In Vitro Synthesis of High Mg Calcite under Ambient Conditions and Its Implication for Biomineralization Process

Instead of calcite or aragonite, thermodynamically unstable magnesium-bearing calcite occurs in many marine organisms such as sea urchin, sea star, corallina algae, and so on. However, the formation process of biogenic high-magnesium calcite has been an enigma. In this work, high-magnesium calcite in pure phase was synthesized in large yield via polymer-stabilized amorphous calcium magnesium carbonate (ACMC) precursors under mild conditions for the first time. The magnesium contents in Mg-bearing calcite can be exquisitely tuned from 15 to 40 mol % by changing the Mg/Ca ratio in mother solutions. We found appropriate polymer concentration windows for the synthesis of pure phase high Mg-calcite under defined crystallization conditions. It is proposed that the role of dextran sulfate sodium salt was to restrain the formation of aragonite, and the main role of poly(acrylic acid) was to stabilize ACMC. In this work, we designed a strategy to prepare thermodynamically unstable high Mg-calcite; that is, the pre...

[1]  Shuhong Yu,et al.  Confined crystallization of polycrystalline high-magnesium calcite from compact Mg-ACC precursor tablets and its biological implications , 2011 .

[2]  S. Weiner,et al.  Role of Magnesium Ion in the Stabilization of Biogenic Amorphous Calcium Carbonate: A Structure−Function Investigation , 2010 .

[3]  Xurong Xu,et al.  Magnesium-aspartate-based crystallization switch inspired from shell molt of crustacean , 2009, Proceedings of the National Academy of Sciences.

[4]  P. Dove,et al.  Carboxylated molecules regulate magnesium content of amorphous calcium carbonates during calcification , 2009, Proceedings of the National Academy of Sciences.

[5]  Z. Shao,et al.  Microspheres of Calcium Carbonate Composite Regulated by Sodium Polyacrylates with Various Ways , 2009 .

[6]  S. Weiner,et al.  The grinding tip of the sea urchin tooth exhibits exquisite control over calcite crystal orientation and Mg distribution , 2009, Proceedings of the National Academy of Sciences.

[7]  Helmut Cölfen,et al.  Stable Prenucleation Calcium Carbonate Clusters , 2008, Science.

[8]  L. Gower.  Biomimetic model systems for investigating the amorphous precursor pathway and its role in biomineralization. , 2008, Chemical reviews.

[9]  F. Meldrum,et al.  Controlling mineral morphologies and structures in biological and synthetic systems. , 2008, Chemical reviews.

[10]  P. Dove,et al.  Peptides Enhance Magnesium Signature in Calcite: Insights into Origins of Vital Effects , 2008, Science.

[11]  A. Freer,et al.  Biomineralization: elemental and organic influence in carbonate systems. , 2008, Chemical reviews.

[12]  N. Sommerdijk,et al.  Biomimetic CaCO3 mineralization using designer molecules and interfaces. , 2008, Chemical reviews.

[13]  S. Weiner,et al.  Amorphous calcium phosphate is a major component of the forming fin bones of zebrafish: Indications for an amorphous precursor phase , 2008, Proceedings of the National Academy of Sciences.

[14]  Sidney R. Cohen,et al.  Sea Urchin Tooth Design: An “All‐Calcite” Polycrystalline Reinforced Fiber Composite for Grinding Rocks , 2008 .

[15]  P. Dove,et al.  New insights into mechanisms of biomolecular control on growth of inorganic crystals , 2007 .

[16]  Xingguo Cheng,et al.  Biomimetic synthesis of calcite films by a polymer-induced liquid-precursor (PILP) process: 1. Influence and incorporation of magnesium , 2007 .

[17]  M. Epple,et al.  Monohydrocalcite and Its Relationship to Hydrated Amorphous Calcium Carbonate in Biominerals , 2007 .

[18]  S. Valiyaveettil,et al.  In vitro study of magnesium-calcite biomineralization in the skeletal materials of the seastar Pisaster giganteus. , 2007, Chemistry.

[19]  G. Mayer,et al.  Rigid Biological Systems as Models for Synthetic Composites , 2005, Science.

[20]  M. Antonietti,et al.  Amorphous layer around aragonite platelets in nacre. , 2005, Proceedings of the National Academy of Sciences of the United States of America.

[21]  S. Weiner,et al.  Sea Urchin Spine Calcite Forms via a Transient Amorphous Calcium Carbonate Phase , 2004, Science.

[22]  G. Wegner,et al.  Amorphous Calcium Carbonate: Synthesis and Potential Intermediate in Biomineralization , 2004 .

[23]  Steve Weiner,et al.  Taking Advantage of Disorder: Amorphous Calcium Carbonate and Its Roles in Biomineralization , 2003 .

[24]  S. Weiner,et al.  Mollusk Shell Acidic Proteins: In Search of Individual Functions , 2003, Chembiochem : a European journal of chemical biology.

[25]  S. Weiner,et al.  The Transient Phase of Amorphous Calcium Carbonate in Sea Urchin Larval Spicules: The Involvement of Proteins and Magnesium Ions in Its Formation and Stabilization , 2003 .

[26]  F. Meldrum,et al.  The role of magnesium in stabilising amorphous calcium carbonate and controlling calcite morphologies , 2003 .

[27]  J. Aizenberg,et al.  Effect of magnesium ions on oriented growth of calcite on carboxylic acid functionalized self-assembled monolayer. , 2003, Journal of the American Chemical Society.

[28]  Joanna Aizenberg,et al.  Direct Fabrication of Large Micropatterned Single Crystals , 2003, Science.

[29]  S. Weiner,et al.  Biologically Formed Amorphous Calcium Carbonate , 2003, Connective tissue research.

[30]  Joanna Aizenberg,et al.  Calcitic microlenses as part of the photoreceptor system in brittlestars , 2001, Nature.

[31]  P. Dove,et al.  The role of Mg2+ as an impurity in calcite growth. , 2000, Science.

[32]  Yamashita,et al.  Effects of Carboxylic Acids on Calcite Formation in the Presence of Mg2+ Ions. , 1999, Journal of colloid and interface science.

[33]  Y. Dauphin.  Infrared Spectra and Elemental Composition in Recent Biogenic Calcites: Relationships between the ν4 Band Wavelength and Sr and Mg Concentrations , 1999 .

[34]  P. Dove,et al.  Thermodynamics of calcite growth: baseline for understanding biomineral formation , 1998, Science.

[35]  J. Aizenberg,et al.  Stabilization of amorphous calcium carbonate by specialized macromolecules in biological and synthetic precipitates , 1996 .

[36]  N. Wada,et al.  Effects of calcium-binding polysaccharides from calcareous algae on calcium carbonate polymorphs under conditions of double diffusion , 1993 .

[37]  V. Streltsov,et al.  X-ray study of the electron density in calcite, CaCO3 , 1993 .

[38]  S. Weiner,et al.  Interactions between acidic proteins and crystals: stereochemical requirements in biomineralization. , 1985, Proceedings of the National Academy of Sciences of the United States of America.

[39]  D. M. Devery,et al.  Morphological changes in a series of synthetic Mg-calcites , 1981 .

[40]  P. Malone,et al.  Precipitation of Metastable Carbonate Phases from Seawater , 1970, Nature.

[41]  J. Papike,et al.  Primary Protodolomite in Echinoid Skeletons , 1969 .

[42]  R. Sippel,et al.  Synthesis of magnesium calcites , 1967 .

[43]  R. Garrels,et al.  Observations on the Solubility of Skeletal Carbonates in Aqueous Solutions , 1962, Science.

[44]  H. C. Heard,et al.  Lattice constants of the calcium magnesium carbonates , 1961 .

[45]  K. Chave.  Aspects of the Biogeochemistry of Magnesium 1. Calcareous Marine Organisms , 1954, The Journal of Geology.

[46]  C. Chalar,et al.  Monohydrocalcite in calcareous corpuscles of Mesocestoides corti. , 2008, Experimental parasitology.

[47]  C. Gabrielli,et al.  Characterization of CaCO3 hydrates by micro‐Raman spectroscopy , 2002 .

[48]  S. Weiner,et al.  Formation of High‐Magnesian Calcites via an Amorphous Precursor Phase: Possible Biological Implications , 2000 .

[49]  M. Gazzano,et al.  Magnesium calcite crystallizatin from water–alcohol mixtures , 1996 .

[50]  D. Hood,et al.  The influence of organic material on the polymorphic crystallization of calcium carbonate , 1965 .