Growth Of Inorganic Crystals Research Articles

Biomineralization-Inspired Confined-Space Fabrication of Polyimide Aerogels.

The biomineralization process endows biominerals with unique hierarchically porous structures and physical-chemical properties by filling the restricted microreaction space with amorphous phases before the growth of inorganic crystals. In this paper, a confined-space fabrication method inspired by biomineralization for preparing hierarchically porous polyimide (PI) aerogels and PI-derived carbon aerogels is introduced. The confined structure is established through a self-assembly method of vacuum impregnation and ultrasound-assisted freeze-drying. The hierarchically porous structure is controlled by adjusting the structure characteristics of the confined space and secondary aerogels. Subsequently, a variety of performance demonstrations are conducted to demonstrate the mechanical properties and application prospects in the fields of thermal insulation and electromagnetic shielding of the prepared aerogel.

Data-Driven Reactivity Predictions between a Solute and Solvent for Inorganic Crystal Growth in Solution

Data-Driven Reactivity Predictions between a Solute and Solvent for Inorganic Crystal Growth in Solution

Spin Coating Promotes the Epitaxial Growth of AgCN Microwires on 2D Materials.

Epitaxial growth of inorganic crystals on 2D materials is expected to greatly advance nanodevices and nanocomposites. However, because pristine surfaces of 2D materials are chemically inert, it is difficult to grow inorganic crystals epitaxially on 2D materials. Previously, successful results were achieved only by vapor-phase deposition at high temperature, and solution-based deposition including spin coating made the epitaxial growth unaligned, sparse, or nonuniform on 2D materials. Here, we show that solvent-controlled spin coating can uniformly deposit a dense layer of epitaxial AgCN microwires onto various 2D materials. Adding ethanol to an aqueous AgCN solution facilitates uniform formation of the thin supersaturated solution layer during spin coating, which promotes heterogeneous crystal nucleation on 2D material surfaces over homogeneous nucleation in the bulk solution. Microscopic analysis confirms highly aligned, uniform, and dense growth of epitaxial AgCN microwires on graphene, MoS2, hBN, WS2, and WSe2. The epitaxial microwires, which are optically observable and chemically removable, enable crystallographic mapping of grains in millimeter-sized polycrystalline graphene as well as precise control of twist angles (<∼1°) in van der Waals heterostructures. In addition to these practical applications, our study demonstrates the potential of 2D materials as epitaxial templates even in spin coating of inorganic crystals.

Guiding epitaxial crystallization of amorphous solids at the nanoscale: Interfaces, stress, and precrystalline order.

The crystallization of amorphous solids impacts fields ranging from inorganic crystal growth to biophysics. Promoting or inhibiting nanoscale epitaxial crystallization and selecting its final products underpin applications in cryopreservation, semiconductor devices, oxide electronics, quantum electronics, structural and functional ceramics, and advanced glasses. As precursors for crystallization, amorphous solids are distinguished from liquids and gases by the comparatively long relaxation times for perturbations of the mechanical stress and for variations in composition or bonding. These factors allow experimentally controllable parameters to influence crystallization processes and to drive materials toward specific outcomes. For example, amorphous precursors can be employed to form crystalline phases, such as polymorphs of Al2O3, VO2, and other complex oxides, that are not readily accessible via crystallization from a liquid or through vapor-phase epitaxy. Crystallization of amorphous solids can further be guided to produce a desired polymorph, nanoscale shape, microstructure, or orientation of the resulting crystals. These effects enable advances in applications in electronics, magnetic devices, optics, and catalysis. Directions for the future development of the chemical physics of crystallization from amorphous solids can be drawn from the structurally complex and nonequilibrium atomic arrangements in liquids and the atomic-scale structure of liquid-solid interfaces.

Bottom-Up Synthesis of Helical Plasmonic Nanorods and Their Application in Generating Circularly Polarized Luminescence.

Chiral growth and chirality transfer associated with plasmonic nanostructures have rejuvenated the field of chirality. As the precise regioselective growth of inorganic crystals into chiral shapes at the nanoscale is extremely challenging, "bottom-up" synthesis of intrinsically chiral nanoparticles with structural stability is obviously attractive and important. With the thiolated bimolecular cosurfactants, we demonstrated a chemical strategy for the synthesis of intrinsically helical plasmonic nanorods (HPNRs) with strong and tailorable plasmonic circular dichroism (PCD) responses, deriving from the zwitterionic interactions between the -NH3+ and -COO- groups of the cysteine molecules (Cys). The influence of structural parameters of HPNRs on PCD responses was analyzed systematically by theoretical simulations. Among the different structural parameters, the pitch depth was found to have the greatest impact on the PCD signals, in agreement with the experimental results. Moreover, the obtained HPNRs with the strong, tunable, and stable chiroptical properties were found to be able to induce circularly polarized luminescence of achiral luminophores. Due to the generality of this effect, this chiral plasmonic nanostructure may have great potential for use in the fields of chiral sensors, chiral catalysis, and displays.

Acidic Monetite Complex Paste with Bleaching Property for In-depth Occlusion of Dentinal Tubules.

BackgroundDentin hypersensitivity (DH) is a common dental clinical condition presented with a short and sharp pain in response to physical and chemical stimuli. Currently no treatment regimen demonstrates long-lasting efficacy in treating DH, and unesthetic yellow tooth color is a concern to many patients with DH.AimTo develop a bi-functional material which can occlude dentinal tubules in-depth and remineralize dentin for long-lasting protection of the dentin–pulp complex from stimuli and bleach the tooth at the same time.MethodsA mixture containing CaO, H3PO4, polyethylene glycol and H2O2 at a specific ratio was mechanically ground using a planetary ball. The mineralizing complex paste was characterized by X-ray diffraction (XRD) and scanning electron microscopy (SEM). Dentin was exposed to the synthesized paste for 8 h and 24 h in vitro. The mineralizing property was evaluated using SEM and microhardness tests. Red tea-stained tooth slices were exposed to the synthesized paste for 8 h and 24 h in vitro. The bleaching effect was characterized by a spectrophotometer.ResultsThe complex paste had very a fine texture, was injectable, and had a gel-like property with 2.6 (mass/volume) % H2O2 concentration. The X-ray diffraction pattern showed that the inorganic phase was mainly monetite (CaHPO4). The mineralizing complex paste induced the growth of inorganic crystals on the dentin surface and in-depth occlusion of dentin tubules by up to 80 μm. The regenerated crystals were integrated into the dentin tissue on the dentin surface and the wall of dentinal tubules with a microhardness of up to 126 MPa (versus 137 Mpa for dentin). The paste also bleached the stained dental slices.ConclusionThe mineralizing complex paste is a promising innovative material for efficient DH management by remineralizing dentin and in-depth occlusion of dentin tubules, as well as tooth bleaching.

Bioactive Core-Shell CaF2 Upconversion Nanostructure for Promotion and Visualization of Engineered Bone Reconstruction.

Inorganic ion metabolism plays significant roles in various life processes including signal transduction, substance exchange, and cellular constructions. Regulation and monitoring of ion metabolism offer great promise to modulate biological activities and provide insights into related mechanisms. Here, a synergistic nanodepot based on a bioactive core-shell CaF2 upconversion nanostructure that integrates multiple mineral ions for metabolic regulation was built for the acceleration and monitoring of the biomineralization process. Multiple mineral ions released from the nanodepots can accelerate the growth of inorganic crystals and enhance the production of organic matrixes, synergistically facilitating the regeneration of bone defects in vivo. During the process, such a nanodepot can be constructed to specifically recognize osteoblasts for the monitoring of biomineralization. This nanoprobe represents an efficient strategy to promote and monitor biomineralization-related metabolic activities with applications in fundamental research, disease diagnosis, and regenerative medicine.

Graphene Quantum Dots-Driven Multiform Morphologies of β-NaYF4:Gd3+/Tb3+ Phosphors: The Underlying Mechanism and Their Optical Properties.

Dimension and shape tunable architectures of inorganic crystals are of extreme interest because of morphology-dependent modulation of the properties of the materials. Herein, for the first time, we present a novel impurity-driven strategy where we studied the influence of in situ incorporation of graphene quantum dots (GQDs) on the growth of β-NaYF4:Gd3+/Tb3+ phosphor crystals via a hydrothermal route. The GQDs function as a nucleation site and by changing the concentration of GQDs, the morphology of β-NaYF4:Gd3+/Tb3+ phosphors was changed from rod to flowerlike structure to disklike structure, without phase transformation. The influence of size and functionalization of GQDs on the size and shape of phosphor crystals were also systematically studied and discussed. Plausible mechanisms of formation of multiform morphologies are proposed based on the heterogeneous nucleation and growth. Most interestingly, the experimental results indicate that the photoluminescence properties of β-NaYF4:Gd3+/Tb3+ phosphor crystals are strongly dependent on the crystallite size and morphology. This study would be suggestive for the precisely controlled growth of inorganic crystals; consequently, it will open new avenues and thus may possess potential applications in the field of materials and biological sciences.

A Benchmarking Study of Peptide–Biomineral Interactions

A long-standing goal in the field of biomineralization has been to achieve a molecular-level mechanistic understanding of how proteins participate in the nucleation and growth of inorganic crystals (both in vitro and in vivo). Computational methods offer an approach to explore these interactions and propose mechanisms at the atomic scale; however, to have confidence in the predictions of a computational method, the method must first be validated against a benchmark experimental data set of protein–mineral interactions. Relatively little work has been done to test the ability of computation to reproduce experimental results on mineral systems with biologically relevant additives present. The goal of this work is to develop a standard and varied benchmark to test whether a computational method is able to match experimental results at the length and time scales of biomineral–peptide interactions. We compare the results of the RosettaSurface algorithm to an experimental benchmark of kinetic and thermodynamic ...

無機結晶のらせん状成長とキラルな有機分子によるキラリティ制御( 結晶成長の基礎-多様な展開)

無機結晶のらせん状成長とキラルな有機分子によるキラリティ制御( 結晶成長の基礎-多様な展開)

Organic crystal lattices in the axial filament of silica spicules of Demospongiae.

The skeletal system of Demospongiae consists of siliceous spicules, which are composed of an axial channel containing an organic axial filament (AF) surrounded by a compact layer of hydrated amorphous silica. Here we report the ultrastructural investigations of the AF of siliceous spicules from two Demospongiae: Suberites domuncula and Tethya aurantium. Electron microscopy, electron diffraction and elemental mapping analyses on both longitudinal and transversal cross-sections yield that spicules's AF consist of a three-dimensional crystal lattice of six-fold symmetry. Its structure, which is the result of a biological growth process, is a crystalline assembly characterized by a lattice of organic cages (periodicity in the range of 6nm) filled with enzymatically-produced silica. In general, the six-fold lattice symmetry is reflected by the morphology of the AF, which is characterized by six-fold facets. This seems to be the result of a lattice energy minimization process similar to the situation found during the growth of inorganic crystals. Our structural exploitation of three-dimensional organic lattices generated by biological systems is expected to contribute for explaining the relation between axial filament's ultrastructure and spicule's ultimate morphology.

Strain-relief by single dislocation loops in calcite crystals grown on self-assembled monolayers.

Most of our knowledge of dislocation-mediated stress relaxation during epitaxial crystal growth comes from the study of inorganic heterostructures. Here we use Bragg coherent diffraction imaging to investigate a contrasting system, the epitaxial growth of calcite (CaCO3) crystals on organic self-assembled monolayers, where these are widely used as a model for biomineralization processes. The calcite crystals are imaged to simultaneously visualize the crystal morphology and internal strain fields. Our data reveal that each crystal possesses a single dislocation loop that occupies a common position in every crystal. The loops exhibit entirely different geometries to misfit dislocations generated in conventional epitaxial thin films and are suggested to form in response to the stress field, arising from interfacial defects and the nanoscale roughness of the substrate. This work provides unique insight into how self-assembled monolayers control the growth of inorganic crystals and demonstrates important differences as compared with inorganic substrates.

Advanced Biomimetic Approach for Crystal Growth in Nonaqueous Media: Morphology and Orientation Control of Pentacosadiynoic Acid and Applications

In nature, biological macromolecules control the growth of inorganic crystals under mild conditions in aqueous media. Inspired by biomineralization, biomimetic approaches have been studied for growth control of inorganic crystals in aqueous media by using organic molecules and polymers. The approaches were not applied to nonaqueous systems for the development of functional organic materials. Here, we have applied biomimetic approaches to growth control of organic crystals in nonaqueous media. Morphology and orientation of 10,12-pentacosadiynoic acid (PCDA) crystals, a diacetylene derivative, were controlled in organic media with the additive organic polymers and surface-modified substrates. The oriented PCDA ribbons were obtained by an advanced biomimetic approach. After topochemical polymerization, the resultant polydiacetylenes (PDA) ribbons were applied to the thermochromic materials with intercalation of metal ions and the semiconductor layer of an organic field-effect transistor. The present work imp...

Silk fibroin/sodium alginate fibrous hydrogels regulated hydroxyapatite crystal growth.

Use of organic templates for controlling the growth of inorganic crystals is one of the research topics in biomimetic field. In particular, oriented growth of hydroxyapatite (HAp) in organic fibrous matrix is provided a new view angle to study biomineralization of bone and its potential biomedical applications. The crystallization of HAp in fibrous hydrogels could mimic such biomineralization. In this paper, we report HAp nanorod crystal synthesized successfully by a biomimetic method using calcium chloride and ammonium dihydrogen phosphate as reagents in the presence of silk fibroin/sodium alginate (SF/SA) fibrous hydrogels. The effects of influence factors such as mineral times, pH, and temperature on controlling HAp nanorod crystals are discussed. The elongated HAp nanorods with rectangular column are grown with the increase of mineral times in biomimetic process. By changing pH, HAp nanorod crystals are obtained at alkaline condition in fibrous hydrogels. Moreover, compared to other temperatures, rod-shaped HAp crystals were formed at 20°C. The results imply this to be an effective method for preparing HAp crystals with controllable morphology for bone repair application.

Antifreeze Effect of Carboxylated ε-Poly-l-lysine on the Growth Kinetics of Ice Crystals

Some biological substances control the nucleation and growth of inorganic crystals. Antifreeze proteins, which prohibit ice crystal growth in living organisms, promise are also important as biological antifreezes for medical applications and in the frozen food industries. In this work, we investigated the crystallization of ice in the presence of a new cryoprotector, carboxylated ε-poly-L-lysine (COOH-PLL). In order to reveal the characteristics and the mechanism of its antifreeze effect, free-growth experiments of ice crystals were carried out in solutions with various COOH-PLL concentrations and degrees of supercooling, and the depression of the freezing point and growth rates of the tips of ice dendrites were obtained using optical microscopy. Hysteresis of growth rates and depression of the freezing point was revealed in the presence of COOH-PLL. The growth-inhibition effect of COOH-PLL molecules could be explained on the basis of the Gibbs-Thomson law and the use of Langmuir's adsorption isotherm. Theoretical kinetic curves for hysteresis calculated on the basis of Punin-Artamonova's model were in good agreement with experimental data. We conclude that adsorption of large biological molecules in the case of ice crystallization has a non-steady-state character and occurs more slowly than the process of embedding of crystal growth units.

In situ studies of a platform for metastable inorganic crystal growth and materials discovery.

Rapid shifts in the energy, technological, and environmental demands of materials science call for focused and efficient expansion of the library of functional inorganic compounds. To achieve the requisite efficiency, we need a materials discovery and optimization paradigm that can rapidly reveal all possible compounds for a given reaction and composition space. Here we provide such a paradigm via in situ X-ray diffraction measurements spanning solid, liquid flux, and recrystallization processes. We identify four new ternary sulfides from reactive salt fluxes in a matter of hours, simultaneously revealing routes for ex situ synthesis and crystal growth. Changing the flux chemistry, here accomplished by increasing sulfur content, permits comparison of the allowable crystalline building blocks in each reaction space. The speed and structural information inherent to this method of in situ synthesis provide an experimental complement to computational efforts to predict new compounds and uncover routes to targeted materials by design.

Biopolymer-Mediated Inorganic Crystal Growth at Reduced Temperature with Enhanced Kinetics and Morphological Direction

We describe and develop an example of the successful application of a broadly applicable biomimetic growth process to the crystal growth of the complex inorganic quaternary high-temperature superconducting ceramic oxide YBa2Cu3O7−δ. By combining effective biopolymer mediation with established synthetic single crystal growth processes, we leverage a reduction in the required growth temperature from 1045 to 920 °C to enable the successful use of a molten salt synthesis technique in place of the high-temperature solution method commonly employed. Further, the influence of the biopolymer on the seed crystal nucleation provides for morphological control of the synthesis product, offering the potential for designed macromorphologies through biopolymer selection or customization. The method described is directly applicable to other difficult-to-synthesize materials that presently rely on similar conventional techniques, or for which such approaches have been found to fail, thereby providing a novel route to the successful bulk synthesis of complex refractory materials.

Oriented attachment explains cobalt ferrite nanoparticle growth in bioinspired syntheses

Oriented attachment has created a great debate about the description of crystal growth throughout the last decade. This aggregation-based model has successfully described biomineralization processes as well as forms of inorganic crystal growth, which could not be explained by classical crystal growth theory. Understanding the nanoparticle growth is essential since physical properties, such as the magnetic behavior, are highly dependent on the microstructure, morphology and composition of the inorganic crystals. In this work, the underlying nanoparticle growth of cobalt ferrite nanoparticles in a bioinspired synthesis was studied. Bioinspired syntheses have sparked great interest in recent years due to their ability to influence and alter inorganic crystal growth and therefore tailor properties of nanoparticles. In this synthesis, a short synthetic version of the protein MMS6, involved in nanoparticle formation within magnetotactic bacteria, was used to alter the growth of cobalt ferrite. We demonstrate that the bioinspired nanoparticle growth can be described by the oriented attachment model. The intermediate stages proposed in the theoretical model, including primary-building-block-like substructures as well as mesocrystal-like structures, were observed in HRTEM measurements. These structures display regions of substantial orientation and possess the same shape and size as the resulting discs. An increase in orientation with time was observed in electron diffraction measurements. The change of particle diameter with time agrees with the recently proposed kinetic model for oriented attachment.

Synthesis of NaYF4 microcrystals with different morphologies and enhanced up-conversion luminescence properties

In this paper, NaYF4 microcrystals with a variety of morphologies, such as microsphere, hexagonal prism, microtube and octahedron shapes, have been synthesized via a hydrothermal method using sodium poly(4-styrenesulfonate) (PSS) as a template. The structural and kinetic factors that govern the phase and shape evolution of NaYF4 microcrystals have been systematically studied. And the influence of reaction time, pH values, fluoride sources and reaction temperature on the phase and shape of the as-synthesized NaYF4 was systematically investigated and discussed. It is found that PSS can be employed as a shape modifier, which is responsible for the shape evolution. The possible formation mechanism for the products with various architectures has been presented. The up-conversion (UC) properties of Yb(3+)/Ho(3+), Yb(3+)/Er(3+) or Yb(3+)/Tm(3+) codoped NaYF4 samples were studied. In particular, the luminescence intensity can be markedly enhanced by Li(+) doping, the related mechanism has been discussed. Furthermore, a systematic study on the UC emissions of Yb(3+)/Tm(3+) codoped NaYF4 samples with microsphere, hexagonal prism, microtube and octahedron shapes has shown that the optical properties of these phosphors are strongly dependent on their morphologies and sizes. This study would be suggestive for the precisely controlled growth of inorganic crystals, especially for those rare earth fluoride compounds.

Influence of the synthetic polypeptide c25-mms6 on cobalt ferrite nanoparticle formation

Nanoparticle syntheses utilizing biomimetic approaches have advanced in recent years. Polypeptides, with their ability to influence inorganic crystal growth, are a topic of great interest. Their effect on the particle formation has not been completely understood yet. Here we report a bioinspired synthesis of cobalt ferrite nanoparticles carried out in vitro under mild conditions using a short, synthetic polypeptide c25-mms6. The influence of c25-mms6 on the nanoparticle formation was investigated by comparing the particles synthesized with the polypeptide to particles synthesized under equivalent conditions without c25-mms6. A separation into D small,av = 10 nm small, superparamagnetic spheres and D big,av = 48 nm disc-like single-domain particles was observed. Non-stoichiometric cobalt ferrite particles with a shape-dependent stoichiometry were produced in the polypeptide-free synthesis. Stoichiometric D small,av = 10 nm CoFe2O4 spheres and D big,av = 60–70 nm Co2FeO4 ferromagnetic discs were obtained in the polypeptide-enhanced synthesis. The results indicate that the polypeptide acts as a catalyst during the multistep biomineralization process and allows the formation of stoichiometric phases which cannot be synthesized at room temperature using conventional bottom-up syntheses.