Deposition of calcium carbonate films by a polymer-induced liquid-precursor (PILP) process

Gower, Laurie B.; Odom, Damian J

doi:10.1016/s0022-0248(99)00749-6

Cited by 558 publications

(704 citation statements)

References 23 publications

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“…4). Consequently, despite the recent reports of prenucleation clusters (41)(42)(43), liquid-liquid separation (44)(45)(46), and multiphase aggregationbased pathways of calcite formation (41,42,47) in bulk solutions, the results presented here provide strong evidence that the classical theory of nucleation provides a good description of calcite formation on ionized surfaces and that interfacial energy is a useful concept even when critical nuclei are in the nanometer range. Calculations of γ assume rhombohedral nuclei.…”

Section: Significancecontrasting

confidence: 54%

Reconciling disparate views of template-directed nucleation through measurement of calcite nucleation kinetics and binding energies

Hamm

Giuffre

Han

et al. 2014

Proc. Natl. Acad. Sci. U.S.A.

136

173

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The physical basis for how macromolecules regulate the onset of mineral formation in calcifying tissues is not well established. A popular conceptual model assumes the organic matrix provides a stereochemical match during cooperative organization of solute ions. In contrast, another uses simple binding assays to identify good promoters of nucleation. Here, we reconcile these two views and provide a mechanistic explanation for template-directed nucleation by correlating heterogeneous nucleation barriers with crystal-substrate-binding free energies. We first measure the kinetics of calcite nucleation onto model substrates that present different functional group chemistries (carboxyl, thiol, phosphate, and hydroxyl) and conformations (C11 and C16 chain lengths). We find rates are substrate-specific and obey predictions of classical nucleation theory at supersaturations that extend above the solubility of amorphous calcium carbonate. Analysis of the kinetic data shows the thermodynamic barrier to nucleation is reduced by minimizing the interfacial free energy of the system, γ. We then use dynamic force spectroscopy to independently measure calcitesubstrate-binding free energies, ΔG b . Moreover, we show that within the classical theory of nucleation, γ and ΔG b should be linearly related. The results bear out this prediction and demonstrate that low-energy barriers to nucleation correlate with strong crystal-substrate binding. This relationship is general to all functional group chemistries and conformations. These findings provide a physical model that reconciles the long-standing concept of templated nucleation through stereochemical matching with the conventional wisdom that good binders are good nucleators. The alternative perspectives become internally consistent when viewed through the lens of crystal-substrate binding.B iological systems are unique in their ability to organize minerals into functional materials with complex patterns and architectures. A substantial body of evidence suggests specialized macromolecules, particularly proteins (1, 2) and carbohydrates (3, 4), provide preferential sites for nucleation to direct the placement, timing, and orientation of crystals (5), both intra-and extracellular. Within the biomineralization community, the conventional view of biologically directed nucleation is that macromolecular matrices present an interfacial match to the crystal lattice that assists in forming the crystal nucleus. This cooperative view of directed nucleation is rooted in the collective action of multiple residues that guide the organization of ions into a configuration defining the energetic minimum for the system. A series of in vitro observations have reinforced this picture by showing that highly ordered organic monolayers can control the location and orientation of calcite crystals precipitated from solution (6). In this approach, good templates are revealed through a direct functional assay, i.e., nucleation. Over the years, this view of mineralization, both in the context of natural stru...

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Section: Significancecontrasting

confidence: 54%

Reconciling disparate views of template-directed nucleation through measurement of calcite nucleation kinetics and binding energies

Hamm

Giuffre

Han

et al. 2014

Proc. Natl. Acad. Sci. U.S.A.

136

173

View full text Add to dashboard Cite

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“…Section 3.1). Furthermore, it is worth noting that the influence of aspartate monomers on the initially nucleated phase is to some degree reminiscent of its polymeric analogue, given that polyaspartate is known to stabilize a metastable liquid-like precursor under certain circumstances, commonly referred to as PILP [58][59][60]. Titration experiments performed with pAsp present demonstrated the prolonged occurrence of a highly soluble phase with varying composition (K sp % 2 Á 10 À7 M 2 ), likely corresponding to PILP [46].…”

Section: Solubility Productsmentioning

confidence: 93%

The multiple effects of amino acids on the early stages of calcium carbonate crystallization

Picker¹,

Kellermeier²,

Seto³

et al. 2012

Zeitschrift Für Kristallographie - Crystalline Materials

109

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Abstract. Proteins have found their way into many of Nature's structures due to their structural stability, diversity in function and composition, and ability to be regulated as well as be regulators themselves. In this study, we investigate the constitutive amino acids that make up some of these proteins which are involved in CaCO 3 mineralization -either in nucleation, crystal growth, or inhibition processes. By assaying all 20 amino acids with vapor diffusion and in situ potentiometric titration, we have found specific amino acids having multiple effects on the early stages of CaCO 3 crystallization. These same amino acids have been independently implicated as constituents in liquid-like precursors that form mineralized tissues, processes believed to be key effects of biomineralization proteins in several biological model systems.

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“…Physiologically relevant liquid-like forms of organic as well as inorganic species have recently gained much research attention (Bewernitz et al 2012;Brangwynne et al 2015;Demichelis et al 2011;Gower and Odom 2000;Hyman et al 2014). As the roles of liquid-like precursors and coacervate phases of inorganic as well as organic systems are gradually being deciphered, their biological consequences emerge as significant in the field of mineralization.…”

Section: Mineralization and Liquid-like Phasesmentioning

confidence: 99%

“…As the roles of liquid-like precursors and coacervate phases of inorganic as well as organic systems are gradually being deciphered, their biological consequences emerge as significant in the field of mineralization. Stabilization of a transient inorganic liquid and amorphous phase by polymeric additives establishes a phase which exhibits liquid-like properties such as shape-adaptability (pseudomorphic transformation) and surface tension (Berg et al 2013;Bewernitz et al 2012;Gower and Odom 2000;Meldrum and Cölfen 2008;Olszta et al 2009). Such phases are suggested to play a fundamental role as a precursor phase in the morphogenesis of calcium-based biominerals such as enamel and bone (Olszta et al 2009).…”

Section: Mineralization and Liquid-like Phasesmentioning

confidence: 99%

Mineralization and non-ideality: on nature’s foundry

Rao¹,

Cölfen

2016

Biophys Rev

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Understanding how ions, ion-clusters and particles behave in non-ideal environments is a fundamental question concerning planetary to atomic scales. For biomineralization phenomena wherein diverse inorganic and organic ingredients are present in biological media, attributing biomaterial composition and structure to the chemistry of singular additives may not provide a holistic view of the underlying mechanisms. Therefore, in this review, we specifically address the consequences of physico-chemical non-ideality on mineral formation. Influences of different forms of non-ideality such as macromolecular crowding, confinement and liquid-like organic phases on mineral nucleation and crystallization in biological environments are presented. Novel prospects for the additive-controlled nucleation and crystallization are accessible from this biophysical view. In this manner, we show that non-ideal conditions significantly affect the form, structure and composition of biogenic and biomimetic minerals.

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Deposition of calcium carbonate films by a polymer-induced liquid-precursor (PILP) process

Cited by 558 publications

References 23 publications

Reconciling disparate views of template-directed nucleation through measurement of calcite nucleation kinetics and binding energies

Reconciling disparate views of template-directed nucleation through measurement of calcite nucleation kinetics and binding energies

The multiple effects of amino acids on the early stages of calcium carbonate crystallization

Mineralization and non-ideality: on nature’s foundry

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