In situ techniques in biomimetic mineralization studies of calcium carbonate

Dey, Archan; With, G. de; Sommerdijk, Nico A. J. M.

doi:10.1039/b811842f

Cited by 119 publications

(93 citation statements)

References 66 publications

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“…In many cases, the precipitation of CaCO 3 from solution is described as a multistep process, with amorphous phases first precipitated before transformation to more stable crystalline forms according to Ostwald's rule of stages (9). Moreover, in biological systems, time-dependent spectroscopy measurements indicated that a hydrated amorphous calcium carbonate (ACC) is first deposited and then undergoes dehydration before crystallization (10).…”

mentioning

confidence: 99%

A classical view on nonclassical nucleation

Smeets

Finney

Habraken

et al. 2017

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

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Understanding and controlling nucleation is important for many crystallization applications. Calcium carbonate (CaCO 3 ) is often used as a model system to investigate nucleation mechanisms. Despite its great importance in geology, biology, and many industrial applications, CaCO 3 nucleation is still a topic of intense discussion, with new pathways for its growth from ions in solution proposed in recent years. These new pathways include the socalled nonclassical nucleation mechanism via the assembly of thermodynamically stable prenucleation clusters, as well as the formation of a dense liquid precursor phase via liquid-liquid phase separation. Here, we present results from a combined experimental and computational investigation on the precipitation of CaCO 3 in dilute aqueous solutions. We propose that a dense liquid phase (containing 4-7 H 2 O per CaCO 3 unit) forms in supersaturated solutions through the association of ions and ion pairs without significant participation of larger ion clusters. This liquid acts as the precursor for the formation of solid CaCO 3 in the form of vaterite, which grows via a net transfer of ions from solution according to z Ca 2+ + z CO 3 2− → z CaCO 3 . The results show that all steps in this process can be explained according to classical concepts of crystal nucleation and growth, and that long-standing physical concepts of nucleation can describe multistep, multiphase growth mechanisms.calcium carbonate | nucleation | crystal growth | cryo-electron microscopy | molecular simulation I n the process of forming a solid phase from a supersaturated solution, nucleation is the key step governing the timescale of the transition. Controlling nucleation is an essential aspect in many crystallization processes, where distinct crystal polymorphism, size, morphology, and other characteristics are required. It is, therefore, important to obtain a fundamental understanding of nucleation mechanisms.More than 150 years ago, a basic theoretical framework, classical nucleation theory (CNT) (1, 2), was developed to describe such nucleation events. CNT describes the formation of nuclei from the dynamic and stochastic association of monomeric units (e.g., ions, atoms, or molecules) that overcome a free-energy barrier at a critical nucleus size and grow out to a mature bulk phase. Calcium carbonate (CaCO 3 ) is a frequently used model system to study nucleation (3-5); however, despite the many years of effort, there are still phenomena associated with CaCO 3 crystal formation where the applicability of classical nucleation concepts have been questioned (6). These include certain microstructures and habits of biominerals formed by organisms (7), or geological mineral deposits with unusual mineralogical and textural patterns (8).Three anhydrous crystalline polymorphs of CaCO 3 are observed in nature: vaterite, aragonite, and calcite in order of increasing thermodynamic stability. In many cases, the precipitation of CaCO 3 from solution is described as a multistep process, with amorphous phases first pr...

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mentioning

confidence: 99%

A classical view on nonclassical nucleation

Smeets

Finney

Habraken

et al. 2017

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

Self Cite

207

212

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“…Although acidic macromolecules are known to affect growth habits and phase selection, or even to completely inhibit precipitation in solution (Sommerdijk & With, 2008;Meldrum & C€ olfen, 2008;Gower, 2008), little is known about the role of matrix-immobilized acidic macromolecules in directing mineralization. This lack of understanding is, in part, due to the difficulty of studying biomimetic mineralization systems with sufficient spatial and temporal resolution (Dey et al, 2010). However, liquid phase transmission electron microscopy (LP-TEM) can visualize events in situ in thin liquid volumes (about 500 nm in height) confined within two electron transparent silicon nitride (SiN) membranes.…”

Section: In Situ Observations Of Biomineralization Processesmentioning

confidence: 99%

Ciscem 2014

Jonge

2015

Advances in Imaging and Electron Physics

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“…Damit können Ansätze, die aus dem biologischen Gebiet stammen, wirkungsvoll mit solchen aus den Materialwissenschaften kombiniert werden. [50] Wir danken P. H. H. Bomans für seine Unterstützung bei der Durchführung der Kryo-TEM. Die beschriebenen Forschungsarbeiten werden vom Dutch Polymer Institute (DPI) (Fördernummer 688) unterstützt.…”

Section: Schlussfolgerungen Und Ausblickunclassified

Abbildung selbstorganisierter Strukturen: Interpretation von TEM‐ und Kryo‐TEM‐Aufnahmen

2010

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In der Materialchemie werden in Lösung gezüchtete Nanostrukturen oft mithilfe der Transmissionselektronenmikroskopie (TEM) untersucht. Häufig werden die TEM‐Proben bei der Probenvorbereitung getrocknet und kontrastiert, und bei der Bildaufnahme selbst kommt es zur Wechselwirkung zwischen der Probe und dem Elektronenstrahl. Beide Prozesse rufen zur Vorsicht bei der Interpretation der erhaltenen elektronenmikroskopischen Aufnahmen auf. Alternativ dazu kann durch kryogene Probenpräparation und anschließende Abbildung mit kryogener Niederdosis‐TEM ein beinahe nativer solvatisierter Zustand konserviert werden. In unserem Kurzaufsatz geben wir eine kritische Analyse der Probenvorbereitung und, noch wichtiger, der Datenaufnahme und Interpretation von elektronenmikroskopischen Aufnahmen. Die Übersicht soll auch Leitlinien für die Anwendung von (Kryo‐)TEM als leistungsstarkes und zuverlässiges Hilfsmittel für die Analyse kolloidaler und selbstorganisierter Strukturen mit Abmessungen im Nanometerbereich bieten.

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In situ techniques in biomimetic mineralization studies of calcium carbonate

Cited by 119 publications

References 66 publications

A classical view on nonclassical nucleation

A classical view on nonclassical nucleation

Ciscem 2014

Abbildung selbstorganisierter Strukturen: Interpretation von TEM‐ und Kryo‐TEM‐Aufnahmen

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