OALibJ  Vol.6 No.6 , June 2019
The Role of Mg2 and BSA Langmuir Monolayers in Controlling Polymorph and Morphology of CaCO3 Crystal
Abstract: Mg2 and bovine serum albumin (BSA) Langmuir monolayers were used as effective crystal nucleation, growth modifiers and template to control the crystallization of CaCO3. Scanning electron microscopy (SEM), and X-ray diffraction (XRD) were used to characterize the polymorph and morphology of crystals obtained at different experimental conditions, respectively. The results indicated that various morphologies such as abacus-bead-like particles, spherical-shaped particles, wood block-like particles, pignut-shell-like particles and the rolling pole shaped particles have been formed at the interface of air-solution. The polymorph of calcium carbonate obtained undergo an evolvement from calcite to vaterite and aragonite with increasing of the molar ratio of Mg2 to Ca2 , which indicated that the ability of Mg2 to induce the formation of aragonite was enhanced as the molar ratio of Mg2 to Ca2 increased. When the molar ratio reached 3, the samples obtained were all aragonite phase of calcium carbonate, which suggests that the presence of Mg2 of subphase solutions was helpful for the formation of aragonite phase in the systems of Mg2 -BSA Langmuir monolayers. The possible formation mechanisms of CaCO3 in different systems were discussed in the paper.
Cite this paper: Xue, Z. and Xue, N. (2019) The Role of Mg2 and BSA Langmuir Monolayers in Controlling Polymorph and Morphology of CaCO3 Crystal. Open Access Library Journal, 6, 1-8. doi: 10.4236/oalib.1105389.

[1]   Donners, J.J.J., Nolte, R.J.M. and Sommerdijk, N.A.J.M. (2002) A Shape-Persistent Polymeric Crystallization Template for CaCO3. Journal of the American Chemical Society, 124, 9700-9701.

[2]   Fu, G., Valiyaveettil, S., Wopenka, B. and Morse, D.E. (2005) CaCO3 Biomineralization: Acidic 8-kDa Proteins Isolated from Aragonitic Abalone Shell Nacre Can Specifically Modify Calcite Crystal Morphology. Biomacromolecules, 6, 1289-1298.

[3]   Liang, P., Shen, Q., Zhao, Y., Zhou, Y., Wei, H., Lieberwirth, I., Huang, Y., Wang, D. and Xu, D. (2004) Petunia-Shaped Superstructures of CaCO3 Aggregates Modulated by Modified Chitosan. Langmuir, 20, 10444-10448.

[4]   Macaskie, L.E., Yong, P., Paterson-Beedle, M., Thackray, A.C., Marquis, P.M., Sammons, R.L., Nott, K.P. and Hall, L.D. (2005) A Novel Non Line-of-Sight Method for Coating Hydroxyapatite onto the Surfaces of Support Materials by Biomineralization. Journal of Biotechnology, 118, 187-200.

[5]   Kokubo, T. (2005) Design of Bioactive Bone Substitutes Based on Biomineralization Process. Materials Science and Engineering: C, 25, 97-104.

[6]   Fan, Y.W., Duan, K. and Wang, R.Z. (2005) A Composite Coating by Electrolysis-Induced Collagen Self-Assembly and Calcium Phosphate Mineralization. Biomaterials, 26, 1623-1623.

[7]   Nancollas, G.H. and Wu, W. (2000) Biomineralization Mechanisms: A Kinetics and Interfacial Energy Approach. Journal of Crystal Growth, 211, 137-142.

[8]   Eiden-Abmann, S., Viertelhaus, M., Heib, A., Hoetzer, K.A. and Felsche, J. (2002) The Influence of Amino Acids on the Biomineralization of Hydroxyapatite in Gelatin. Journal of Inorganic Biochemistry, 91, 481-486.

[9]   Falini, G., Gazzano, M. and Ripamonti, A. (1996) Magnesium Calcite Crystallizatin from Water-Alcohol Mixtures. Chemical Communications, No. 9, 1037-1038.

[10]   Xie, A.J., Yuan, Z.W. and Shen, Y.H. (2005) Biomimetic Morphogenesis of Calcium Carbonate in the Presence of a New Amino-Carboxyl-Chelating-Agent. Journal of Crystal Growth, 276, 265-274.

[11]   Loste, E., Wilson, R.M., Seshadri, R. and Meldrum, F.C. (2003) The Role of Magnesium in Stabilising Amor-phous Calcium Carbonate and Controlling Calcite Morphologies. Journal of Crystal Growth, 254, 206-218.

[12]   Han, Y.J. and Aizen-berg, J. (2003) Effect of Magnesium Ions on Oriented Growth of Calcite on Carboxylic Acid Functionalized Self-Assembled Monolayer. Journal of the American Chemical Society, 125, 4032-4033.

[13]   Han, Y.J. and Aizenberg, J. (2003) Journal of the American Chemical Society, 3, 13.

[14]   Davis, K.J., Dove, P.M. and De Yoreo, J.J. (2000) The Role of Mg2+ as an Impurity in Calcite Growth. Science, 290, 1134-1137.

[15]   Wada, N., Yamashita, K. and Umegaki, T. (1999) Effects of Carboxylic Acids on Calcite Formation in the Presence of Mg2+ Ions. Journal of Colloid and Interface Science, 212, 357-364.

[16]   Jiao, Y.F., Feng, Q.L. and Li, X.M. (2006) The Co-Effect of Collagen and Magnesium Ions on Calcium Carbonate Biomineralization. Materials Science and Engineering: C, 26, 648-652.

[17]   Xie, A.J., Shen, Y.H., Li, X.Y., Yuan, Z.W., Qiu, L.G., Zhang, C.Y. and Yang, Y.F. (2007) The Role of Mg2+ and Mg2+/Amino Acid in Controlling Polymorph and Morphology of Calcium Carbonate Crystal. Materials Chemistry and Physics, 101, 87-92.

[18]   Zhu, L.Y., Zhao, Q.R., Zheng, X.W. and Xie, Y.J. (2006) Formation of Star-Shaped Calcite Crystals with Mg2+ Inorganic Mineralizer without Organic Template. Journal of Solid State Chemistry, 179, 1247-1252.

[19]   Tong, H., Ma, W.T., Wang, L.L., Wan, P., Hu, J.M. and Cao, L.X. (2004) Control over the Crystal Phase, Shape, Size and Aggregation of Calcium Carbonate via a L-Aspartic Acid Inducing Process. Biomaterials, 25, 3923-3929.

[20]   Falini, G., Albeck, S., Weiner, S. and Addadi, L. (1996) Control of Aragonite or Calcite Polymorphism by Mollusk Shell Macromolecules. Science, 271, 67-69.

[21]   Falini, G., Gazzano, M. and Ripamonti, A. (1994) Crystallization of Calcium Carbonate in Presence of Magnesium and Polyelectrolytes. Journal of Crystal Growth, 137, 577-584.

[22]   Sugawara, A. and Kato, T. (2000) Aragonite CaCO3 Thin-Film Formation by Cooperation of Mg2+ and Organic Polymer Matrices. Chemical Communications, No. 6, 487-488.

[23]   Meldruma, F.C. and Hyde, S.T. (2001) Morphological Influence of Magnesium and Organic Additives on the Precipitation of Calcite. Journal of Crystal Growth, 231, 544-558.

[24]   Kitano, Y. (1962) The Be-havior of Various Inorganic Ions in the Separation of Calcium Carbonate from a Bicar-bonate Solution. Bulletin of the Chemical Society of Japan, 35, 1973.

[25]   Noyes, R.M. (1962) Thermodynamics of Ion Hydration as a Measure of Effective Dielectric Properties of Water. Journal of the American Chemical Society, 84, 513-522.

[26]   McCanley, J.W. and Roy, R. (1974) Controlled Nucleation and Crystal Growth of Various CaCO3 Phases by the Silica Gel Technique. American Mineralogist, 59, 947-963.

[27]   Yu, J.G., Tang, H., Cheng, B. and Zhao, X.J. (2004) Morphological Control of Calcium Oxalate Particles in the Presence of Poly-(Styrene-Alt-Maleic Acid). Journal of Solid State Chemistry, 177, 3368-3374.

[28]   Zhang, D.B., Qi, L.M., Ma, J.M. and Cheng, H.M. (2002) Morphological Control of Calcium Oxalate Dihydrate by a Double-Hydrophilic Block Copolymer. Chemistry of Materials, 14, 2450-2457.

[29]   Fernandez-Diaz, L., Putnis, A., Prieto, M. and Putnis, C.V. (1996) The Role of Magnesium in the Crystallization of Calcite and Aragonite in a Porous Medium. Journal of Sedimentary Research, 66, 482-491.

[30]   Raz, S., Hamilton, P.C., Wilt, F.H., Weiner, S. and Addadi, L. (2003) The Transient Phase of Amorphous Calcium Carbonate in Sea Urchin Larval Spicules: The Involvement of Proteins and Magnesium Ions in Its Formation and Stabilization. Advanced Functional Materials, 13, 480-486.