Stable Prenucleation Mineral Clusters Are Liquid-like Ionic Polymers

Overview

Journal Nat Commun

Specialty Biology

Date 2011 Dec 22

PMID 22186886

Citations 74

Authors

Raffaella Demichelis

Paolo Raiteri

Julian D Gale

David Quigley

Denis Gebauer

Affiliations

Soon will be listed here.

Abstract

Calcium carbonate is an abundant substance that can be created in several mineral forms by the reaction of dissolved carbon dioxide in water with calcium ions. Through biomineralization, organisms can harness and control this process to form various functional materials that can act as anything from shells through to lenses. The early stages of calcium carbonate formation have recently attracted attention as stable prenucleation clusters have been observed, contrary to classical models. Here we show, using computer simulations combined with the analysis of experimental data, that these mineral clusters are made of an ionic polymer, composed of alternating calcium and carbonate ions, with a dynamic topology consisting of chains, branches and rings. The existence of a disordered, flexible and strongly hydrated precursor provides a basis for explaining the formation of other liquid-like amorphous states of calcium carbonate, in addition to the non-classical behaviour during growth of amorphous calcium carbonate.

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References

Grossfield A, Ren P, Ponder J . Ion solvation thermodynamics from simulation with a polarizable force field. J Am Chem Soc. 2003; 125(50):15671-82. DOI: 10.1021/ja037005r. View

Tribello G, Bruneval F, Liew C, Parrinello M . A molecular dynamics study of the early stages of calcium carbonate growth. J Phys Chem B. 2009; 113(34):11680-7. DOI: 10.1021/jp902606x. View

Raiteri P, Gale J . Water is the key to nonclassical nucleation of amorphous calcium carbonate. J Am Chem Soc. 2010; 132(49):17623-34. DOI: 10.1021/ja108508k. View

Metzler R, Tribello G, Parrinello M, Gilbert P . Asprich peptides are occluded in calcite and permanently disorder biomineral crystals. J Am Chem Soc. 2010; 132(33):11585-91. DOI: 10.1021/ja103089r. View

Wolf S, Muller L, Barrea R, Kampf C, Leiterer J, Panne U . Carbonate-coordinated metal complexes precede the formation of liquid amorphous mineral emulsions of divalent metal carbonates. Nanoscale. 2011; 3(3):1158-65. PMC: 3111071. DOI: 10.1039/c0nr00761g. View

Radha A, Forbes T, Killian C, Gilbert P, Navrotsky A . Transformation and crystallization energetics of synthetic and biogenic amorphous calcium carbonate. Proc Natl Acad Sci U S A. 2010; 107(38):16438-43. PMC: 2944757. DOI: 10.1073/pnas.1009959107. View

Meldrum F, Colfen H . Controlling mineral morphologies and structures in biological and synthetic systems. Chem Rev. 2008; 108(11):4332-432. DOI: 10.1021/cr8002856. View

Coleyshaw E, Crump G, Griffith W . Vibrational spectra of the hydrated carbonate minerals ikaite, monohydrocalcite, lansfordite and nesquehonite. Spectrochim Acta A Mol Biomol Spectrosc. 2003; 59(10):2231-9. DOI: 10.1016/s1386-1425(03)00067-2. View

Sommerdijk N, de With G . Biomimetic CaCO3 mineralization using designer molecules and interfaces. Chem Rev. 2008; 108(11):4499-550. DOI: 10.1021/cr078259o. View

10.

Hamm L, Wallace A, Dove P . Molecular dynamics of ion hydration in the presence of small carboxylated molecules and implications for calcification. J Phys Chem B. 2010; 114(32):10488-95. DOI: 10.1021/jp9108893. View

11.

Wolf S, Leiterer J, Pipich V, Barrea R, Emmerling F, Tremel W . Strong stabilization of amorphous calcium carbonate emulsion by ovalbumin: gaining insight into the mechanism of 'polymer-induced liquid precursor' processes. J Am Chem Soc. 2011; 133(32):12642-9. PMC: 3170880. DOI: 10.1021/ja202622g. View

12.

Schroder D, Duchackova L, Tarabek J, Karwowska M, Fijalkowski K, Oncak M . Direct observation of triple ions in aqueous solutions of nickel(II) sulfate: a molecular link between the gas phase and bulk behavior. J Am Chem Soc. 2011; 133(8):2444-51. DOI: 10.1021/ja105408a. View

13.

de Greef T, Meijer E . Materials science: supramolecular polymers. Nature. 2008; 453(7192):171-3. DOI: 10.1038/453171a. View

14.

Gale J, Raiteri P, van Duin A . A reactive force field for aqueous-calcium carbonate systems. Phys Chem Chem Phys. 2011; 13(37):16666-79. DOI: 10.1039/c1cp21034c. View

15.

Kohn J, Millett I, Jacob J, Zagrovic B, Dillon T, Cingel N . Random-coil behavior and the dimensions of chemically unfolded proteins. Proc Natl Acad Sci U S A. 2004; 101(34):12491-6. PMC: 515087. DOI: 10.1073/pnas.0403643101. View

16.

Rodriguez-Blanco J, Shaw S, Benning L . The kinetics and mechanisms of amorphous calcium carbonate (ACC) crystallization to calcite, via vaterite. Nanoscale. 2010; 3(1):265-71. DOI: 10.1039/c0nr00589d. View

17.

Olszta M, Odom D, Douglas E, Gower L . A new paradigm for biomineral formation: mineralization via an amorphous liquid-phase precursor. Connect Tissue Res. 2003; 44 Suppl 1:326-34. View

18.

Pouget E, Bomans P, Goos J, Frederik P, de With G, Sommerdijk N . The initial stages of template-controlled CaCO3 formation revealed by cryo-TEM. Science. 2009; 323(5920):1455-8. DOI: 10.1126/science.1169434. View

19.

Aizenberg J, Tkachenko A, Weiner S, Addadi L, HENDLER G . Calcitic microlenses as part of the photoreceptor system in brittlestars. Nature. 2001; 412(6849):819-22. DOI: 10.1038/35090573. View

20.

Gebauer D, Gunawidjaja P, Ko J, Bacsik Z, Aziz B, Liu L . Proto-calcite and proto-vaterite in amorphous calcium carbonates. Angew Chem Int Ed Engl. 2010; 49(47):8889-91. DOI: 10.1002/anie.201003220. View