Intercalation of sea urchin proteins in calcite: study of a crystalline composite material

Sea urchin skeletal elements are composed of single crystals of calcite. Unlike their synthetic counterparts, these crystals do not have well-developed cleavage and are consequently much more resistant to fracture. This phenomenon is due in part to the presence of acidic glycoproteins occluded within the crystals. By means of x-ray diffraction with synchrotron radiation, it is shown that the presence of the protein in synthetic calcite only slightly decreases the coherence length but significantly increases the angular spread of perfect domains of the crystals. In biogenic calcite, the coherence length is 1/3 to 1/4 as much as that in synthetic calcite and the angular spread is 20 to 50 times as wide. It is proposed that the presence of macromolecules concentrated at mosaic boundaries that are oblique to deavage planes is responsible for the change in fracture properties. These results may be important in the material sciences, because of the unusual nature of this material, namely, a composite based on the controlled intercalation of macromolecules inside single-crystal lattices.     

Biological control of crystal texture: a widespread strategy for adapting crystal properties to function

Textures of calcite crystals from a variety of mineralized tissues belonging to organisms from four phyla were examined with high-resolution synchrotron x-ray radiation. Significant differences in coherence length and angular spread were observed between taxonomic groups. Crystals from polycrystalline skeletal ensembles were more perfect than those that function as single-crystal elements. Different anisotropic effects on crystal texture were observed for sea urchin and mollusk calcite crystals, whereas none was found for the foraminifer, Patellina, and the control calcite crystals. These results show that the manipulation of crystal texture in different organisms is under biological control and that crystal textures in some tissues are adapted to function. A better understanding of this apparently widespread biological phenomenon may provide new insights for improving synthetic crystal-containing materials.     

Direct fabrication of large micropatterned single crystals

Micropatterning of single crystals for technological applications is a complex, multistep process. Nature provides alternative fabrication strategies, when crystals with exquisite micro-ornamentation directly develop within preorganized frameworks. We report a bio-inspired approach to growing large micropatterned single crystals. Micropatterned templates organically modified to induce the formation of metastable amorphous calcium carbonate were imprinted with calcite nucleation sites. The template-directed deposition and crystallization of the amorphous phase resulted in the fabrication of millimeter-sized single calcite crystals with sub-10-micron patterns and controlled crystallographic orientation. We suggest that in addition to regulating the shape, micropatterned frameworks act as sites for stress and impurity release during the amorphous-to-crystalline transition. The proposed mechanisms may have direct biological relevance and broad implications in materials synthesis.     

Polycrystalline echinoderm calcite and its fracture mechanics

Polycrystalline calcite was revealed by scanning electron microscopy of fractured skeletal ossicles of the sea star Echinaster spinulosus (Echinodermata, Asteroidea). Whisker-like calcite crystals were observed in specimens that were loaded in stress relaxation before being fractured; rapidly broken surfaces were smooth and glassy. The crystallites were 1300 angstroms wide and at least 3600 angstroms long and were packed together in lamellae. The lamellae were wound into spirals that formed the trabecular bars. All the crystallites in an ossicle appear to be aligned in the same direction. Geometric considerations indicate that the requirement for packing the crystallites smoothly may explain the high magnesium ion concentration of echinoderm calcite.     

Skeletal low-magnesium calcite in living scleractinian corals

The skeletons of living specimens of the scleractinian coral Porites lobata have been found to contain up to 46 +/- 5 percent low-magnesium calcite even though free of gross detrital inclusions and boring or encrusting organisms. The calcite crystals occur in the interior of skeletal structures, have dimensions of 20 micrometers or less, and are surrounded by typical aragonite needles. Biogenic deposition seems to be the most likely source of the calcite, although the evidence does not rule out diagenesis of metastable.     

UNMINERALIZED FOSSIL BACTERIA

Unmineralized bacterial cells, mostly Micrococcus sp., but including also Streptococcus sp. and Actinomyces sp., were found in enormous numbers in lake beds of the Newark Canyon Formation of Early Cretaceous age, Eureka County, Nevada. The micrococci are black, and have an average diameter about 0.5 micro. Similar black micrococci (0.4 to 0.7 micro) were found in profusion in the bottom mud of Green Lake, New York. About 80 percent of this mud consists of minute idiomorphic calcite crystals and about 20 percent of these contain enormous numbers of the black micrococci. It is suggested that the Early Cretaceous bacterial cells owe their preservation to occlusion in calcite crystals that grew in a black, bacterial mud in a meromictic lake in which part of the Newark Canyon Formation accumulated.     

Attempt to date early South african hominids by using fission tracks in calcite

Calcite crystals extracted from marrow cavities of bones found in hominid-bearing breccias from Makapansgat and Swartkrans were studied for fossil tracks. The absence of the expected numbers of tracks in these and in calcites from Beds I and II, Olduvai Gorge, combined with the results of laboratory heating experiments, indicates that track annealing has occurred at ambient temperatures and precludes the widespread use of calcite for fission track dating.     

Sea urchin spine calcite forms via a transient amorphous calcium carbonate phase

The skeletons of adult echinoderms comprise large single crystals of calcite with smooth convoluted fenestrated morphologies, raising many questions about how they form. By using water etching, infrared spectroscopy, electron diffraction, and environmental scanning electron microscopy, we show that sea urchin spine regeneration proceeds via the initial deposition of amorphous calcium carbonate. Because most echinoderms produce the same type of skeletal material, they probably all use this same mechanism. Deposition of transient amorphous phases as a strategy for producing single crystals with complex morphology may have interesting implications for the development of sophisticated materials.     

Biomolecular interactions at phospholipid-decorated surfaces of liquid crystals

The spontaneous assembly of phospholipids at planar interfaces between thermotropic liquid crystals and aqueous phases gives rise to patterned orientations of the liquid crystals that reflect the spatial and temporal organization of the phospholipids. Strong and weak specific-binding events involving proteins at these interfaces drive the reorganization of the phospholipids and trigger orientational transitions in the liquid crystals. Because these interfaces are fluid, processes involving the lateral organization of proteins (such as the formation of protein- and phospholipid-rich domains) are also readily imaged by the orientational response of the liquid crystal, as are stereospecific enzymatic events. These results provide principles for label-free monitoring of aqueous streams for molecular and biomolecular species without the need for complex instrumentation.     

Deep ultraviolet light-emitting hexagonal boron nitride synthesized at atmospheric pressure

Materials emitting light in the deep ultraviolet region around 200 nanometers are essential in a wide-range of applications, such as information storage technology, environmental protection, and medical treatment. Hexagonal boron nitride (hBN), which was recently found to be a promising deep ultraviolet light emitter, has traditionally been synthesized under high pressure and at high temperature. We successfully synthesized high-purity hBN crystals at atmospheric pressure by using a nickel-molybdenum solvent. The obtained hBN crystals emitted intense 215-nanometer luminescence at room temperature. This study demonstrates an easier way to grow high-quality hBN crystals, through their liquid-phase deposition on a substrate at atmospheric pressure.     

Premelting at defects within bulk colloidal crystals

Premelting is the localized loss of crystalline order at surfaces and defects at temperatures below the bulk melting transition. It can be thought of as the nucleation of the melting process. Premelting has been observed at the surfaces of crystals but not within. We report observations of premelting at grain boundaries and dislocations within bulk colloidal crystals using real-time video microscopy. The crystals are equilibrium close-packed, three-dimensional colloidal structures made from thermally responsive microgel spheres. Particle tracking reveals increased disorder in crystalline regions bordering defects, the amount of which depends on the type of defect, distance from the defect, and particle volume fraction. Our observations suggest that interfacial free energy is the crucial parameter for premelting in colloidal and atomic-scale crystals.     

Crystal growth of silicon and germanium in metal films

Amorphous silicon in contact with silver films and amorphous germanium in contact with aluminum films form crystalline precipitates when heated to temperatures well below those at which any liquid phase is present. Crystallization occurs by an initial dissolution of the semiconductor into the metal filmsolvent followed by the growth of crystals out of the solvent.     

Synthesis of zeolite as ordered multicrystal arrays

Zeolites are crystalline nanoporous aluminosilicates widely used in industry. In order for zeolites to find applications as innovative materials, they need to be organized into large two- and three-dimensional (2D and 3D) arrays. We report that uniformly aligned polyurethane films can serve as templates for the synthesis of uniformly aligned 2D and possibly 3D arrays of silicalite-1 crystals, in which the orientations of the crystals are controlled by the nature of the polymers. We propose that the supramolecularly organized organic-inorganic composites that consist of the hydrolyzed organic products and the seed crystals are responsible for this phenomenon.     

Optical switching and image storage by means of azobenzene liquid-crystal films

Liquid crystals are promising materials for optical switching and image storage because of their high resolution and sensitivity. Azobenzene liquid crystals (LCs) have been developed, in which azobenzene moieties play roles as both mesogens and photosensitive chromophores. Azobenzene LC films showed a nematic phase in trans isomers and no LC phase in cis isomers. Trans-cis photoisomerization of azobenzene with a laser pulse resulted in a nematic-to-isotropic phase transition with a rapid optical response of 200 microseconds.     

Molecular recognition at crystal interfaces

Nucleation, growth, and dissolution of crystals have been studied by stereochemical approach involving molecular recognition at interfaces. A methodology is described for using ;;tailor-made' additives designed to interact stereospecifically with crystal surfaces during growth and dissolution. This procedure was instrumental in controlling crystal morphology and in revising the concept of the structure and symmetry of solid solutions. Consequently, it was applied to the transformation of centrosymmetric single crystals into solid solutions with polar arrangement displaying second-harmonic generation and to the performance of asymmetric synthesis of guest molecules inside centrosymmetric host crystals. The method has led to a discovery of a new ;;relay' mechanism explaining the effect of solvent on crystal growth. Finally, it allowed for the design of auxiliary molecules that act as promoters or inhibitors of crystal nucleation that can be used to resolve enantiomers and crystallize desired polymorphs.     

Direct observation of structural defects in laser-deposited superconducting y-ba-cu-o thin films

The defect structure of in situ pulsed, laser-deposited, thin films of the high-transition temperature superconductor Y-Ba-Cu-O has been observed directly by atomic resolution electron microscopy. In a thin film with the nominal composition YBa(2)Cu(3)O(7) (123), stacking defects corresponding to the cationic stoichiometry of the 248, 247, and 224 compounds have been observed. Other defects observed include edge dislocations and antiphase boundaries. These defects, which are related to the nonequilibrium processing conditions, are likely to be responsible for the higher critical currents observed in these films as compared to single crystals.     

Phase-separated composite films for liquid crystal displays

A method of preparing liquid crystal devices by phase separation of liquid crystal from its solution in a prepolymer, which results in adjacent layers of liquid crystal and polymer, is described. Liquid crystals in these phase-separated composite films exhibit electro-optical properties not observed in devices prepared by conventional methods, polymer dispersion, or polymer-stabilization methods. Devices incorporating ferroelectric liquid crystals have gray scale and switch 100 times faster at low fields than conventional surface-stabilized devices. This method makes it possible to prepare devices with liquid crystal film thickness comparable to optical wavelengths.     

Chemical Solution Routes to Single-Crystal Thin Films

Epitaxial thin films of inorganic single crystals can be grown on single-crystal substrates with a variety of different solution chemistries. This review emphasizes chemical solution deposition, in which a solution is used to deposit a layer of precursor molecules that decompose to low-density, polycrystalline films during heating. Ways to control film cracking during deposition and heat treatment and why many precursors synthesize metastable crystalline structures are discussed, and the different mechanisms that convert the polycrystalline film into a single crystal are reviewed. Hydrothermal epitaxy, in which single crystal thin films are directly synthesized on templating substrates in an aqueous solution at temperatures <150°C, is also discussed.     

Visualization of dislocation dynamics in colloidal crystals

The dominant mechanism for creating large irreversible strain in atomic crystals is the motion of dislocations, a class of line defects in the crystalline lattice. Here we show that the motion of dislocations can also be observed in strained colloidal crystals, allowing detailed investigation of their topology and propagation. We describe a laser diffraction microscopy setup used to study the growth and structure of misfit dislocations in colloidal crystalline films. Complementary microscopic information at the single-particle level is obtained with a laser scanning confocal microscope. The combination of these two techniques enables us to study dislocations over a range of length scales, allowing us to determine important parameters of misfit dislocations such as critical film thickness, dislocation density, Burgers vector, and lattice resistance to dislocation motion. We identify the observed dislocations as Shockley partials that bound stacking faults of vanishing energy. Remarkably, we find that even on the scale of a few lattice vectors, the dislocation behavior is well described by the continuum approach commonly used to describe dislocations in atomic crystals.     

Synthesis of two-dimensional polymers

A synthetic pathway is described to construct "in bulk" two-dimensional (2D) polymers shaped as molecular sheets. A chiral oligomeric precursor is used that contains two reactive sites, a polymerizable group at one terminus and a reactive stereogenic center near the middle of the molecule. The bulk reaction yields bilayer 2D polymers of molecular weight in the order of millions and a monodisperse thickness of 50.2 angstroms. The 2D molecular objects form through molecular recognition by the oligomers, which self-organize into layers that place the reactive groups within specific planes. The oligomers become catenated by two different stitching reactions involving the reactive sites. At room temperature, stacks of these molecular objects can organize as single crystals and at higher temperatures melt into smectic liquid crystals. Nonlinear optical experiments reveal that solid films containing the 2D polymers form structures that are thermally and temporally more stable than those containing analogous 1D polymers. This observation suggests that the transformation of common polymers from a 1D to a 2D architecture may produce generations of organic materials with improved properties.