Crystallization of (012) oriented calcite single crystals underneath monolayers of tetra(carboxymethoxy)calix[4]arenes

Volkmer, Dirk; Fricke, Marc; Vollhardt, D.; Siegel, Stefan

doi:10.1039/b206912a

Cited by 48 publications

(48 citation statements)

References 40 publications

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“…15) [93,94]. The fact that identically oriented calcite crystals are obtained under monolayers of differently sized calix [4]arenes gives a strong indication against the assumption that an epitaxial match between the monolayer and the juxtaposed crystal surface is required for inducing a certain crystal growth behavior.…”

Section: Crystallization Of Caco 3 Beneath Monolayers Of Macrocyclic mentioning

confidence: 96%

“…The viewing direction is parallel to the monolayer surface normal, and crystals are observed from below the aqueous subphase. (Reprinted from [93] with permission) [4]arene (13) -were investigated, which differ from each other by the bulkiness of hydrophobic substituents at the upper-rim of the macrocyclic backbone (Scheme 4).…”

Section: Crystallization Of Caco 3 Beneath Monolayers Of Macrocyclic mentioning

confidence: 99%

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Crystallization of Calcium Carbonate Beneath Insoluble Monolayers: Suitable Models of Mineral–Matrix Interactions in Biomineralization?

Fricke

Volkmer

2006

Topics in Current Chemistry

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Section: Crystallization Of Caco 3 Beneath Monolayers Of Macrocyclic mentioning

confidence: 96%

Section: Crystallization Of Caco 3 Beneath Monolayers Of Macrocyclic mentioning

confidence: 99%

Crystallization of Calcium Carbonate Beneath Insoluble Monolayers: Suitable Models of Mineral–Matrix Interactions in Biomineralization?

Fricke

Volkmer

2006

Topics in Current Chemistry

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“…Complementary investigations by our group, [10] among others, [11] in which non-immobilized monolayers of amphiphilic macrocycles were employed, on the other hand have shown that the average charge distribution at the template surface is the predominant factor that governs the selection of crystal polymorphs and the orientation of crystals.…”

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confidence: 98%

Morphosynthesis of Nacre‐Type Laminated CaCO₃ Thin Films and Coatings

et al. 2005

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“…Note that a well-developed, preferred orientation of the [012] type was also detected for synthetic calcite growth on monolayer templates consisting of alkanethiols terminated by COO -groups on a gold substrate, [34] or macromolecules of calixarenes and resorcarenes. [35,36] In order to explain anisotropic lattice distortions, we assume that the intracrystalline organic molecules are not just adhering to the specific crystal planes. Since these macromolecules are rich in aspartic and glutamic residues, [37] their COO -groups could coherently substitute some of the carbonate groups in the calcite structure.…”

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The Microstructure of Biogenic Calcite: A View by High‐Resolution Synchrotron Powder Diffraction

2006

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Biogenic crystals, i.e., crystals produced by living organisms, have attracted a great deal of attention in latter years because of their fascinating microstructures and superior properties. [1][2][3] The interrelation between the microstructure of materials and their properties is a key issue of materials science. Impressive examples of scientific achievements in this field include our ability to control the strength of metals and alloys by annealing-mediated grain size, [4] and bandgap engineering in semiconductor thin film structures by lattice mismatch-mediated interfacial strains. [5] At the same time, unique methods for controlling microstructure and, hence, crystal properties, exist in nature. In fact, organisms can control the polymorphism, [6][7][8] morphology, [9] orientation, and size of crystalline blocks [10] in biogenic crystals by means of organic molecules involved in the biomineralization process. These organic molecules can stabilize an amorphous precursor phase, [11][12][13][14] which might also play an important role in the control of the material properties of the end product. However, not much is yet known about the molecular mechanisms that control the interaction between the organic phase and the growing mineral. In this paper, we shed additional light on these interactions by tracking the microstructure modifications in biogenic calcite after heat treatments at elevated temperatures. Our findings allow us to better understand the microstructure of biocomposites on a nanometer scale, which we believe is of great importance to future design and fabrication of bio-inspired advanced materials. At the end of the 1980s, Berman et al. [15] showed that occluded organic molecules are located within biogenic calcite (CaCO 3 ) crystals and proposed that these intracrystalline molecules reveal chemical recognition to specific atomic planes. The researchers suggested that during biomineralization, the organic macromolecules adhere to specific planes and impede crystal growth in the perpendicular direction, which respectively lowers the size of coherently scattered crystal blocks. [15][16][17] This fact indicates that organisms can also control the preferred orientation (texture) of biogenic crystals. By measuring the "coherent lengths" for X-ray scattering along different directions in biogenic calcite crystals and then comparing these values with those in synthetic calcite, the researchers were able to determine the crystallographic planes on which the organic molecules presumably adhere. However, to date we have practically no information about the specific types of macromolecules, their conformation states, and how exactly they match the mineral structure. Very recently we showed that organisms could control not only the texture, but in some sense the atomic structure of biogenic crystals. Specifically, by using high-resolution X-ray powder diffraction at dedicated synchrotron beam lines, we found anisotropic lattice distortions in mollusk-made aragonite [18] and calcite, [19] as compared to their ...

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Crystallization of (012) oriented calcite single crystals underneath monolayers of tetra(carboxymethoxy)calix[4]arenes

Cited by 48 publications

References 40 publications

Crystallization of Calcium Carbonate Beneath Insoluble Monolayers: Suitable Models of Mineral–Matrix Interactions in Biomineralization?

Crystallization of Calcium Carbonate Beneath Insoluble Monolayers: Suitable Models of Mineral–Matrix Interactions in Biomineralization?

Morphosynthesis of Nacre‐Type Laminated CaCO₃ Thin Films and Coatings

The Microstructure of Biogenic Calcite: A View by High‐Resolution Synchrotron Powder Diffraction

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Crystallization of (012) oriented calcite single crystals underneath monolayers of tetra(carboxymethoxy)calix[4]arenes

Cited by 48 publications

References 40 publications

Crystallization of Calcium Carbonate Beneath Insoluble Monolayers: Suitable Models of Mineral–Matrix Interactions in Biomineralization?

Crystallization of Calcium Carbonate Beneath Insoluble Monolayers: Suitable Models of Mineral–Matrix Interactions in Biomineralization?

Morphosynthesis of Nacre‐Type Laminated CaCO3 Thin Films and Coatings

The Microstructure of Biogenic Calcite: A View by High‐Resolution Synchrotron Powder Diffraction

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Morphosynthesis of Nacre‐Type Laminated CaCO₃ Thin Films and Coatings