Chiral acidic amino acids induce chiral hierarchical structure in calcium carbonate

Jiang, Wenge; Pacella, Michael S.; Athanasiadou, Dimitra; Nelea, Valentin; Vali, Hojatollah; Hazen, Robert M.; Gray, Jeffrey J.; McKee, Marc D.

doi:10.1038/ncomms15066

Cited by 143 publications

(180 citation statements)

References 54 publications

(88 reference statements)

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“…At a higher magnification, FE-SEM imaging disclosed a nanogranular structure made up of oriented vaterite nanoparticles (Figure 5d). The latter observation points to a structural development via (oriented) nanoparticle aggregation (Figure 5d), as reported by Jiang et al [40]. …”

Section: Particle Size and Phase Evolutionsupporting

confidence: 62%

Hydration Effects on the Stability of Calcium Carbonate Pre-Nucleation Species

et al. 2017

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Recent experimental evidence and computer modeling have shown that the crystallization of a range of minerals does not necessarily follow classical models and theories. In several systems, liquid precursors, stable pre-nucleation clusters and amorphous phases precede the nucleation and growth of stable mineral phases. However, little is known on the effect of background ionic species on the formation and stability of pre-nucleation species formed in aqueous solutions. Here, we present a systematic study on the effect of a range of background ions on the crystallization of solid phases in the CaCO 3 -H 2 O system, which has been thoroughly studied due to its technical and mineralogical importance, and is known to undergo non-classical crystallization pathways. The induction time for the onset of calcium carbonate nucleation and effective critical supersaturation are systematically higher in the presence of background ions with decreasing ionic radii. We propose that the stabilization of water molecules in the pre-nucleation clusters by background ions can explain these results. The stabilization of solvation water hinders cluster dehydration, which is an essential step for precipitation. This hypothesis is corroborated by the observed correlation between parameters such as the macroscopic equilibrium constant for the formation of calcium/carbonate ion associates, the induction time, and the ionic radius of the background ions in the solution. Overall, these results provide new evidence supporting the hypothesis that pre-nucleation cluster dehydration is the rate-controlling step for calcium carbonate precipitation.

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Section: Particle Size and Phase Evolutionsupporting

confidence: 62%

Hydration Effects on the Stability of Calcium Carbonate Pre-Nucleation Species

et al. 2017

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“…Previous studies show that calcite crystals grown in the presence of either L or D aspartic acid present asymmetry associated with the distribution of crystal steps and terraces [88,89], and even the CaCO3 polymorph could be controlled by the chirality of an interacting amino acid [90]. The amplification of these interactions at macroscopic length scales is demonstrated by the distinct chirality of vaterite toroids and the helicity of potassium dichromate crystals tuned by the enantiospecificity of amino acids [91,92]. In view of mineral nucleation, we show that the sugar enantiomers present distinct interactions with mineral precursors and as a consequence affect the nucleation process in a pH-dependent manner.…”

Section: Discussionmentioning

confidence: 99%

Modulating Nucleation by Kosmotropes and Chaotropes: Testing the Waters

2017

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Abstract:Water is a fundamental solvent sustaining life, key to the conformations and equilibria associated with solute species. Emerging studies on nucleation and crystallization phenomena reveal that the dynamics of hydration associated with mineral precursors are critical in determining material formation and growth. With certain small molecules affecting the hydration and conformational stability of co-solutes, this study systematically explores the effects of these chaotropes and kosmotropes as well as certain sugar enantiomers on the early stages of calcium carbonate formation. These small molecules appear to modulate mineral nucleation in a class-dependent manner. The observed effects are finite in comparison to the established, strong interactions between charged polymers and intermediate mineral forms. Thus, perturbations to hydration dynamics of ion clusters by co-solute species can affect nucleation phenomena in a discernable manner.

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“…Insulators can also be well observed without any coating layer. In this review, except for those observations in HiVac, we focus on observations of samples in the gaseous modes (LoVac or ESEM). Note that in most ESEM experiments, water vapor is used as the background gas.…”

Section: Recent Applicationsmentioning

confidence: 99%

Applications of ESEM on Materials Science: Recent Updates and a Look Forward

et al. 2019

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The microscopic understanding of materials relies on the development of microscopy. Historically, the technological evolution from optical microscopes to electron microscopes has directly stimulated many discoveries of new physical and chemical fundamentals as well as advanced materials. Scanning electron microscopy (SEM) is, undoubtedly, the most widely used tool for microscopic characterization in modern materials science. Especially, the incorporation of a gas pressure around the sample area of conventional SEM, i.e., the environmental scanning electron microscope (ESEM), has opened new possibilities in observing samples in their natural states, leading to unprecedented chances for studying the details of biological, organic, and hydrated samples. What is more, in recent years, in situ ESEM studies concerning materials change and chemical reactions have played a more important role in the field of materials science. Herein, the recent applications of ESEM in materials science are comprehensively reviewed, in terms of common static observations for various materials and in situ investigations of dynamic processes in controlled experimental environments. Moreover, the problems concerning state‐of‐the‐art ESEM experiments are discussed, as well as possible solutions. Looking forward, the rapid developments on instrumentation and fundamental science of ESEM can bring a clear vision of materials in the near future.

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Chiral acidic amino acids induce chiral hierarchical structure in calcium carbonate

Cited by 143 publications

References 54 publications

Hydration Effects on the Stability of Calcium Carbonate Pre-Nucleation Species

Hydration Effects on the Stability of Calcium Carbonate Pre-Nucleation Species

Modulating Nucleation by Kosmotropes and Chaotropes: Testing the Waters

Applications of ESEM on Materials Science: Recent Updates and a Look Forward

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