Crystal nucleation and growth of spherulites demonstrated by coral skeletons and phase-field simulations

Sun, Chang; Gránásy, László; Stifler, Cayla A.; Zaquin, Tal; Chopdekar, Rajesh V.; Tamura, Nobumichi; Weaver, James C.; Zhang, Jun A.Y.; Goffredo, Stefano; Falini, Giuseppe; Marcus, Matthew A.; Pusztai, Tamás; Schoeppler, Vanessa; Mass, Tali; Gilbert, Pupa

doi:10.1016/j.actbio.2020.06.027

Cited by 27 publications

(54 citation statements)

References 98 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…6). This model is consistent with all of the experimental evidence currently available (22,25,26,33,42,60,61) and supersedes the incomplete model proposed by Mass et al (33).…”

Section: Discussionsupporting

confidence: 90%

“…Sixth, crystalline fibers radiate from CoCs and form spherulites ( 21 , 22 ), as each crystal fiber grows at the expense of the amorphous precursor phases. All three mineral phases persist in CoCs, as previously observed ( 33 , 39 ).…”

Section: Resultsmentioning

confidence: 99%

“…The morphology and crystal structure of coral skeletons and their layer-by-layer deposition are well understood ( 9 , 17 – 19 ). The aragonite structures include nanoparticulate centers of calcification (CoCs), rich in Mg and organics ( 20 ), elongated acicular crystals termed fibers, radiating out of CoCs, and forming plumose spherulites ( 21 ), with their crystalline c -axes along the radial direction ( 21 ), and randomly oriented crystals called sprinkles, which were only recently observed and were proposed to be proto-fibers: That is, the first nucleated seed of each fiber crystal ( 22 ). When sprinkle crystal c -axes are radially oriented they elongate radially to become fibers; when they are not, they can’t grow and thus remain microscopic (0.2 to 20 μm), or they disappear in a coarsening process ( 22 ).…”

mentioning

confidence: 99%

“…The mechanism of crystal growth, either ion by ion or particle by particle ( 23 ), in coral skeleton is poorly understood and a subject of intense investigation ( 15 , 22 , 24 – 28 ), especially because it is relevant to understand how corals are responding to climate change, including ocean acidification and warming ( 1 – 5 , 18 , 28 ). Because the crystal deposition and growth mechanisms are not yet understood, they cannot be used to maximize the impact of interventions and decision making ( 29 , 30 ).…”

mentioning

confidence: 99%

See 3 more Smart Citations

From particle attachment to space-filling coral skeletons

Sun

Stifler

Chopdekar

et al. 2020

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

Self Cite

View full text Add to dashboard Cite

Reef-building corals and their aragonite (CaCO3) skeletons support entire reef ecosystems, yet their formation mechanism is poorly understood. Here we used synchrotron spectromicroscopy to observe the nanoscale mineralogy of fresh, forming skeletons from six species spanning all reef-forming coral morphologies: Branching, encrusting, massive, and table. In all species, hydrated and anhydrous amorphous calcium carbonate nanoparticles were precursors for skeletal growth, as previously observed in a single species. The amorphous precursors here were observed in tissue, between tissue and skeleton, and at growth fronts of the skeleton, within a low-density nano- or microporous layer varying in thickness from 7 to 20 µm. Brunauer-Emmett-Teller measurements, however, indicated that the mature skeletons at the microscale were space-filling, comparable to single crystals of geologic aragonite. Nanoparticles alone can never fill space completely, thus ion-by-ion filling must be invoked to fill interstitial pores. Such ion-by-ion diffusion and attachment may occur from the supersaturated calcifying fluid known to exist in corals, or from a dense liquid precursor, observed in synthetic systems but never in biogenic ones. Concomitant particle attachment and ion-by-ion filling was previously observed in synthetic calcite rhombohedra, but never in aragonite pseudohexagonal prisms, synthetic or biogenic, as observed here. Models for biomineral growth, isotope incorporation, and coral skeletons’ resilience to ocean warming and acidification must take into account the dual formation mechanism, including particle attachment and ion-by-ion space filling.

show abstract

“…6). This model is consistent with all of the experimental evidence currently available (22,25,26,33,42,60,61) and supersedes the incomplete model proposed by Mass et al (33).…”

Section: Discussionsupporting

confidence: 90%

Section: Resultsmentioning

confidence: 99%

mentioning

confidence: 99%

mentioning

confidence: 99%

See 2 more Smart Citations

From particle attachment to space-filling coral skeletons

Sun

Stifler

Chopdekar

et al. 2020

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

Self Cite

View full text Add to dashboard Cite

show abstract

“…This information can reveal structural and mechanical properties in CaCO 3 biominerals (5). Coral biomineralization is a subject of intense studies, and the mechanisms of crystal nucleation and growth in coral skeletons are only beginning to be revealed (6)(7)(8)(9).…”

mentioning

confidence: 99%

X-ray linear dichroic ptychography

Zhou

Rana

et al. 2021

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

Self Cite

View full text Add to dashboard Cite

Biominerals such as seashells, coral skeletons, bone, and tooth enamel are optically anisotropic crystalline materials with unique nanoscale and microscale organization that translates into exceptional macroscopic mechanical properties, providing inspiration for engineering new and superior biomimetic structures. Using Seriatopora aculeata coral skeleton as a model, here, we experimentally demonstrate X-ray linear dichroic ptychography and map the c-axis orientations of the aragonite (CaCO3) crystals. Linear dichroic phase imaging at the oxygen K-edge energy shows strong polarization-dependent contrast and reveals the presence of both narrow (<35°) and wide (>35°) c-axis angular spread in the coral samples. These X-ray ptychography results are corroborated by four-dimensional (4D) scanning transmission electron microscopy (STEM) on the same samples. Evidence of co-oriented, but disconnected, corallite subdomains indicates jagged crystal boundaries consistent with formation by amorphous nanoparticle attachment. We expect that the combination of X-ray linear dichroic ptychography and 4D STEM could be an important multimodal tool to study nano-crystallites, interfaces, nucleation, and mineral growth of optically anisotropic materials at multiple length scales.

show abstract

Magnesium Ions Direct the Solid‐State Transformation of Amorphous Calcium Carbonate Thin Films to Aragonite, Magnesium‐Calcite, or Dolomite

Zhang

Nahi

Chen

et al. 2022

Adv Funct Materials

View full text Add to dashboard Cite

Amorphous calcium carbonate (ACC) is a common precursor to crystalline calcium carbonate, and is of particular importance in biomineralization, where its crystallization in privileged environments ensures a pseudomorphic transformation. While organisms regulate this process using organic molecules and magnesium ions to selectively form calcite or aragonite, it has proven highly challenging to replicate this polymorph selectivity synthetically. Here, it is demonstrated that remarkable control can be achieved over the chemical composition and structure of crystalline calcium carbonate by using heat to drive a pseudomorphic transformation of ACC thin films. The crystal polymorph can be tuned from low magnesium‐calcite to pure aragonite, high magnesium‐calcite, and ultimately dolomite according to the magnesium content of the ACC, and mosaics of large single crystals are generated at elevated temperatures rather than the spherulitic structures formed at room temperature. This methodology also enables an in situ investigation of the ACC crystallization mechanism using transmission electron microscopy. Finally, the approach can be combined with templating methods to generate arrays of large aragonite single crystals with preselected morphologies. These results demonstrate that exceptional control can be achieved through the solid‐state transformation of Mg‐ACC, which has relevance to both synthetic and biological systems.

show abstract

Crystal nucleation and growth of spherulites demonstrated by coral skeletons and phase-field simulations

Cited by 27 publications

References 98 publications

From particle attachment to space-filling coral skeletons

From particle attachment to space-filling coral skeletons

X-ray linear dichroic ptychography

Magnesium Ions Direct the Solid‐State Transformation of Amorphous Calcium Carbonate Thin Films to Aragonite, Magnesium‐Calcite, or Dolomite

Contact Info

Product

Resources

About