Oriented crystallization of calcite single crystals grown underneath monolayers of tetracarboxyresorc[4]arenes

Volkmer, Dirk; Fricke, Marc; Agena, Ceno; Mattay, Jochen

doi:10.1039/b202208g

Cited by 42 publications

(42 citation statements)

References 33 publications

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“…16) [93][94][95]. However, in spite of these fundamental differences in molecular structure, crystallization assays employing monolayers of 14 gave (01.2) oriented calcite crystals that were virtually indistinguishable from those that grew beneath monolayers of 12 or 13.…”

Section: Influence Of Coordination Geometrymentioning

confidence: 82%

“…Right: Structural formula of tetracarboxy-resorc [4]arene 14, which according to X-ray analytical investigations and NMR studies assumes a C 2v -symmetric boat conformation [95] In summary, the results of these investigations demonstrated that neither calixarene nor resorcarene derivatives have a tendency to form highly ordered liquid-crystalline phases during compression. Moreover, the growth of (01.2) oriented calcite crystals exclusively occurred at low surface pressure (π = 0.…”

Section: Scheme 5 Leftmentioning

confidence: 92%

“…In order to answer this critical question, a second type of macrocyclic ligands, the tetracarboxy-resorc [4]arene rccc -5,11,17,23-tetracarboxy-4,6,10,12,16,18, 22,24-octa-O-methyl-2,8,14,20-tetra(n-undecyl)resorc [4]arene (14; Scheme 5), was designed and used in crystallization assays [95].…”

Section: Influence Of Coordination Geometrymentioning

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: Influence Of Coordination Geometrymentioning

confidence: 82%

Section: Scheme 5 Leftmentioning

confidence: 92%

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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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“…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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confidence: 99%

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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“…The so-called molecular recognition is assumed to facilitate the nucleation of calcite [9,37] alter the habit of the growing crystal [2,35,36] or trigger the crystallisation of a specific polymorph [8,10,38]. However, the postulated mechanism of epitaxial growth of calcium carbonate on macromolecular arrangements has been discussed critically recently [33][34][35][36][37][38][39][40][41].…”

Section: Discussionmentioning

confidence: 99%

Growth of calcium carbonate in polyacrylamide hydrogel: Investigation of the influence of polymer content

Helbig

2008

Journal of Crystal Growth

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Oriented crystallization of calcite single crystals grown underneath monolayers of tetracarboxyresorc[4]arenes

Cited by 42 publications

References 33 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?

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

Growth of calcium carbonate in polyacrylamide hydrogel: Investigation of the influence of polymer content

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