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Here, we report the high pressure phase and morphology behavior of ordered anatase titanium dioxide (TiO2) nanocrystal arrays. One-dimensional TiO2 nanorods and nanorices were synthesized and self-assembled into ordered mesostructures. Their phase and morphological transitions at both atomic scale and mesoscale under pressure were studied using in situ synchrotron wide- and small-angle x-ray scattering (WAXS and SAXS) techniques. At the atomic scale, synchrotron WAXS reveals a pressure-induced irreversible amorphization up to 35 GPa in both samples but with different onset pressures. On the mesoscale, no clear phase transformations were observed up to 20 GPa by synchrotron SAXS. Intriguingly, sintering of TiO2 nanorods at mesoscale into nano-squares or nano-rectangles, as well as nanorices into nanowires, were observed for the first time by transmission electron microscopy. Such pressure-induced nanoparticle phase-amorphization and morphological changes provide valuable insights for design and engineering structurally stable nanomaterials. 

Understanding gene regulatory networks is essential to elucidate developmental processes and environmental responses. Here, we studied regulation of a maize (Zea mays) transcription factor gene using designer transcription activator-like effectors (dTALes), which are synthetic Type III TALes of the bacterial genus Xanthomonas and serve as inducers of disease susceptibility gene transcription in host cells. The maize pathogen Xanthomonas vasicola pv. vasculorum was used to introduce 2 independent dTALes into maize cells to induced expression of the gene glossy3 (gl3), which encodes a MYB transcription factor involved in biosynthesis of cuticular wax. RNA-seq analysis of leaf samples identified, in addition to gl3, 146 genes altered in expression by the 2 dTALes. Nine of the 10 genes known to be involved in cuticular wax biosynthesis were upregulated by at least 1 of the 2 dTALes. A gene previously unknown to be associated with gl3, Zm00001d017418, which encodes aldehyde dehydrogenase, was also expressed in a dTALe-dependent manner. A chemically induced mutant and a CRISPR-Cas9 mutant of Zm00001d017418 both exhibited glossy leaf phenotypes, indicating that Zm00001d017418 is involved in biosynthesis of cuticular waxes. Bacterial protein delivery of dTALes proved to be a straightforward and practical approach for the analysis and discovery of pathway-specific genes in maize.

 

Metal-organic frameworks (MOF) are an emerging class of microporous materials with promising applications. MOF nanocrystals, and their assembled super-structures, can display unique properties and reactivities when compared with their bulk analogues. MOF nanostructures of 0-D, 2-D, and 3-D dimensions can be routinely obtained by controlling reaction conditions and ligand additives, while formation of 1-D MOF nanocrystals (nanowires and nanorods) and super-structures has been relatively rare. We report here a facile templated interfacial synthesis methodology for the preparation of a series of 1-D MOF nano- and micro-structures with precisely controlled shapes and sizes. Specifically, by applying track-etched polycarbonate (PCTE) membranes as the templates and at the oil/water interface, we rapidly and reproducibly synthesize zeolitic imidazolate framework-8 (ZIF-8) and ZIF-67 nano- and micro structures of sizes ranging from 10 nm to 20 μm. We also identify a size confinement effect on MOF crystal growth, which leads to single crystals under the most restricted conditions and inter-grown polycrystals at larger template pore sizes, as well as surface directing effects that influence the crystallographic preferred orientation. Our findings provide a potentially generalizable method for controlling the size, morphology, and crystal orientations of MOF nanomaterials, as well as offering fundamental understanding into MOF crystal growth mechanisms.

 

Hybrid organic–inorganic composites possessing both electronic and magnetic properties are promising materials for a wide range of applications. Controlled and ordered arrangement of the organic and inorganic components is key for synergistic cooperation toward desired functions. In this work, we report the self-assemblies of core–shell composite nanofibers from conjugated block copolymers and magnetic nanoparticles through the cooperation of orthogonal non-covalent interactions. We show that well-defined core–shell conjugated polymer nanofibers can be obtained through solvent induced self-assembly and polymer crystallization, while hydroxy and pyridine functional groups located at the shell of nanofibers can immobilize magnetic nanoparticles via hydrogen bonding and coordination interactions. These precisely arranged nanostructures possess electronic properties intrinsic to the polymers and are simultaneously responsive to external magnetic fields. We applied these composite nanofibers in organic solar cells and found that these non-covalent interactions led to controlled thin film morphologies containing uniformly dispersed nanoparticles, although high loadings of these inorganic components negatively impact device performance. Our methodology is general and can be utilized to control the spatial distribution of functionalized organic/inorganic building blocks, and the magnetic responsiveness and optoelectronic activities of these nanostructures may lead to new opportunities in energy and electronic applications.