem 75:145
Boanini E, Torricelli P, Gazzano M, Giardino R, Bigi A (2006) Biomaterials 27:4428
Boanini E, Bigi A (2006) Thin Solid Films 497:53
Cölfen H, Antonietti M (1998) Langmuir 14:582
Cölfen H, Qi L (2000) Chem Eur J 7:106
Sedlak M, Cölfen H (2001) Macromol Chem Phys 202:587
Cölfen H (2001) Macromol Rapid Commun 22:587
Yu S-H, Cölfen H, Hartmann J, Antonietti M (2002) Adv Funct Mater 12:541
Cölfen H, Mann S (2003) Angew Chem Int Ed Engl 42:2350
Yu S-H, Cölfen H, Antonietti M (2003) J Phys Chem B 107:7396
Rudloff J, Cölfen H (2004) Langmuir 20:991
Peytcheva A, Cölfen H, Schnablegger H, Antonietti M (2002) Coll Polym Sci 280:218
Antonietti M, Breulmann M, Göltner CG, Cölfen H, Wong KKW, Walsh D, Mann S (1998) Chem Eur J 4:2493
Yu S-H, Cölfen H (2004) J Mater Chem 14:2124
Niederberger M, Cölfen H (2006) Phys Chem Chem Phys 8:3271
Xu A-W, Antonietti M, Cölfen H, Fang Y-P (2006) Adv Funct Mater 16:903
Wang T, Cölfen H, Antonietti M (2006) Chem Eur J 12:5722
Meldrum FC, Cölfen H (2008) Chem Rev 108:4332
Amjad Z (2005) Phosphorus Res Bull 18:7
Amjad Z (1997) Phosphorus Res Bull 7:45
Amjad Z (1989) Langmuir 5:1222
Amjad Z (2005) Phosphorus Res Bull 18:1
Amjad Z, Zuhl RW (2002) Phosphorus Res Bull 13:51
Tsortos A, Nancollas GH (2002) J Colloid Interface Sci 250:159
Tang R, Darragh M, Orme CA, Guan X, Hoyer JR, Nancollas GH (2005) Angew Chem Int Ed 44:3698
Tang R, Wang L, Orme CA, Bonstein T, Bush PJ, Nancollas GH (2004) Angew Chem Int Ed 43:2697
Burke EM, Guo Y, Colon L, Rhima M, Veis A, Nancollas GH (2000) Coll Surf B 17:49
Walsh D, Boanini E, Tanaka J, Mann S (2005) J Mater Chem 15:1043
Taubert, A.; Furrer, E.; Meier, W. Chem. Commun. 2004, 2170.
Perkin KK, Turner JL, Wooley KL, Mann S (2005) Nano Lett 5:1457
Casse O, Colombani O, Kita-Tokarczyk K, Müller AHE, Meier W, Taubert A (2008) Faraday Discuss 139:179
Ngankam PA, Lavalle P, Voegel JC, Szyk L, Decher G, Schaaf P, Cuisinier FJG (2000) J Am Chem Soc 122:8998
Ball V, Michel M, Boulmedais F, Hemmerle J, Haikel Y, Schaaf P, Voegel JC (2006) Cryst Growth Des 6:327
Michel M, Arntz Y, Fleith G, Toquant J, Haikel Y, Voegel J-C, Schaaf P, Ball V (2006) Langmuir 22:2358
Shkilnyy A, Brandt J, Mantion A, Paris O, Schlaad H, Taubert A (2009) Chem Mater 21:1572
Shkilnyy A, Friedrich A, Tiersch B, Schöne S, Fechner M, Koetz J, Schläpfer C-W, Taubert A (2008) Langmuir 24:2102
Shkilnyy A, Gräf R, Hiebl B, Neffe AT, Friedrich A, Hartmann J, Taubert A (2009) Macromol Biosci 9:179
Junginger M, Kita-Tokarczyk K, Schuster T, Reiche J, Schacher FA, Müller AHE, Cölfen H, Taubert A (2010) Macromol Biosci 10:1084
Junginger M, Bleek K, Kita-Tokarczyk K, Reiche J, Shkilnyy A, Schacher F, Müller AHE (2010) Taubert Nanoscale 2:2440
Van Veldhoven PP, Mannaerts GP (1987) Anal Biochem 161:45
Wang L, Nancollas GH (2009) Dalton Trans 15:2665
Wu W, Nancollas GH (1999) Sulfur and Silicon 144–146:125
Wang L, Nancollas GH (2008) Chem Rev 108:4628
Acknowledgment
We thank I. Zenke for the help with XRD, R. Pitschke, H. Runge, and Dr. L. Kind for their help with electron microscopy, and Dr. H. Schlaad for useful discussion. A.S. acknowledges the MPI of Colloids and Interfaces for a postdoctoral fellowship. We thank the MPI of Colloids and Interfaces (Colloid Chemistry Department), the Fonds der Chemischen Industrie, and the University of Potsdam for financial support.
Author information
Authors and Affiliations
Corresponding author
Electroni c supplementary material
ESM 1
(PDF 823 kb)
Rights and permissions
About this article
Cite this article
Shkilnyy, A., Schöne, S., Rumplasch, C. et al. Calcium phosphate mineralization with linear poly(ethylene imine): a time-resolved study. Colloid Polym Sci 289, 881–888 (2011). https://doi.org/10.1007/s00396-011-2403-2
Received:
Revised:
Accepted:
Published:
Issue Date:
DOI: https://doi.org/10.1007/s00396-011-2403-2