Direct Nanoscale Imaging Reveals the Growth of Calcite Crystals via Amorphous Nanoparticles

Rodríguez-Navarro, Carlos; Burgos-Cara, Alejandro; Elert, Kerstin; Putnis, Christine V.; Ruíz-Agudo, Encarnación

doi:10.1021/acs.cgd.5b01180

Cited by 98 publications

(111 citation statements)

References 45 publications

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“…An interplay between these factors is reflected in the mesocrystalline organization of the sea urchin spine, which is derived from the biogenic crystallization of an amorphous mineral precursor in the presence of ionic and (bio) polymeric additives ,. Combining the mechanisms of material formation by particle‐attachment and phase transformation, crystal growth can proceed by the attachment of amorphous particles to crystalline surfaces . Analogous to the roles of atoms, molecular and ions in the Kossel model for layer‐by‐layer crystal growth, amorphous particles attach and organize on crystalline surfaces .…”

Section: On the Nature Of Materials Precursorsmentioning

confidence: 99%

“…Challenges in material science not only focus on the synthetic control over particle size and structure, but also strive towards the construction of complex materials with hierarchical organizations. Recent advances in the field of nucleation and crystallization inspire novel strategies for fabricating remarkable material architectures organized at different length scales . The related mechanistic pathways not only elucidate the emergence of non‐equilibrium material morphologies and organizations, but also complement the inadequacies of classical notions.…”

Section: Introductionmentioning

confidence: 99%

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From Solute, Fluidic and Particulate Precursors to Complex Organizations of Matter

Rao

Cölfen

2018

The Chemical Record

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The organization of matter from its constitutive units recruits intermediate states with distinctive degrees of self-association and molecular order. Existing as clusters, droplets, gels as well as amorphous and crystalline nanoparticles, these precursor forms have fundamental contributions towards the composition and structure of inorganic and organic architectures. In this personal account, we show that the transitions from atoms, molecules or ionic species to superstructures of higher order are intertwined with the interfaces and interactions of precursor and intermediate states. Structural organizations distributed across different length scales are explained by the multistep nature of nucleation and crystallization, which can be guided towards functional hybrid materials by the strategic application of additives, templates and reaction environments. Thus, the non-classical pathways for material formation and growth offer conceptual frameworks for elucidating, inducing and directing fascinating material organizations of biogenic and synthetic origins.

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Section: On the Nature Of Materials Precursorsmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

From Solute, Fluidic and Particulate Precursors to Complex Organizations of Matter

Rao

Cölfen

2018

The Chemical Record

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“…17 Rodrigues-Navarro also showed this effect. 18 Thus, both aragonite growth by CPA and by ion attachment are faster along the c-axis.Spherulites are found in a wide variety of materials systems, including geologic minerals, 19,20 metal alloys, 21 nonmetallic elements, 5,22 salts, 23,24 organic molecules, 13,25 proteins, 26 and a vast number of synthetic 2,3,27,28 and natural 4 polymers.Many biominerals have also been described as spherulitic based on their morphologies, including coral skeletons, 10,11,29,30 avian eggshells, 31−33 fish otoliths, 12,34,35 crustacean statoliths, 36 sponges, 37 and kidney stones. 38,39 The only evidence of spherulites in biominerals obtained from crystal orientation analysis, however, is in bioinduced, kidney stones, which are calcium oxalate monohydrate pathological biominerals.…”

mentioning

confidence: 99%

“…17 Rodrigues-Navarro also showed this effect. 18 Thus, both aragonite growth by CPA and by ion attachment are faster along the c-axis.…”

mentioning

confidence: 99%

Spherulitic Growth of Coral Skeletons and Synthetic Aragonite: Nature’s Three-Dimensional Printing

Sun¹,

Marcus

Frazier³

et al. 2017

ACS Nano

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Coral skeletons were long assumed to have a spherulitic structure, that is, a radial distribution of acicular aragonite (CaCO 3 ) crystals with their c-axes radiating from series of points, termed centers of calcification (CoCs). This assumption was based on morphology alone, not on crystallography. Here we measure the orientation of crystals and nanocrystals and confirm that corals grow their skeletons in bundles of aragonite crystals, with their caxes and long axes oriented radially and at an angle from the CoCs, thus precisely as expected for feather-like or "plumose" spherulites. Furthermore, we find that in both synthetic and coral aragonite spherulites at the nanoscale adjacent crystals have similar but not identical orientations, thus demonstrating by direct observation that even at nanoscale the mechanism of spherulite formation is non-crystallographic branching (NCB), as predicted by theory. Finally, synthetic aragonite spherulites and coral skeletons have similar angle spreads, and angular distances of adjacent crystals, further confirming that coral skeletons are spherulites. This is important because aragonite grows anisotropically, 10 times faster along the c-axis than along the a-axis direction, and spherulites fill space with crystals growing almost exclusively along the c-axis, thus they can fill space faster than any other aragonite growth geometry, and create isotropic materials from anisotropic crystals. Greater space filling rate and isotropic mechanical behavior are key to the skeleton's supporting function and therefore to its evolutionary success. In this sense, spherulitic growth is Nature's 3D printing. KEYWORDS: Ion attachment, crystallization by particle attachment, CPA, biomineralization, PEEM, PIC-mapping, mesocrystal S pherulites are polycrystalline structures in which acicular crystals radiate from a common center and grow approximately synchronously so the final shape of a spherulite resembles a sphere. 1−7 Figure 1 shows two types of spherulites: "spherical spherulite", in which the crystal fibers start from a point, or "plumose spherulite", in which crystal fibers radiate at an angle from the line. 7 Spherulites start forming as an aggregate of parallel acicular crystals termed "fibers", then form a "sheaf of wheat" structure, and with the growth of more fibers eventually become complete spheres. 8 In an ideal spherulite, fibers radiate from the center and contain all possible orientations within the sphere. Since the fast-growing axis in aragonite (CaCO 3 ) is the c-axis, 9 in spherulites each fiber elongation direction coincides with the crystalline c-axis. 10,11 In real spherulites, biogenic 12 and synthetic, 7 the crystal orientations are not perfectly radial nor continuously varying with angle, they deviate slightly from radial and exhibit small but abrupt changes in orientation, termed "branching". In Figure 1 branching angles are smaller than 30°in direction and in crystal lattice orientation. This is distinct from crystallographic branching, which occurs in sno...

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“…The involvement of nonclassical nucleation pathways has been implied by previous studies, but only recently, direct evidence regarding the actual mechanism of calcite growth via an amorphous phase was reported. Rodriguez-Navarro et al used in situ AFM to show that calcite can grow via a nonclassical particle-mediated colloidal crystal growth mechanism involving a layer-by-layer attachment of amorphous calcium carbonate (ACC) precursors, followed by restructuring and fusion with the calcite substrate in perfect crystallographic registry [173]. The transformation of ACC to calcite occurs through interface-coupled dissolution-reprecipitation and affects the nanogranular texture of the colloidal growth layer regulated by organic molecules.…”

Section: Calcitementioning

confidence: 99%

In Situ Atomic Force Microscopy Studies on Nucleation and Self-Assembly of Biogenic and Bio-Inspired Materials

Zeng

Vitale-Sullivan

2017

Minerals

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Through billions of years of evolution, nature has been able to create highly sophisticated and ordered structures in living systems, including cells, cellular components and viruses. The formation of these structures involves nucleation and self-assembly, which are fundamental physical processes associated with the formation of any ordered structure. It is important to understand how biogenic materials self-assemble into functional and highly ordered structures in order to determine the mechanisms of biological systems, as well as design and produce new classes of materials which are inspired by nature but equipped with better physiochemical properties for our purposes. An ideal tool for the study of nucleation and self-assembly is in situ atomic force microscopy (AFM), which has been widely used in this field and further developed for different applications in recent years. The main aim of this work is to review the latest contributions that have been reported on studies of nucleation and self-assembly of biogenic and bio-inspired materials using in situ AFM. We will address this topic by introducing the background of AFM, and discussing recent in situ AFM studies on nucleation and self-assembly of soft biogenic, soft bioinspired and hard materials.

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Direct Nanoscale Imaging Reveals the Growth of Calcite Crystals via Amorphous Nanoparticles

Cited by 98 publications

References 45 publications

From Solute, Fluidic and Particulate Precursors to Complex Organizations of Matter

From Solute, Fluidic and Particulate Precursors to Complex Organizations of Matter

Spherulitic Growth of Coral Skeletons and Synthetic Aragonite: Nature’s Three-Dimensional Printing

In Situ Atomic Force Microscopy Studies on Nucleation and Self-Assembly of Biogenic and Bio-Inspired Materials

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