Retrosynthesis of Nacre via Amorphous Precursor Particles

Gehrke, Nicole; Nassif, Nadine; Pinna, Nicola; Antonietti, Markus; Gupta, Himadri S.; Cölfen, Helmut

doi:10.1021/cm052150k

Cited by 130 publications

(147 citation statements)

References 24 publications

(43 reference statements)

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“…In different species, in fact, nonconfluent forming nacre tablets appear as cylinders in Pinctada margaritifera, 38 as hexagonal crystals in Atrina rigida, 32 or as polygons in Haliotis, 54,55 but they all converge toward final irregular polygonal patterns similar to that of Figure 5A at confluence. This demonstrates that crystals fill space until they can, 56 independent of their crystal facet preferences. Clearly, faster-growing crystals fill space more rapidly than slow-growing ones; thus, the final tablet-to-tablet boundary is closer in morphology to the crystal facet orientation preferred by the slow-growing tablet.…”

Section: Discussionmentioning

confidence: 89%

Gradual Ordering in Red Abalone Nacre

Gilbert

Metzler²,

Zhou³

et al. 2008

J. Am. Chem. Soc.

128

138

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Red abalone (Haliotis rufescens) nacre is a layered composite biomineral that contains crystalline aragonite tablets confined by organic layers. Nacre is intensely studied because its biologically controlled microarchitecture gives rise to remarkable strength and toughness, but the mechanisms leading to its formation are not well understood. Here we present synchrotron spectromicroscopy experiments revealing that stacks of aragonite tablet crystals in nacre are misoriented with respect to each other. Quantitative measurements of crystal orientation, tablet size, and tablet stacking direction show that orientational ordering occurs not abruptly but gradually over a distance of 50 µm. Several lines of evidence indicate that different crystal orientations imply different tablet growth rates during nacre formation. A theoretical model based on kinetic and gradual selection of the fastest growth rates produces results in qualitative and quantitative agreement with the experimental data and therefore demonstrates that ordering in nacre is a result of crystal growth kinetics and competition either in addition or to the exclusion of templation by acidic proteins as previously assumed. As in other natural evolving kinetic systems, selection of the fastest-growing stacks of tablets occurs gradually in space and time. These results suggest that the self-ordering of the mineral phase, which may occur completely independently of biological or organic-molecule control, is fundamental in nacre formation.

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Section: Discussionmentioning

confidence: 89%

Gradual Ordering in Red Abalone Nacre

Gilbert

Metzler²,

Zhou³

et al. 2008

J. Am. Chem. Soc.

128

138

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“…On crystallization, the collagenous matrix encloses organized assemblies of hydroxyapatite nanoparticles formed on phase transformation [38]. Mineralization of the insoluble matrix of nacre material in the presence of PAA also reports morphologies structurally analogous to the natural biomineral [39]. These studies demonstrate the crucial role of anionic biomacromolecules in determining non-equilibrium crystal morphologies and hierarchical structures that are typical of natural composite biominerals.…”

Section: Introductionmentioning

confidence: 73%

On Mineral Retrosynthesis of a Complex Biogenic Scaffold

2017

Self Cite

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Synergistic relations between organic molecules and mineral precursors regulate biogenic mineralization. Given the remarkable material properties of the egg shell as a biogenic ceramic, it serves as an important model to elucidate biomineral growth. With established roles of complex anionic biopolymers and a heterogeneous organic scaffold in egg shell mineralization, the present study explores the regulation over mineralization attained by applying synthetic polymeric counterparts (polyethylene glycol, poly(acrylic acid), poly(aspartic acid) and poly(4-styrenesulfonic acid-co-maleic acid)) as additives during remineralization of decalcified eggshell membranes. By applying Mg 2+ ions as a co-additive species, mineral retrosynthesis is achieved in a manner that modulates the polymorph and structure of mineral products. Notable features of the mineralization process include distinct local wettability of the biogenic organic scaffold by mineral precursors and mineralization-induced membrane actuation. Overall, the form, structure and polymorph of the mineralization products are synergistically affected by the additive and the content of Mg 2+ ions. We also revisit the physicochemical nature of the biomineral scaffold and demonstrate the distinct spatial distribution of anionic biomolecules associated with the scaffold-mineral interface, as well as highlight the hydrogel-like properties of mammillae-associated macromolecules.

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“…Setting the conditions such that these pathways can also be used in technical crystallization processes has lead to the generation of complex synthetic crystalline structures, which are indeed organic-inorganic hybrid materials, often exhibiting hierarchy. Mimicking nacre as a layered hybrid structure has been pursued within the Max Planck Society (MPS) [85][86][87][88][89], and elsewhere [90][91]. Indeed, nacre is a layered composite of calcium carbonate mineral and macromolecules with 3000-fold fracture resistance compared to the mineral itself.…”

Section: Biomimetic Materials Synthesismentioning

confidence: 99%

Biomimetic Materials in Our World: A Review.

Solomon¹

2013

IOSR-JAC

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Retrosynthesis of Nacre via Amorphous Precursor Particles

Cited by 130 publications

References 24 publications

Gradual Ordering in Red Abalone Nacre

Gradual Ordering in Red Abalone Nacre

On Mineral Retrosynthesis of a Complex Biogenic Scaffold

Biomimetic Materials in Our World: A Review.

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