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- Biomineralisation (1)
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- LACC (1)
- Nonclassical crystallization (1)
- PILP (1)
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Nonclassical crystallization typically occurs via the attachment of individual nanoparticles. Intuitively, materials synthesized via this route should exhibit pronounced surface roughness and porosity as a hallmark of the formation process via particle accretion. Here, we demonstrate that nonclassical mineralization of calcium carbonate allows synthesis of ultra-smooth and dense surfaces with unprece-dented root-mean-square roughness of 0.285 nm, simply by con-trolling the hydration state of the nanosized building blocks using Mg doping. High fidelity coating of corrugated substrates can even be achieved. Nonclassical crystallization can thus lead to space-filling inorganic solid-state materials transgressing the implicit porosity commonly expected for particle-driven self-organization processes.
The impact of the ovo proteins ovalbumin and lysozyme—present in the first stage of egg shell formation—on the homogeneous formation of the liquid amorphous calcium carbonate (LACC) precursor, was studied by a combination of complementing methods: in situ WAXS, SANS, XANES, TEM, and immunogold labeling. Lysozyme (pI = 9.3) destabilizes the LACC emulsion whereas the glycoprotein ovalbumin (pI = 4.7) extends the lifespan of the emulsified state remarkably. In the light of the presented data: (a) Ovalbumin is shown to behave commensurable to the 'polymer-induced liquid precursor' (PILP) process proposed by Gower et al. Ovalbumin can be assumed to take a key role during eggshell formation where it serves as an effective stabilization agent for transient precursors and prevents undirected mineralization of the eggshell. (b) It is further shown that the emulsified LACC carries a negative surface charge and is electrostatically stabilized. (c) We propose that the liquid amorphous calcium carbonate is affected by polymers by depletion stabilization and de-emulsification rather than 'induced' by acidic proteins and polymers during a so-called polymer-induced liquid-precursor process. The original PILP coating effect, first reported by Gower et al., appears to be a result of a de-emulsification process of a stabilized LACC phase. The behavior of the liquid amorphous carbonate phase and the polymer-induced liquid-precursor phase itself can be well described by colloid chemical terms: electrostatic and depletion stabilization and de-emulsification by depletion destabilization.
During the mineralisation of metal carbonates MCO3 (M = Ca, Sr, Ba, Mn, Cd, Pb) liquid-like amorphous intermediates emerge. These intermediates that form via a liquid/liquid phase separation behave like a classical emulsion and are stabilized electrostatically. The occurrence of these intermediates is attributed to the formation of highly hydrated networks whose stability is mainly based on weak interactions and the variability of the metal-containing pre-critical clusters. Their existence and compositional freedom are evidenced by electrospray ionization mass spectrometry (ESI-MS). Liquid intermediates in non-classical crystallisation pathways seem to be more common than assumed.