Nanostructured Calcite Single Crystals with Gyroid Morphologies

Finnemore, Alexander S.; Scherer, Maik R. J.; Langford, R. M.; Mahajan, Sumeet; Ludwigs, Sabine; Meldrum, Fiona C.; Steiner, Ullrich

doi:10.1002/adma.200900615

Cited by 102 publications

(121 citation statements)

References 38 publications

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“…Quenching the crystallization of the amorphous top layer after only 10 min followed by dissolution of the remaining amorphous material reveals facetted seed crystallization in the pores (also Supplementary Figs S4 and S5). Facets are suppressed while the mineral is in contact with a soft organic material, but crystallinity is nevertheless propagated through the pores, in agreement with previous studies 23,24 .…”

Section: Fabricationsupporting

confidence: 81%

“…2c is based on the biological strategy using ACC [23][24][25][26] . Using the ammonium carbonate diffusion technique with a PAA-containing 1:5 Ca 2 + :Mg 2 + solution (Mg 2 + and PAA suppress calcite rhombohdra formation) 27 yields stable polymer-induced liquid precursor droplets, which wet the carboxyl terminated substrate and coalesce into a ACC film, rich in Mg and PAA (cal org ) 28,29 .…”

Section: Fabricationmentioning

confidence: 99%

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Biomimetic layer-by-layer assembly of artificial nacre

et al. 2012

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nacre is a technologically remarkable organic-inorganic composite biomaterial. It consists of an ordered multilayer structure of crystalline calcium carbonate platelets separated by porous organic layers. This microstructure exhibits both optical iridescence and mechanical toughness, which transcend those of its constituent components. Replication of nacre is essential for understanding this complex biomineral, and paves the way for tough coatings fabricated from cheap abundant materials. Fabricating a calcitic nacre imitation with biologically similar optical and mechanical properties will likely require following all steps taken in biogenic nacre synthesis. Here we present a route to artificial nacre that mimics the natural layer-bylayer approach to fabricate a hierarchical crystalline multilayer material. Its structure-function relationship was confirmed by nacre-like mechanical properties and striking optical iridescence. our biomimetic route uses the interplay of polymer-mediated mineral growth, combined with layer-by-layer deposition of porous organic films. This is the first successful attempt to replicate nacre, using CaCo 3 .

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Section: Fabricationsupporting

confidence: 81%

Section: Fabricationmentioning

confidence: 99%

Biomimetic layer-by-layer assembly of artificial nacre

et al. 2012

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“…Current engineering approaches also aim to produce single gyroid motifs from a double gyroid template (e.g., ref. 45). The biological development of triply periodic, cubic, photonic crystals in butterflies may offer a convenient template for the design and manufacture of devices for photonic applications based on biomimicry or positive cast dielectric infiltration (43)(44)(45).…”

Section: Resultsmentioning

confidence: 99%

Structure, function, and self-assembly of single network gyroid ( I 4 ₁ 32) photonic crystals in butterfly wing scales

Saranathan

Osuji

Mochrie

et al. 2010

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

438

412

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Complex three-dimensional biophotonic nanostructures produce the vivid structural colors of many butterfly wing scales, but their exact nanoscale organization is uncertain. We used small angle X-ray scattering (SAXS) on single scales to characterize the 3D photonic nanostructures of five butterfly species from two families (Papilionidae, Lycaenidae). We identify these chitin and air nanostructures as single network gyroid (I4 1 32) photonic crystals. We describe their optical function from SAXS data and photonic band-gap modeling. Butterflies apparently grow these gyroid nanostructures by exploiting the self-organizing physical dynamics of biological lipid-bilayer membranes. These butterfly photonic nanostructures initially develop within scale cells as a core-shell double gyroid (Ia3d), as seen in block-copolymer systems, with a pentacontinuous volume comprised of extracellular space, cell plasma membrane, cellular cytoplasm, smooth endoplasmic reticulum (SER) membrane, and intra-SER lumen. This double gyroid nanostructure is subsequently transformed into a single gyroid network through the deposition of chitin in the extracellular space and the degeneration of the rest of the cell. The butterflies develop the thermodynamically favored double gyroid precursors as a route to the optically more efficient single gyroid nanostructures. Current approaches to photonic crystal engineering also aim to produce single gyroid motifs. The biologically derived photonic nanostructures characterized here may offer a convenient template for producing optical devices based on biomimicry or direct dielectric infiltration.biological meta-materials | organismal color | biomimetics | biological cubic mesophases

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“…[4][5][6][7][8] Calcium carbonate, in addition to being an important material for industrial applications, is also present in many living organisms, which has also led to much work on the growth mechanisms that give the very particular morphologies observed in nature. [9][10][11][12] In the current study, the precipitation of calcium carbonate from relatively concentrated solutions (0.02 M) involves the formation of an initial "precursor" gel phase which, without the use of seeds, transforms into a mixture of both calcite and or vaterite, [13][14][15] even in the presence of polyacrylic acids. 16 The vast amount of literature on the calcium carbonate system provides extensive information on the kinetic parameters and solubility.…”

Section: Introductionmentioning

confidence: 99%

Contribution of Aggregation to the Growth Mechanism of Seeded Calcium Carbonate Precipitation in the Presence of Polyacrylic Acid

et al. 2010

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Our work investigates the precipitation mechanism of a seeded calcium carbonate reaction, by using cryogenic TEM to observe the early stages of the reaction. The early precipitation of a hydrated phase is proposed as an intermediate phase before transformation into calcite. Thermodynamic modeling in conjunction with pH, surface potential measurements, and colloidal stability modeling demonstrate that calcite growth is dominated by agglomeration. This is in agreement with the cryogenic TEM observations, which suggest oriented attachment dominates early aggregation. The final stage of the reaction is described by a ripening mechanism that is significantly inhibited when high concentrations of polyacrylic acid (PAA) are used. The different concentrations of PAA lead to significant differences in the final particle substructure observed using cross section TEM. At low PAA concentrations, single crystal particles result, coherent with the proposed early oriented attachment mechanism and interfacial energy calculations. A core shell model is proposed for high PAA concentrations, whereas internal ripening of nanosized pores has been observed for low PAA concentrations, suggesting trapped solvent during the rapid initial particle formation at the relatively high supersaturations (S ) 30) investigated.

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Nanostructured Calcite Single Crystals with Gyroid Morphologies

Cited by 102 publications

References 38 publications

Biomimetic layer-by-layer assembly of artificial nacre

Biomimetic layer-by-layer assembly of artificial nacre

Structure, function, and self-assembly of single network gyroid ( I 4 ₁ 32) photonic crystals in butterfly wing scales

Contribution of Aggregation to the Growth Mechanism of Seeded Calcium Carbonate Precipitation in the Presence of Polyacrylic Acid

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Nanostructured Calcite Single Crystals with Gyroid Morphologies

Cited by 102 publications

References 38 publications

Biomimetic layer-by-layer assembly of artificial nacre

Biomimetic layer-by-layer assembly of artificial nacre

Structure, function, and self-assembly of single network gyroid ( I 4 1 32) photonic crystals in butterfly wing scales

Contribution of Aggregation to the Growth Mechanism of Seeded Calcium Carbonate Precipitation in the Presence of Polyacrylic Acid

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Structure, function, and self-assembly of single network gyroid ( I 4 ₁ 32) photonic crystals in butterfly wing scales