Incorporation of organic and inorganic impurities into the lattice of metastable vaterite

Seknazi, Eva; Mijowska, Sylwia; Polishchuk, Iryna; Pokroy, Boaz

doi:10.1039/c9qi00849g

Cited by 16 publications

(14 citation statements)

References 52 publications

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“…[20] Many of these protein mixtures have been tested in vitro for their abilityt oi nhibitt he precipitation of CaCO 3 , [10] or to modify the size and morphologyo fc alcite crystals. [21] More surprisingly, proteins, [22,23] or their most elementary building blocks, amino acids, [24][25][26][27] were found to induce anisotropic lattice distortions in their calcitic, aragonitic, or vateritic crystalline hosts. Several synthetic assays also showedt hat other molecules can be incorporated into calcite, such as gels, [28,29] diblock copolymer particles, [30] and manym ore.…”

Section: Introductionmentioning

confidence: 99%

Acidic Monosaccharides become Incorporated into Calcite Single Crystals**

Lang

Mijowska

Polishchuk

et al. 2020

Chemistry A European J

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Carbohydrates, along with proteins and peptides, are known to represent a major class of biomacromolecules involved in calcium carbonate biomineralization. However, in spite of multiple physical and biochemical characterizations, the explicit role of saccharide macromolecules (long chains of carbohydrate molecules) in mineral deposition is not yet understood. In this study, we investigated the influence of two common acidic monosaccharides (MSs), the two simplest forms of acidic carbohydrates, namely glucuronic and galacturonic acids, on the formation of calcite crystals in vitro. We show here that the size, morphology, and microstructure of calcite crystals are altered when they are grown in the presence of these MSs. More importantly, these MSs were found to become incorporated into the calcite crystalline lattice and induce anisotropic lattice distortions, a phenomenon widely studied for other biomolecules related to CaCO3 biomineralization, but never before reported in the case of single MSs. Changes in the calcite lattice induced by MSs incorporation were precisely determined by high‐resolution synchrotron powder X‐ray diffraction. We believe that the results of this research may deepen our understanding of the interaction of saccharide polymers with an inorganic host and shed light on the implications of carbohydrates for biomineralization processes.

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Section: Introductionmentioning

confidence: 99%

Acidic Monosaccharides become Incorporated into Calcite Single Crystals**

Lang

Mijowska

Polishchuk

et al. 2020

Chemistry A European J

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“…It forms by interaction between additives and calcium or carbonate ions, which lowers the concentration of free ions, thus inducing the formation of vaterite. ,, Slow nucleation rates delay the formation of the more stable polymorphs (aragonite and calcite), so that vaterite can form . Indeed, vaterite crystals were successfully synthesized by using additives containing charged groups such as amines, − carboxyl groups, ,− sulfonic groups, , amino acids, , peptides, polyols, , and proteins. , Vaterite crystals have been synthesized in aqueous solutions, − ,,,,,− alcohol–water mixed solvents, ,,, DMF–water mixed solvents, , and nonaqueous solvents. ,, Wetting and hydration of ions in alcohol–water solvents are very different from those found in aqueous solutions, which may affect the formation of nucleation and crystal growth centers. The low solubility and high supersaturation of CaCO 3 in alcohols are in favor of the formation of kinetic products (thermodynamically unstable phases such as vaterite).…”

Section: Introductionmentioning

confidence: 99%

Vaterite Microdisc Mesocrystals Exposing the (001) Facet Formed via Transformation from Proto-Vaterite Amorphous Calcium Carbonate

Zhang

Yan

et al. 2020

Crystal Growth & Design

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Vaterite is the thermodynamically least stable phase of the three anhydrous calcium carbonate phases. So far there have been no reports showing the synthesis of pure phase vaterite single crystals exposing the (001) facet without the aid of any additive. Herein, single crystalline vaterite microdiscs exposing the (001) facet with high surface energy have been successfully obtained for the first time in isopropanol without the presence of any additives. The process progresses via amorphous calcium carbonate (ACC) precursors. To study this, Ca K-edge extended X-ray absorption fine structure characterization was performed under cryo-condition. The results indicate that the ACC precursor has a short-range order structure similar to that of vaterite, previously named “proto-vaterite ACC”. Molecular dynamic (MD) simulations indicate that the binding energy between the (001) facet of vaterite and isopropanol is much higher than those of other facets of vaterite with isopropanol, which might be the reason for the formation of vaterite microdiscs exposing the (001) facet. In summary, the thermodynamically less stable phase vaterite microdiscs exposing the (001) facet were realized for the first time without the presence of any additive, and its formation mechanism was investigated in detail based on the experimental results and MD simulations.

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“…Figure presents the resulting HR-SEM micrographs. Without any additives, the crystals exhibit the characteristic rhombohedral morphology of calcite. ,, When nucleotides are added, the spherical morphology of vaterite appears in the shape of the crystals . Furthermore, employing energy-dispersive spectroscopy (EDS) in the SEM confirmed that P atoms can indeed be detected within the vaterite crystals (Figure S8).…”

Section: Resultsmentioning

confidence: 86%

“…The field of bio-inspired crystal growth encompasses research that aims at developing novel materials using strategies found in Nature. , In the realm of CaCO 3 , efforts were made to understand the impact of various crystallization conditions and additives on the resulting structure, shape, and physical properties of the crystals. For the last decade, our group, − as well as others, ,− have shown that calcite and vaterite, two of the anhydrous polymorphs of CaCO 3 , can incorporate both organic and inorganic additives. Specifically, it was demonstrated that the building blocks of proteins and polysaccharides, namely, amino acids (AAs) ,, and monosaccharides (MSs), respectively, can be incorporated into the crystal lattice of the host, and induce changes in its lattice parameters.…”

Section: Introductionmentioning

confidence: 88%

Effect of Nucleotides on the Phase and Crystal Structure of Synthetic Calcium Carbonate

Lang

Polishchuk

Katsman

et al. 2023

Crystal Growth & Design

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The interactions of organic hereditary materials (i.e., DNA and RNA) with inorganic minerals are of key importance in many fields of research, from archeology and paleontology to medicine. It was previously shown that the building blocks of the main structural biomacromolecules, amino acids and monosaccharides, can be incorporated into the crystal lattice of calcium carbonate (CaCO 3 ), the most abundant biomineral. Here, we continue this reductionist approach and study how the mineral host is affected when grown in the presence of mono-or triphosphate nucleotides�the building blocks of nucleic acids. We show that the nucleotides facilitate the stabilization of the amorphous polymorph of CaCO 3 , as well as promote the formation of vaterite, its least thermodynamically stable anhydrous crystalline phase. We use high-resolution powder X-ray diffraction, and a variety of chemical analysis tools, to demonstrate the mechanism by which nucleotides become incorporated within the vaterite lattice.

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Incorporation of organic and inorganic impurities into the lattice of metastable vaterite

Abstract: Highly substituted Mg-vaterite and Ba-vaterite were synthesized in the presence of aspartic acid and characterized by means of synchrotron XRD.

Cited by 16 publications

References 52 publications

Acidic Monosaccharides become Incorporated into Calcite Single Crystals**

Acidic Monosaccharides become Incorporated into Calcite Single Crystals**

Vaterite Microdisc Mesocrystals Exposing the (001) Facet Formed via Transformation from Proto-Vaterite Amorphous Calcium Carbonate

Effect of Nucleotides on the Phase and Crystal Structure of Synthetic Calcium Carbonate

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