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The functionalities of peptide microstructures and nanostructures can be enhanced by controlling their crystallinity. Gaining control over the crystallinity within the desired structure, however, remains a challenge. We have developed a three-dimensional (3D) printing method that enables spatioselective programming of the crystallinity of diphenylalanine (FF) dipeptide microarchitectures. A femtoliter ink meniscus is used to spatially control reprecipitation self-assembly, enabling the printing of a freestanding FF microstructure with programmed shape and crystallinity. The self-assembly crystallization of FF can be switched on and off at will by controlling the evaporation of the binary solvent. The evaporation-dependent crystallization was theoretically studied by the numerical simulation of supersaturation fields in the meniscus. We found that a 3D-printed FF microarchitecture with spatially programmed crystallinity can carry a 3D digital optical anisotropy pattern, applicable to generating polarization-encoded anticounterfeiting labels. This crystallinity-controlled additive manufacturing will pave the new way for facilitating the creation of peptide-based devices.
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Dipeptídeos , Impressão Tridimensional , Dipeptídeos/química , Peptídeos , Solventes/químicaRESUMO
Hybrid perovskites are emerging as a promising, high-performance luminescent material; however, the technological challenges associated with generating high-resolution, free-form perovskite structures remain unresolved, limiting innovation in optoelectronic devices. Here, we report nanoscale three-dimensional (3D) printing of colored perovskite pixels with programmed dimensions, placements, and emission characteristics. Notably, a meniscus comprising femtoliters of ink is used to guide a highly confined, out-of-plane crystallization process, which generates 3D red, green, and blue (RGB) perovskite nanopixels with ultrahigh integration density. We show that the 3D form of these nanopixels enhances their emission brightness without sacrificing their lateral resolution, thereby enabling the fabrication of high-resolution displays with improved brightness. Furthermore, 3D pixels can store and encode additional information into their vertical heights, providing multilevel security against counterfeiting. The proof-of-concept experiments demonstrate the potential of 3D printing to become a platform for the manufacture of smart, high-performance photonic devices without design restrictions.
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Direct mass-transfer via liquid nanodroplets is one of the most powerful approaches for additive micro/nanofabrication. Electrohydrodynamic (EHD) dispensing has made the delivery of nanosized droplets containing diverse materials a practical reality; however, in its serial form it has insufficient throughput for large-area processing. Here, a parallel, nanoscale EHD method is developed that offers both improved productivity and material diversity in 3D nanoprinting. The method exploits a double-barreled glass nanopipette filled with material inks to parallelize nanodripping ejections, enabling a dual 3D nanoprinting process. It is discovered that an unusual electric field distribution created by cross talk of neighboring pipette apertures can be used to steer the microscopic ejection paths of the ink at will, enabling on-demand control over shape, placement, and material mixing in 3D printed nanostructures. After thorough characterizations of the printing conditions, the parallel fabrication of nanomeshes and nanowalls of silver, CdSe/ZnS quantum dots, and their composites, with programmed designs is demonstrated. This method is expected to advance productivity in the heterogeneous integration of functional 3D nanodevices in a facile manner.
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Bimetallic nanoparticles often show properties superior to their single-component counterparts. However, the large parameter space, including size, structure, composition, and spatial arrangement, impedes the discovery of the best nanoparticles for a given application. High-throughput methods that can control the composition and spatial arrangement of the nanoparticles are desirable for accelerated materials discovery. Herein, we report a methodology for synthesizing bimetallic alloy nanoparticle arrays with precise control over their composition and spatial arrangement. A dual-channel nanopipet is used, and nanofluidic control in the nanopipet further enables precise tuning of the electrodeposition rate of each element, which determines the final composition of the nanoparticle. The composition control is validated by finite element simulation as well as electrochemical and elemental analyses. The scope of the particles demonstrated includes Cu-Ag, Cu-Pt, Au-Pt, Cu-Pb, and Co-Ni. We further demonstrate surface patterning using Cu-Ag alloys with precise control of the location and composition of each pixel. Additionally, combining the nanoparticle alloy synthesis method with scanning electrochemical cell microscopy (SECCM) allows for fast screening of electrocatalysts. The method is generally applicable for synthesizing metal nanoparticles that can be electrodeposited, which is important toward developing automated synthesis and screening systems for accelerated material discovery in electrocatalysis.
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Thermometry, the process of measuring temperature, is one of the most fundamental tasks not only for understanding the thermodynamics of basic physical, chemical, and biological processes but also for thermal management of microelectronics. However, it is a challenge to acquire microscale temperature fields in both space and time. Here, a 3D printed micro-thermoelectric device that enables direct 4D (3D Space + Time) thermometry at the microscale is reported. The device is composed of freestanding thermocouple probe networks, fabricated by bi-metal 3D printing with an outstanding spatial resolution of a few µm. It shows that the developed 4D thermometry can explore dynamics of Joule heating or evaporative cooling on microscale subjects of interest such as a microelectrode or a water meniscus. The utilization of 3D printing further opens up the possibility to freely realize a wide range of on-chip, freestanding microsensors or microelectronic devices without the design restrictions by manufacturing processes.
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Hyperlipidemia is a major contributor for atherosclerosis and hypolipidemic drugs such as statin are highly prescribed to treat elevated lipid level in plasma. Rubus coreanus, which is widely cultivated in south eastern Asia, have been reported to show significant cholesterol lowering action in hyperlipidemic subjects. Our objective was to determine the cellular effect of Rubus coreanus extract (RCE) on cholesterol biosynthesis in human hepatic cells (HepG2) and to elucidate the molecular mechanism by which it causes change in cholesterol metabolism. RCE treatment lowered cholesterol biosynthesis as well as secretion from HepG2 cells. This effect was associated with lowering the release of apolipoproteins from hepatic cells. RCE treatment also showed an increase in phosphorylation of foxhead box protein 01 (FoXo-1) and 5-adenosine monophosphate-activated protein kinase (AMPK), thus lowering expression of phosphoenolpyruvate carboxykinase (PEPCK) and G6Pase, which might be a major pathway for cholesterol biosynthesis inhibition. Apart from this; RCE also lowered sterol regulatory element-binding protein-1 (SREBP-1) expression in HepG2 cells, showing a long term regulation of cholesterol biosynthesis activity. These results indicate that one of the anti-hyperlipidemic actions of RCE is due to inhibition of cholesterol biosynthesis in hepatic cells and provides first documentation of a hypolipidemic bio-molecular action of Rubus coreanus.
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Colesterol/metabolismo , Ácidos Graxos/metabolismo , Hipolipemiantes/farmacologia , Extratos Vegetais/farmacologia , Rosaceae , Proteínas Quinases Ativadas por AMP/metabolismo , Apolipoproteína A-I/metabolismo , Apolipoproteínas B/metabolismo , Proteína Forkhead Box O1 , Fatores de Transcrição Forkhead/metabolismo , Glucose-6-Fosfatase/metabolismo , Células Hep G2 , Humanos , Hipolipemiantes/análise , Fígado/citologia , Fígado/metabolismo , Extratos Vegetais/análise , Proteínas Serina-Treonina Quinases/metabolismo , Solventes/química , Proteína de Ligação a Elemento Regulador de Esterol 1/metabolismo , Água/químicaRESUMO
Understanding the structure-activity relationship at electrochemical interfaces is crucial in improving the performance of practical electrochemical devices, ranging from fuel cells, electrolyzers, and batteries to electrochemical sensors. However, functional electrochemical interfaces are often complex and contain various surface structures, creating heterogeneity in electrochemical activity. In this Perspective, we highlight the role of heterogeneity in electrochemistry, especially in the context of electrocatalysis. Current methods for revealing the heterogeneity at electrochemical interfaces, including nanoelectrochemistry tools and single-entity approaches, are discussed. Lastly, we provide perspectives on what one can learn by studying heterogeneity and how one can use heterogeneity to design more efficient electrochemical devices.
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Fontes de Energia Elétrica , Eletroquímica/métodosRESUMO
Metal-organic frameworks (MOFs) are a promising nanoporous functional material system; however, the practicality of shaping freeform MOF monoliths, while retaining their porosity, remains a challenge. Here, we demonstrate that meniscus-guided three-dimensional (3D) printing can produce pure MOF monoliths with high gas-uptake performance. The method exploits a femtoliter precursor ink meniscus to highly confine and guide supersaturation-driven crystallization in a layer-by-layer manner to print a pure HKUST-1 micro-monolith with a high spatial resolution of <3 µm. The proposed 3D printing technique does not involve rheological additives, binders, or mechanical forces. Thus, the resulting HKUST-1 monolith displays a prominently high Brunauer-Emmett-Teller surface area of 1192 m2/g, which is superior to monoliths produced using other 3D printing approaches. This technique enables both structural design freedom and high material performance in the manufacturing of MOFs for practical use.
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The quantum defects in nanodiamonds, such as nitrogen-vacancy (NV) centers, are emerging as a promising candidate for nanoscale sensing and imaging, and the controlled placement with respect to target locations is vital to their practical applications. Unfortunately, this prerequisite continues to suffer from coarse positioning accuracy, low throughput, and process complexity. Here, it is reported on direct, on-demand electrohydrodynamic printing of nanodiamonds containing NV centers with high precision control over quantity and position. After thorough characterizations of the printing conditions, it is shown that the number of printed nanodiamonds can be controlled at will, attaining the single-particle level precision. This printing approach, therefore, enables positioning NV center arrays with a controlled number directly on the universal substrate without any lithographic process. The approach is expected to pave the way toward new horizons not only for experimental quantum physics but also for the practical implementation of such quantum systems.
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Continuous-flow microreactors enable ultrafast chemistry; however, their small capacity restricts industrial-level productivity of pharmaceutical compounds. In this work, scale-up subsecond synthesis of drug scaffolds was achieved via a 16 numbered-up printed metal microreactor (16N-PMR) assembly to render high productivity up to 20 g for 10 min operation. Initially, ultrafast synthetic chemistry of unstable lithiated intermediates in the halogen-lithium exchange reactions of three aryl halides and subsequent reactions with diverse electrophiles were carried out using a single microreactor (SMR). Larger production of the ultrafast synthesis was achieved by devising a monolithic module of 4 numbered-up 3D-printed metal microreactor (4N-PMR) that was integrated by laminating four SMRs and four bifurcation flow distributors in a compact manner. Eventually, the 16N-PMR system for the scalable subsecond synthesis of three drug scaffolds was assembled by stacking four monolithic modules of 4N-PMRs.
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Peptide-based materials are emerging as smart building blocks for nanobiodevices due to the programmability of their properties via the molecular constituents or arrangements. Many clever molecular self-assembly approaches have been devised to produce peptide crystalline structures. However, their freeform shaping remains a challenge due to the intrinsic self-assembly nature. Here, we report the fabrication of freeform, crystalline diphenylalanine (FF) peptide structures by combining meniscus-guided 3D printing with molecular self-assembly. Self-assembly in 3D-printed FF arises from mild thermal activation under precise temperature control of the build platform. After thorough characterizations, we demonstrate layer-by-layer, crystalline 3D printing with a high spatial resolution of 2 µm laterally and 200 nm vertically. The 3D-printed FF exhibits piezoelectricity originating from its crystalline character, showing the potential to become a key constituent for bioelectronic devices. We expect this technique to open up the possibility to create functional devices based on self-assembled organic materials without design restrictions.
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Dipeptídeos/química , Impressão Tridimensional , Microscopia de Força Atômica , Microscopia Eletrônica de Varredura , Microscopia Eletrônica de TransmissãoRESUMO
Although there has been extensive development and exploration of small-scale robots, the technological challenges associated with their complicated and high-cost fabrication processes remain unresolved. Here, we report a one-step, bi-material, high-resolution three-dimensional (3D) printing method for the fabrication of multi-stimuli-responsive microactuators. This method exploits a two-phase femtoliter ink meniscus formed on a double-barreled theta micropipette to continuously print a freestanding bilayer microstructure, which undergoes an asymmetric volume change upon the adsorption or desorption of water. We show that the 3D-printed bilayer microstructures exhibit reversible, reproducible actuation in ambient humidity or under illumination with infrared light. Our 3D printing approach can assemble bilayer segments for programming microscale actuation, as demonstrated by proof-of-concept experiments. We expect that this method will serve as the basis for flexible, programmable, one-step routes for the assembly of small-scale intelligent actuators.
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With the growing importance of three-dimensional (3D) nanomaterials and devices, there has been a great demand for high-fidelity, full profile topographic characterizations in a nondestructive manner. A promising route is to employ a high-aspect-ratio (HAR) probe in atomic force microscopy (AFM) imaging. However, the fabrication of HAR-AFM probes continues to suffer from extravagant cost, limited material choice, and complicated manufacturing steps. Here, we report one-step, on-demand electrohydrodynamic 3D printing of metallic HAR-AFM probes with tailored dimensions. Our additive fabrication approach yields a freestanding metallic nanowire with an aspect ratio over 30 directly on a cantilever within tens of seconds, producing a HAR-AFM probe. Furthermore, the benefits associated with unprecedented simplicity in the probe's dimension control, material selection, and regeneration are provided. The 3D-printed HAR-AFM probe exhibits a better fidelity in deep trench AFM imaging than a standard pyramidal probe. We expect this approach to find facile, material-saving manufacturing routes in particular for customizing functional nanoprobes.
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As competing with the established silicon technology, organic-inorganic metal halide perovskites are continually gaining ground in optoelectronics due to their excellent material properties and low-cost production. The ability to have control over their shape, as well as composition and crystallinity, is indispensable for practical materialization. Many sophisticated nanofabrication methods have been devised to shape perovskites; however, they are still limited to in-plane, low-aspect-ratio, and simple forms. This is in stark contrast with the demands of modern optoelectronics with freeform circuitry and high integration density. Here, a nanoprecision 3D printing is developed for organic-inorganic metal halide perovskites. The method is based on guiding evaporation-induced perovskite crystallization in mid-air using a femtoliter ink meniscus formed on a nanopipette, resulting in freestanding 3D perovskite nanostructures with a preferred crystal orientation. Stretching the ink meniscus with a pulling process enables on-demand control of the nanostructure's diameter and hollowness, leading to an unprecedented tubular-solid transition. With varying the pulling direction, a layer-by-layer stacking of perovskite nanostructures is successfully demonstrated with programmed shapes and positions, a primary step for additive manufacturing. It is expected that the method has the potential to create freeform perovskite nanostructures for customized optoelectronics.
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Mosquito larvicidal activity of Piper longum fruit-derived materials against the fourth-instar larvae of Aedes aegypti was examined. A crude methanol extract of P. longum fruits was found to be active against the larvae, and the hexane fraction of the methanol extract showed a strong larvicidal activity of 100% mortality. The biologically active component of P. longum fruits was characterized as pipernonaline by spectroscopic analyses. The LC(50) value of pipernonaline was 0.25 mg/L. The toxicity of pipernonaline is comparable to that of pirimiphos-methyl as a mosquito larvicide. In tests with available components derived from P. longum, no activity was observed with piperettine, piperine, or piperlongumine.
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Aedes , Alcaloides/isolamento & purificação , Frutas/química , Inseticidas/isolamento & purificação , Piperaceae/química , Piperidinas , Extratos Vegetais/química , Aedes/crescimento & desenvolvimento , Alcaloides/química , Animais , Inseticidas/química , Larva , MetanolRESUMO
Oxidized low-density lipoprotein (oxLDL) contributes to atherosclerosis in part by being taken up into macrophages via scavenger receptors and leading to foam cell formation. Herbal compounds that have been used to treat blood stasis (a counterpart of atherosclerosis) for centuries include extracts of medicinal plants in the Rosaceae and Leguminosae families. In this study, we investigated the effect of the unripe Rubus coreanus (Korean black raspberry) fruit extract on oxLDL uptake by murine macrophage cells. In the presence of Rubus coreanus extract (RCE), Dil-labeled oxLDL uptake was inhibited in a dose-dependent manner. SP600125, a specific JNK inhibitor, inhibited the uptake of Dil-oxLDL into macrophages. RCE also inhibited JNK phosphorylation in a time- and dose-dependent manner in macrophages treated with oxLDL. These results indicate that among the mitogen-activated protein kinases, JNK phosphorylation is inhibited by RCE, which is likely the mechanism underlying the RCE-induced inhibition of oxLDL uptake by macrophages.