Calcite Growth in Hydrogels: Assessing the Mechanism of Polymer‐Network Incorporation into Single Crystals

Li, Hanying; Estroff, Lara A.

doi:10.1002/adma.200801498

Cited by 130 publications

(218 citation statements)

References 31 publications

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“…One possibility to explain the similar fluorescence and C-H bonding between abiogenic aragonite and coral skeleton is that organic matter from seawater is trapped in growing aragonite crystals (Benzerara et al, 2011). Tendencies toward higher organic indices with increasing Ar (Figures 5A-C, r 2 between 0.24 and 0.56) may suggest this organic trapping mechanism increases under more rapid crystal growth as has been observed previously for calcite (Li and Estroff, 2009), but this interpretation remains inconclusive due to the lack of statistically significant correlations between the metrics and Ar (0.05 < p < 0.10).…”

Section: Discussion Organic Matter In Abiogenic and Coral Samplesmentioning

confidence: 52%

“…We plotted these metrics against fluid Ar in order to (1) visualize any differences among samples, and (2) assess whether organic matter content correlates with Ar , which could indicate that more organic molecules are trapped in faster growing crystals (Perrin and Smith, 2007;Li and Estroff, 2009;Benzerara et al, 2011). There was a general tendency of increasing fluorescence with Ar in abiogenic samples (Figure 5A), but the large variance within samples precludes any definitive interpretations and the pattern was not significant [r 2 = 0.56, n = 7, p = 0.053, F (1, 5) = 6.397].…”

Section: Resultsmentioning

confidence: 99%

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The Origin and Role of Organic Matrix in Coral Calcification: Insights From Comparing Coral Skeleton and Abiogenic Aragonite

DeCarlo¹,

Ren²,

Farfán³

2018

Front. Mar. Sci.

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Understanding the mechanisms of coral calcification is critical for accurately projecting coral reef futures under ocean acidification and warming. Recent suggestions that calcification is primarily controlled by organic molecules and the biological activity of the coral polyp imply that ocean acidification may not affect skeletal accretion. The basis for these suggestions relies heavily on correlating the presence of organic matter with the orientation and disorder of aragonite crystals in the skeleton, carrying the assumption that organic matter observed in the skeleton was produced by the polyp to control calcification. Here we use Raman spectroscopy to test whether there are differences in organic matter content between coral skeleton and abiogenic aragonites precipitated from seawater, both before and after thermal annealing (heating). We measured the background fluorescence and intensity of C-H bonding signals in the Raman spectra, which are commonly attributed to coral polyp-derived skeletal organic matrix (SOM) and have been used to map its distribution. Surprisingly, we found no differences in either fluorescence or C-H bonding between abiogenic aragonite and coral skeleton. Annealing reduced the molecular disorder in coral skeleton, potentially due to removal of organic matter, but the same effect was also observed in the abiogenic aragonites. The presence of organic molecules in the abiogenic aragonites is further supported by measurements of N content and δ 15 N. Together, our data suggest that some of what has been interpreted in previous studies as polyp-derived SOM may actually be seawater-sourced organic matter or some other signal not unique to biogenic aragonite. Finally, we create a high-resolution Raman map of a Pocillopora skeleton to demonstrate how patterns of fluorescence and elevated calcifying fluid aragonite saturation state ( Ar ) along centers of calcification are consistent with both biological and physico-chemical controls. Our aim is to advance discussion on biological mediation of calcification and the implications for coral resilience in a high-CO 2 world.

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Section: Discussion Organic Matter In Abiogenic and Coral Samplesmentioning

confidence: 52%

Section: Resultsmentioning

confidence: 99%

The Origin and Role of Organic Matrix in Coral Calcification: Insights From Comparing Coral Skeleton and Abiogenic Aragonite

DeCarlo¹,

Ren²,

Farfán³

2018

Front. Mar. Sci.

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“…Properties of the gel matrix such as density, porosity, mechanical stress and chemical nature have a significant bearing on crystal growth. For instance, calcite crystals grown in agarose hydrogels incorporate gel structures depending on the kinetics of crystal growth and the gel strength of the media (Li and Estroff 2009). A weak gel of agarose is pushed away by the growth fronts of the crystal, whereas a strong gel resists deformation, leading to calcite crystals that grow around and incorporate the fibers.…”

Section: Mineralization In Matrices and Gelsmentioning

confidence: 99%

Mineralization and non-ideality: on nature’s foundry

Rao¹,

Cölfen

2016

Biophys Rev

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Understanding how ions, ion-clusters and particles behave in non-ideal environments is a fundamental question concerning planetary to atomic scales. For biomineralization phenomena wherein diverse inorganic and organic ingredients are present in biological media, attributing biomaterial composition and structure to the chemistry of singular additives may not provide a holistic view of the underlying mechanisms. Therefore, in this review, we specifically address the consequences of physico-chemical non-ideality on mineral formation. Influences of different forms of non-ideality such as macromolecular crowding, confinement and liquid-like organic phases on mineral nucleation and crystallization in biological environments are presented. Novel prospects for the additive-controlled nucleation and crystallization are accessible from this biophysical view. In this manner, we show that non-ideal conditions significantly affect the form, structure and composition of biogenic and biomimetic minerals.

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“…On the other hand, the incorporation of polymer networks into the calcium carbonate single crystals follows different mechanisms from the incorporation of particles. Li et al studied the occlusion of 3D agarose hydrogel into the single crystals of calcium carbonate and found that besides the gel concentration and the rate of the crystal growth, the strength of hydrogel was also an important factor for either complete incorporation of gel network into the crystal lattice or total exclusion of the gel material from the crystal structure [30]. Using annular dark-field scanning TEM, they were able to visualize the 3D structure of hydrogel networks inside the single crystals.…”

Section: Introductionmentioning

confidence: 99%

Occlusion of magnetic nanoparticles within calcium carbonate single crystals under external magnetic field

Zhang

Huang

Tao

et al. 2017

Pure and Applied Chemistry

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This work studied the growth of calcium carbonate single crystals on top of the monolayer of Fe 3 O 4 @SiO 2 nanoparticles (NPs) with added external magnetic field. It showed that the occlusion process of the NPs into calcium carbonate single crystals varies as the force balance on the NPs shifts. Under no or weak magnetic field, the NPs are relatively mobile, the separation force from the substrate on NPs due to the growing calcium carbonate crystals is larger than the attraction force to the substrate by the magnetic field. The complete occlusion of the NPs into the single crystals is therefore observed. As the magnetic field strength increases, the balance shifts toward the attraction force. The mobility of NPs decreases and partial occlusion of the NPs into the single crystals is gradually observed. The findings in this study offer further insight into the occlusion process experienced by the NPs and also potential approach in engineering the force balance for the design and generation of composite materials that occlude foreign materials into their matrix.

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Calcite Growth in Hydrogels: Assessing the Mechanism of Polymer‐Network Incorporation into Single Crystals

Cited by 130 publications

References 31 publications

The Origin and Role of Organic Matrix in Coral Calcification: Insights From Comparing Coral Skeleton and Abiogenic Aragonite

The Origin and Role of Organic Matrix in Coral Calcification: Insights From Comparing Coral Skeleton and Abiogenic Aragonite

Mineralization and non-ideality: on nature’s foundry

Occlusion of magnetic nanoparticles within calcium carbonate single crystals under external magnetic field

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