Narrowly Distributed Crystal Orientation in Biomineral Vaterite

Pokroy, Boaz; Kabalah-Amitai, Lee; Polishchuk, Iryna; DeVol, Ross T.; Blonsky, Adam Z.; Sun, Chang‐Yu; Marcus, Matthew A.; Schöll, A.; Gilbert, Benjamin

doi:10.1021/acs.chemmater.5b01542

Cited by 27 publications

(29 citation statements)

References 98 publications

(159 reference statements)

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“…In this case, however, one encounters polycrystalline material and rotation of nanocrystal orientation. The case of the recently reported biomineral vaterite is especially interesting and relevant11, because it exhibits orientation changes between adjacent crystallites within a narrow range of 0 to 30° without any organic interfacial layer that often contributes to the alignment of neighboring crystallites1213. This is a completely unexpected result from the classical theory of crystallization by nucleation and growth, and spherulitic growth mode has been suggested to explain these observations.…”

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confidence: 80%

“…However, its mechanism, in particular the source of non-crystallographic branching in spherulites remains unclear7. So the knowledge of how lattice rotation is introduced is important for understanding the formation of spherulites145671415161718192021222324 as well as biominerals910111213. The ability to control this rotation will help fabricate ‘bio-inspired’ materials that mimic the structure of biominerals and hence their superior properties25.…”

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confidence: 99%

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Rotating lattice single crystal architecture on the surface of glass

Savytskii

Jain

Tamura

et al. 2016

Sci Rep

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Defying the requirements of translational periodicity in 3D, rotation of the lattice orientation within an otherwise single crystal provides a new form of solid. Such rotating lattice single (RLS) crystals are found, but only as spherulitic grains too small for systematic characterization or practical application. Here we report a novel approach to fabricate RLS crystal lines and 2D layers of unlimited dimensions via a recently discovered solid-to-solid conversion process using a laser to heat a glass to its crystallization temperature but keeping it below the melting temperature. The proof-of-concept including key characteristics of RLS crystals is demonstrated using the example of Sb2S3 crystals within the Sb-S-I model glass system for which the rotation rate depends on the direction of laser scanning relative to the orientation of initially formed seed. Lattice rotation in this new mode of crystal growth occurs upon crystallization through a well-organized dislocation/disclination structure introduced at the glass/crystal interface. Implications of RLS growth on biomineralization and spherulitic crystal growth are noted.

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confidence: 80%

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confidence: 99%

Rotating lattice single crystal architecture on the surface of glass

Savytskii

Jain

Tamura

et al. 2016

Sci Rep

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“…The angular distance Δc is a direct measurement of misorientation between the c-axes of two adjacent crystals. 40 The histogram in Figure 7a clearly shows that almost all the pairs of adjacent crystals measured have an angular distance between 0°−30°, and the ) an SA spherulite. Two adjacent domains with homogeneous color in PIC-maps were selected and their angular distance Δc, that is, the difference in orientation of their c-axes were calculated as described in Figure S8 caption.…”

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confidence: 93%

“…38,39 Spherulitic growth was suspected to take place in vaterite spicules based on their crystal orientations. 40 Benzerara et al showed in a Porites coral skeleton a radial distribution of aragonite crystal orientations strongly suggestive of spherulitic structure, but did not explicitly conclude that it was spherulitic. 41 For all other biominerals, high resolution, quantitative crystal orientation analysis has not been done.…”

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confidence: 98%

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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“…As such, this concept could be associated, if not actually considered as interchangeable, with the notion of meso-crystals defined for the growth by oriented attachment of nanoparticles building up single crystals. 29 It also appears that a surface fractal aggregate model could explain various aspects of the concept of mosaicity that characterises the formation of inorganic [30][31][32] and macromolecular [33][34][35][36] single crystals.…”

Section: Introductionmentioning

confidence: 99%

Not just fractal surfaces, but surface fractal aggregates: Derivation of the expression for the structure factor and its applications

Besselink

Stawski

Driessche

et al. 2016

The Journal of Chemical Physics

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Densely packed surface fractal aggregates form in systems with high local volume fractions of particles with very short diffusion lengths, which effectively means that particles have little space to move. However, there are no prior mathematical models, which would describe scattering from such surface fractal aggregates and which would allow the subdivision between inter-and intraparticle interferences of such aggregates. Here, we show that by including a form factor function of the primary particles building the aggregate, a finite size of the surface fractal interfacial sub-surfaces can be derived from a structure factor term. This formalism allows us to define both a finite specific surface area for fractal aggregates and the fraction of particle interfacial sub-surfaces at the perimeter of an aggregate. The derived surface fractal model is validated by comparing it with an ab initio approach that involves the generation of a "brick-in-a-wall" von Koch type contour fractals. Moreover, we show that this approach explains observed scattering intensities from in situ experiments that followed gypsum (CaSO 4 ·2H 2 O) precipitation from highly supersaturated solutions. Our model of densely packed "brick-in-a-wall" surface fractal aggregates may well be the key precursor step in the formation of several types of mosaic-and meso-crystals. C

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Narrowly Distributed Crystal Orientation in Biomineral Vaterite

Cited by 27 publications

References 98 publications

Rotating lattice single crystal architecture on the surface of glass

Rotating lattice single crystal architecture on the surface of glass

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

Not just fractal surfaces, but surface fractal aggregates: Derivation of the expression for the structure factor and its applications

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