Project description:Two-dimensional covalent organic frameworks (2D COFs) are composed of structurally precise, permanently porous, layered polymer sheets. 2D COFs have traditionally been synthesized as polycrystalline aggregates with small crystalline domains. Only recently have a small number of 2D COFs been obtained as single crystals, which were prepared by a seeded growth approach via the slow introduction of monomers, which favored particle growth over nucleation. However, these procedures are slow and operationally difficult, making it desirable to develop polymerization methods that do not require the continuous addition of reactants over days or weeks. Here, we achieve the rapid growth of boronate ester-linked COFs by chemically suppressing nucleation via addition of an excess of a monofunctional competitor, 4-tert-butylcatechol (TCAT), into the polymerization. In situ X-ray scattering measurements show that TCAT suppresses colloid nucleation, which enables seeded growth polymerizations in the presence of high monomer concentrations. Kinetic Monte Carlo simulations reveal that TCAT limits oligomers to sizes below the critical nucleus size and that in-plane expansion is restricted compared to out-of-plane oriented attachment of oligomers. The simulations are consistent with transmission electron micrographs, which show that the particles grow predominantly in the stacking direction. This mechanistic insight into the role of the modulators in 2D polymerizations enables the size and aspect ratio of COF colloids to be controlled under operationally simple conditions. This chemically controlled growth strategy will accelerate the discovery and exploration of COF materials and their emergent properties.
Project description:Tooth enamel is a hard yet resilient biomaterial that derives its unique mechanical properties from decussating bundles of apatite crystals. To understand enamel crystal nucleation and growth at a nanoscale level and to minimize preparation artifacts, the developing mouse enamel matrix was imaged in situ using graphene liquid cells and atomic resolution scanning transmission electron and cryo-fracture electron microscopy. We report that 1-2 nm diameter mineral precipitates aggregated to form larger 5 nm particle assemblies within ameloblast secretory vesicles or annular organic matrix subunits. Further evidence for the fusion of 1-2 nm mineral precipitates into 5 nm mineral aggregates via particle attachment was provided by matrix-mediated calcium phosphate crystal growth studies. As a next step, aggregated particles organized into rows of 3-10 subunits and developed lattice suprastructures with 0.34 nm gridline spacings corresponding to the (002) planes of apatite crystals. Mineral lattice suprastructures superseded closely matched organic matrix patterns, suggestive of a combination of organic/inorganic templates guiding apatite crystal growth. Upon assembly of 2-5 nm subunits into crystal ribbons, lattice fringes indicative of the presence of larger ordered crystallites were observed surrounding elongating crystal ribbons, presumably guiding the c-axis growth of composite apatite crystals. Cryo-fracture micrographs revealed reticular networks of an organic matrix on the surface of elongating enamel crystal ribbons, suggesting that protein coats facilitate c-axis apatite crystal growth. Together, these data demonstrate (i) the involvement of particle attachment in enamel crystal nucleation, (ii) a combination of matrix- and lattice-guided crystal growth, and (iii) fusion of individual crystals via a mechanism similar to Ostwald ripening.
Project description:Organisms had to evolve mechanisms that regulate the properties of biogenic crystals to support a wide range of functions, from vision and camouflage to communication and thermal regulation. Yet, the mechanism underlying the formation of diverse intracellular crystals remains enigmatic. Here, we have unraveled the bio-chemical control over crystal morphogenesis in zebrafish iridophores. We show that the chemical composition of the crystals determines their shape, specifically by the ratio between the nucleobases guanine and hypoxanthine. Moreover, we reveal that these variations in composition are genetically controlled through tissue-specific expression of specialized paralogues, which exhibits remarkable substrate selectivity. This orchestrated combination grants the organism with the capacity to generate a broad spectrum of crystal morphologies. Overall, our findings suggest a new mechanism for the morphological and functional diversity of biogenic crystals and may thus inspire the development of genetically designed biomaterials and medical therapeutics.
Project description:The nucleation and growth of crystalline cobalt nanoparticles (Co NPs) under solvothermal conditions can be separated into distinct stages by using (i) polynuclear clusters with multivalent capping ligands to initiate nucleation, and (ii) thermolabile organometallic complexes with low autonucleation potential to promote crystalline growth. Both nucleation and growth take place within an amorphous accretion, formed in the presence of polyvalent surfactants. At the pre-nucleation stage, a calixarene complex with multiple Co2-alkyne ligands (Co16-calixarene 1) undergoes thermal decomposition above 130 °C to form "capped cluster" intermediates that coalesce into well-defined Co nanoclusters, but are resistant to further aggregation. At the post-nucleation stage, a monomer (pentyne-Co4(CO)10, or PTC) with a low thermal activation threshold but a high barrier to autonucleation is introduced, yielding ε-Co NPs with a linear relationship between particle volume and the Co mole ratio ([Cofinal]/[Coseed]). Co nanocrystals can be produced up to 40 nm with a 10-12% size dispersity within the accretion, but their growth rate depends on the activity of the supporting surfactant, with an octapropargyl calixarene derivative (OP-C11R) providing the most efficient transport of reactive Co species through the amorphous matrix. Post-growth digestion with oleic acid releases the Co NPs from the residual accretion, which can then self-assemble by magnetic dipolar interactions into flux-closure rings when stabilized by calixarene-based surfactants. These studies demonstrate that organometallic complexes can be designed to establish rational control over the nucleation and growth of crystalline NPs within an intermediate accretion phase.
Project description:Calcium oxalate raphide crystals are found in bundles in intravacuolar membrane chambers of specialized idioblasts cells of most plant families including many crop plants and are found in most tissues. Raphides are needle-shaped, often with barbed ends, and their morphology and biomineralization pattern have been a focus of much research. In the family Araceae, raphides have been proposed to cause acridity in crops such as taro (Colocasia esculenta (L.) Schott). Acridity is irritation that causes swelling of lips, mouth and throat, as well as itchiness and pain when raw or insufficiently cooked tissues are eaten; this response varies among taro consumers. Since raphides in some other foods do not cause acridity, and since acridity can be inactivated by cooking and/or protease treatment, it is possible that a toxin or allergen-like compound is associated with the crystals. Using two-dimensional (2D) gel electrophoresis and mass spectrometry (MS) peptide sequencing of selected peptides from purified raphides and the results from taro apex transcriptome sequencing, we have shown that profilins, known allergens, are present on raphides. One of the five raphide profilins genes was highly expressed in the apex and had a 17-amino-acid insert that significantly increased that profilin’s epitope peak. This insert was predicted to be coiled and exposed on the surface of the folded peptide. A second profilin had a 2-amino-acid insert that also had a greater B-cell epitope prediction. The taro profilins showed 83 to 92% similarity to known characterized profilins while other raphide peptides showed greater than 90% similarity to other higher plants. The presence on the raphides of peptides normally associated with mitochrondria (ATP synthase), chloroplasts (chaperonin cpn 60 kDa), cytoplasm (actin, profilin) and vacuole (V-type ATPase) indicates a multistage biocrystallation process ending with possible invagination of the tonoplast and addition of mucilage that may be derived from the Golgi. Actin might play a crucial role in the generation of the needle-like raphides. We also showed that commercial allergen test strips for hazelnuts, where profilin is a secondary allergen, have potential for screening in a plant breeding program to reduce acridity and during food processing to avoid over-cooking.
Project description:Dendrite microtubules are polarized with minus-end-out orientation in Drosophila neurons. Nucleation sites concentrate at dendrite branch points, but how they localize is not known. Using Drosophila, we found that canonical Wnt signaling proteins regulate localization of the core nucleation protein γTubulin (γTub). Reduction of frizzleds (fz), arrow (low-density lipoprotein receptor-related protein [LRP] 5/6), dishevelled (dsh), casein kinase Iγ, G proteins, and Axin reduced γTub-green fluorescent protein (GFP) at branch points, and two functional readouts of dendritic nucleation confirmed a role for Wnt signaling proteins. Both dsh and Axin localized to branch points, with dsh upstream of Axin. Moreover, tethering Axin to mitochondria was sufficient to recruit ectopic γTub-GFP and increase microtubule dynamics in dendrites. At dendrite branch points, Axin and dsh colocalized with early endosomal marker Rab5, and new microtubule growth initiated at puncta marked with fz, dsh, Axin, and Rab5. We propose that in dendrites, canonical Wnt signaling proteins are housed on early endosomes and recruit nucleation sites to branch points.
Project description:Surfactants have been widely used as effective additives to increase the solubility and dissolution rates of amorphous solid dispersions (ASDs). However, they may also generate adverse effects on the physical stability of ASDs. In this study, we systematically investigated the impacts of poloxamer, a frequently used surfactant, on the crystallization of amorphous clotrimazole (CMZ). The added poloxamer significantly decreased the glass transition temperature (Tg) of CMZ and accelerated the growth of Form 1 and Form 2 crystals. It was found that the poloxamer had an accelerating effect on Form 1 and Form 2 but showed a larger accelerating effect on Form 1, which resulted from a combined effect of increased mobility and local phase separation at the crystal-liquid interface. Additionally, the added poloxamer exhibited different effects on nucleation of the CMZ polymorphs, which was more complicated than crystal growth. The nucleation rate of Form 1 was significantly increased by the added poloxamer, and the effect increased with increasing P407 content. However, for Form 2, nucleation was slightly decreased or unchanged. The nucleation of Form 2 may have been influenced by the Form 1 crystallization, and Form 2 converted to Form 1 during nucleation. This study increases our understanding of poloxamer and its impacts on the melt crystallization of drugs.
Project description:The roughness of crystal surfaces and the shape of crystals play important roles in multiscale phenomena. For example, the roughness of the crystal surface affects the frictional and optical properties of materials such as ice or silica. Theoretical studies on crystal surfaces based on the symmetry principle proposed that the growing surfaces of crystal growth could be classified in the universal class of Kardar-Parisi-Zhang (KPZ), but experiments rarely observe KPZ properties. To fill this the gap, extensive numerical calculations of the crystal growth rates and the surface roughness (surface width) have been performed for a nanoscale lattice model using the Monte Carlo method. The results indicate that a (001) surface is smooth within the single nucleation growth region. In contrast, the same surface is atomically smooth but thermodynamically rough in the poly-nucleation growth region in conjunction with a KPZ roughness exponent. Inclined surfaces are known to become Berezinskii-Kosterlitz-Thouless (BKT) rough surfaces both at and near equilibrium. The two types of steps associated with the (001) and (111) terraces were found to induce KPZ surface roughness, while the interplay between steps and multilayered islands promoted BKT roughness.
Project description:Control of the crystallization process is central to developing nanomaterials with atomic precision to meet the demands of electronic and quantum technology applications. Semiconductor nanowires grown by the vapor-liquid-solid process are a promising material system in which the ability to form components with structure and composition not achievable in bulk is well-established. Here, we use in situ TEM imaging of Au-catalyzed GaAs nanowire growth to understand the processes by which the growth dynamics are connected to the experimental parameters. We find that two sequential steps in the crystallization process-nucleation and layer growth-can occur on similar time scales and can be controlled independently using different growth parameters. Importantly, the layer growth process contributes significantly to the growth time for all conditions and will play a major role in determining material properties such as compositional uniformity, dopant density, and impurity incorporation. The results are understood through theoretical simulations correlating the growth dynamics, liquid droplet, and experimental parameters. The key insights discussed here are not restricted to Au-catalyzed GaAs nanowire growth but can be extended to most compound nanowire growths in which the different growth species has very different solubility in the catalyst particle.
Project description:To clarify whether a surface can be rough with faceted macrosteps that maintain their shape on the surface, crystal surface roughness is studied by a Monte Carlo method for a nucleation-limited crystal-growth process. As a surface model, the restricted solid-on-solid (RSOS) model with point-contact-type step-step attraction (p-RSOS model) is adopted. At equilibrium and at sufficiently low temperatures, the vicinal surface of the p-RSOS model consists of faceted macrosteps with (111) side surfaces and smooth terraces with (001) surfaces (the step-faceting zone). We found that a surface with faceted macrosteps has an approximately self-affine-rough structure on a 'faceted-rough surface'; the surface width is strongly divergent at the step-disassembling point, which is a characteristic driving force for crystal growth. A 'faceted-rough surface' is realized in the region between the step-disassembling point and a crossover point where the single nucleation growth changes to poly-nucleation growth.