pH-Dependent Schemes of Calcium Carbonate Formation in the Presence of Alginates

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2016
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Vásquez-Quitral, Patricio
Fernández, María S.
Berg, John K.
Sánchez, Marianela
Drechsler, Markus
Neira-Carrillo, Andrónico
Arias, José L.
Gebauer, Denis
Cölfen, Helmut
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Crystal Growth & Design. 2016, 16(3), pp. 1349-1359. ISSN 1528-7483. eISSN 1528-7505. Available under: doi: 10.1021/acs.cgd.5b01488
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From recent studies on bone and shell formation, the importance of polysaccharides in biomineralization processes is gradually being recognized. Through ion-complexation and self-assembly properties, such macromolecules have remarkable effects on mineralization. However, their influences on the different regimes of crystallization including the interactions with precursor species are unclear. The present study therefore addresses calcium carbonate mineralization in the presence of alginates, a class of linear copolymeric saccharides composed of β-1,4 linked d-mannuronic and l-guluronic acid. During mineralization, this biopolymer is found to exert pH-dependent control over mineralization pathways in terms of the stability of prenucleation clusters, inhibitory effect toward nucleation and initially formed postnucleation products. Remarkably in the presence of this macromolecular additive, either amorphous or crystalline vaterite particles can be selectively nucleated in a pH-dependent manner. This is validated by electron microscopy wherein vaterite particles are intimately associated with alginate assemblies after nucleation at pH 9.75. At lower pH, aggregates of amorphous particles are formed. Thus, in addition to the general focus on biochemical properties of additives, solution pH, a physiologically fundamental parameter significantly alters the scheme of mineralization.

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ISO 690RAO, Ashit, Patricio VÁSQUEZ-QUITRAL, María S. FERNÁNDEZ, John K. BERG, Marianela SÁNCHEZ, Markus DRECHSLER, Andrónico NEIRA-CARRILLO, José L. ARIAS, Denis GEBAUER, Helmut CÖLFEN, 2016. pH-Dependent Schemes of Calcium Carbonate Formation in the Presence of Alginates. In: Crystal Growth & Design. 2016, 16(3), pp. 1349-1359. ISSN 1528-7483. eISSN 1528-7505. Available under: doi: 10.1021/acs.cgd.5b01488
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@article{Rao2016-03-02pHDep-33705,
  year={2016},
  doi={10.1021/acs.cgd.5b01488},
  title={pH-Dependent Schemes of Calcium Carbonate Formation in the Presence of Alginates},
  number={3},
  volume={16},
  issn={1528-7483},
  journal={Crystal Growth & Design},
  pages={1349--1359},
  author={Rao, Ashit and Vásquez-Quitral, Patricio and Fernández, María S. and Berg, John K. and Sánchez, Marianela and Drechsler, Markus and Neira-Carrillo, Andrónico and Arias, José L. and Gebauer, Denis and Cölfen, Helmut}
}
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