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Boron nitride nanosheets, quantum dots, and dots: Synthesis, properties, and biomedical applicationsThis review examines three aspects of hexagonal boron nitride (h-BN) nanomaterials: properties, synthesis methods, and biomedical applications. We focus the scope of review on three types of h-BN nanostructures: boron nitride nanosheets (BNNSs, few-layered h-BN, larger than ∼100 nm in lateral dimensions), boron nitride quantum dots (BN QDs, smaller than ∼10 nm in all dimensions, with inherent excitation-dependent fluorescence), and boron nitride dots (BN dots, smaller than ∼10 nm in all dimensions, wide bandgap without noise fluorescence). The synthesis methods of BNNSs, BN QDs, and BN dots are summarized in top-down and bottom-up approaches. Future synthesis research should focus on the scalability and the quality of the products, which are essential for reproducible applications. Regarding biomedical applications, BNNSs were used as nanocarriers for drug delivery, mechanical reinforcements (bone tissue engineering), and antibacterial applications. BN QDs are still limited for non-specific bioimaging applications. BN dots are used for the small dimension to construct high-brightness probes (HBPs) for gene sequence detections inside cells. To differentiate from other two-dimensional materials, future applications should focus on using the unique properties of BN nanostructures, such as piezoelectricity, boron neutron capture therapy (BNCT), and their electrically insulating and optically transparent nature. Examples would be combining BNCT and chemo drug delivery using BNNSs, and using BN dots to form HBPs with enhanced fluorescence by preventing fluorescence quenching using electrically insulating BN dots.more » « less
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In this review, we examine recent progress using boron nitride (BN) and molybdenum disulfide (MoS2) nanostructures for electronic, energy, biomedical, and environmental applications. The scope of coverage includes zero-, one-, and two-dimensional nanostructures such as BN nanosheets, BN nanotubes, BN quantum dots, MoS2 nanosheets, and MoS2 quantum dots. These materials have sizable bandgaps, differentiating them from other metallic nanostructures or small-bandgap materials. We observed two interesting trends: (1) an increase in applications that use heterogeneous materials by combining BN and MoS2 nanostructures with other nanomaterials, and (2) strong research interest in environmental applications. Last, we encourage researchers to study how to remove nanomaterials from air, soil, and water contaminated with nanomaterials. As nanotechnology proceeds into various applications, environmental contamination is inevitable and must be addressed. Otherwise, nanomaterials will go into our food chain much like microplastics.more » « less
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Anion exchange is a facile, post-synthetic method to tune the emission wavelength of colloidal cesium lead halide (CsPbX3, X = Cl, Br, I) perovskite nanocrystals. While colloidal nanocrystals can exhibit size-dependent phase stability and chemical reactivity, the role of size in the mechanism of anion exchange in CsPbX3 nanocrystals has not been elucidated. We used single-particle fluorescence microscopy to monitor the transformation of individual CsPbBr3 nanocrystals to CsPbI3. By systematically varying the size of the nanocrystals and the concentration of substitutional iodide, we observed that smaller nanocrystals exhibit longer transition times in their fluorescence trajectories, while larger nanocrystals undergo a more abrupt transition during anion exchange. Monte Carlo simulations were used to rationalize the size-dependent reactivity, in which we varied how each exchange event affects the probability for further exchange. Greater cooperativity for simulated ion exchange leads to shorter transition times to complete the exchange. We propose that size-dependent miscibility between CsPbBr3 and CsPbI3 at the nanoscale controls the reaction kinetics. Smaller nanocrystals maintain a homogeneous composition during anion exchange. As the nanocrystal size increases, variations in the octahedral tilting patterns of the perovskite crystals lead to different structures for CsPbBr3 and CsPbI3. Thus, an iodide-rich region must first nucleate within larger CsPbBr3 nanocrystals, which is followed by rapid transformation to CsPbI3. While higher concentrations of substitutional anions can suppress this size-dependent reactivity, the inherent differences in reactivity between nanocrystals of different sizes are important to consider when scaling up this reaction for applications in solid-state lighting and biological imaging.more » « less
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Materials with metastable phases can exhibit vastly different properties from their thermodynamically favored counterparts. Methods to synthesize metastable phases without the need for high-temperature or high-pressure conditions would facilitate their widespread use. We report on the electrochemical growth of microcrystals of bismuth selenide, Bi2Se3, in the metastable orthorhombic phase at room temperature in aqueous solution. Rather than direct epitaxy with the growth substrate, the spontaneous formation of a seed layer containing nanocrystals of cubic BiSe enforces the metastable phase. We first used single-crystal silicon substrates with a range of resistivities and different orientations to identify the conditions needed to produce the metastable phase. When the applied potential during electrochemical growth is positive of the reduction potential of Bi3+, an initial, Bi-rich seed layer forms. Electron microscopy imaging and diffraction reveal that the seed layer consists of nanocrystals of cubic BiSe embedded within an amorphous matrix of Bi and Se. Using density functional theory calculations, we show that epitaxial matching between cubic BiSe and orthorhombic Bi2Se3 can help stabilize the metastable orthorhombic phase over the thermodynamically stable rhombohedral phase. The spontaneous formation of the seed layer enables us to grow orthorhombic Bi2Se3 on a variety of substrates including single-crystal silicon with different orientations, polycrystalline fluorine-doped tin oxide, and polycrystalline gold. The ability to stabilize the metastable phase through room-temperature electrodeposition in aqueous solution without requiring a single-crystal substrate broadens the range of applications for this semiconductor in optoelectronic and electrochemical devices.more » « less
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Abstract Protein aggregation results in an array of different size soluble oligomers and larger insoluble fibrils. Insoluble fibrils were originally thought to cause neuronal cell deaths in neurodegenerative diseases due to their prevalence in tissue samples and disease models. Despite recent studies demonstrating the toxicity associated with soluble oligomers, many therapeutic strategies still focus on fibrils or consider all types of aggregates as one group. Oligomers and fibrils require different modeling and therapeutic strategies, targeting the toxic species is crucial for successful study and therapeutic development. Here, we review the role of different‐size aggregates in disease, and how factors contributing to aggregation (mutations, metals, post‐translational modifications, and lipid interactions) may promote oligomers opposed to fibrils. We review two different computational modeling strategies (molecular dynamics and kinetic modeling) and how they are used to model both oligomers and fibrils. Finally, we outline the current therapeutic strategies targeting aggregating proteins and their strengths and weaknesses for targeting oligomers versus fibrils. Altogether, we aim to highlight the importance of distinguishing the difference between oligomers and fibrils and determining which species is toxic when modeling and creating therapeutics for protein aggregation in disease.more » « less
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