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Low-dimensional nanostructures, especially one-dimensional materials, exhibit remarkable anisotropic characteristics due to their low symmetry, making them promising candidates for polarization-sensitive photodetection. Here, we present a chemical vapor deposition synthesis method for tellurium suboxide (TeOx), confirming the practicality of photodetectors constructed from TeOx nanowires (NWs) in high-responsivity, broadband, and polarization-sensitive detection. By precisely controlling the thermodynamics and kinetics of TeOx NWs growth, we achieve large-scale growth of TeOx NWs with highly controllable dimensions and propose a method to induce intrinsic built-in strain in TeOx NWs. Photodetectors based on quasi-one-dimensional TeOx NWs with ohmic contact demonstrate broadband spectral response (638-1550 nm), high responsivity (13 700 mA·W-1), and superior air stability. Particularly, owing to the inherent structural anisotropy of the photodetectors, they exhibit polarization-sensitive photodetection, with anisotropy ratios of 1.70 and 1.71 at 638 and 808 nm, respectively.
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OBJECTIVES: To explore the effects and mechanisms of bilirubin on mitochondrial function and type of macrophage cell death after exposure to cigarette smoke extract (CSE). METHODS: RAW264.7 macrophages were treated with different concentrations of CSE and bilirubin solutions and divided into four groups: control, CSE, bilirubin, and bilirubin + CSE groups. The necrotic and apoptotic states of the macrophages were determined using an Annexin V-fluorescein 5-isothiocyanate/propidium iodide (FITC/PI) staining kit. Cytoplasmic NOD-like receptor family, pyrin domain containing 3 (NLRP3) expression in macrophages was detected by immunofluorescence and the levels of IL-1ß and IL-18 in the supernatants of culture medium were detected by enzyme linked immunosorbent assay (ELISA) test. A JC-1 mitochondrial membrane potential detection kit was used to assess mitochondrial membrane damage and the adenosine triphosphate (ATP) assay kit was used to determine intracellular ATP levels. After the macrophages were stained with reactive oxygen species (ROS) specific dye, 2',7'-Dichlorodihydrofluorescein diacetate (DCFH-DA), the fluorescence intensity and proportion of ROS-positive macrophages were measured using flow cytometry. RESULTS: We observed that compared with those of 0 µM (control group), concentrations of 5, 10, or 20 µΜ bilirubin significantly decreased cell viability, which was increased by bilirubin exposure below 1 µM. The effect of CSE on macrophage viability was concentration- and time-dependent. Bilirubin of 0.2 µM could alleviate the inhibition of macrophage viability caused by 5% CSE. In addition, bilirubin intervention could reduce the occurrence of necrosis and pyroptosis to a certain extent. CONCLUSIONS: CSE could cause mitochondrial dysfunction in macrophages, as demonstrated by a decrease in mitochondrial membrane potential and intracellular ATP levels and an increase in ROS production, while bilirubin could relieve mitochondrial dysfunction caused by CSE.
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Bilirrubina , Macrófagos , Mitocôndrias , Espécies Reativas de Oxigênio , Animais , Camundongos , Mitocôndrias/efeitos dos fármacos , Mitocôndrias/metabolismo , Macrófagos/efeitos dos fármacos , Macrófagos/metabolismo , Células RAW 264.7 , Espécies Reativas de Oxigênio/metabolismo , Potencial da Membrana Mitocondrial/efeitos dos fármacos , Morte Celular/efeitos dos fármacos , Nicotiana/efeitos adversos , Nicotiana/química , Fumaça/efeitos adversos , Apoptose/efeitos dos fármacos , Proteína 3 que Contém Domínio de Pirina da Família NLR/metabolismoRESUMO
The transition from anisotropic to isotropic optical properties in nanostructures plays an important role in developing next-generation intelligent photonic devices. Currently, core-shell nanostructures, frequently accompanied by different growth rates, are typically characterized by anisotropic optical properties at mid-infrared wavelengths. This inherent anisotropy, however, poses formidable challenges in achieving optical isotropy. In this work, an electric field is employed to transform the optical anisotropy of the off-centered core-shell square nanowires into optical isotropy. Based on the finite difference method, the results show that by tuning the electric field reasonably, the anti-crossing behavior of energy levels can be induced to align the energy structures in both eccentric and concentric nanowires. Although the optical anisotropy is strongly dependent on the distance and direction of the core shift, we marks, to the best of our knowledge, the first demonstration that the restored electronic states can effectively neutralize the polarization sensitivity, achieving isotropic optical absorption with wavelengths longer than 10â µm. Our finding indicates that the anti-crossing behavior of energy levels can serve as a viable mechanism to achieve switchable optical isotropy.
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Targeted proteasomal and autophagic protein degradation, often employing bifunctional modalities, is a new paradigm for modulation of protein function. In an attempt to explore protein degradation by means of autophagy we combine arylidene-indolinones reported to bind the autophagy-related LC3B-protein and ligands of the PDEδ lipoprotein chaperone, the BRD2/3/4-bromodomain containing proteins and the BTK- and BLK kinases. Unexpectedly, the resulting bifunctional degraders do not induce protein degradation by means of macroautophagy, but instead direct their targets to the ubiquitin-proteasome system. Target and mechanism identification reveal that the arylidene-indolinones covalently bind DCAF11, a substrate receptor in the CUL4A/B-RBX1-DDB1-DCAF11 E3 ligase. The tempered α, ß-unsaturated indolinone electrophiles define a drug-like DCAF11-ligand class that enables exploration of this E3 ligase in chemical biology and medicinal chemistry programs. The arylidene-indolinone scaffold frequently occurs in natural products which raises the question whether E3 ligand classes can be found more widely among natural products and related compounds.
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Produtos Biológicos , Proteínas Culina , Oxindóis , Ligantes , Proteínas Culina/metabolismo , Ubiquitina-Proteína Ligases/metabolismo , Proteólise , Complexo de Endopeptidases do Proteassoma/metabolismo , Produtos Biológicos/farmacologia , UbiquitinaçãoRESUMO
We study the stability and characteristics of two-dimensional circular quantum droplets (QDs) with embedded hidden vorticity (HV), i.e., opposite angular momenta in two components, formed by binary Bose-Einstein condensates (BECs) trapped in a radially periodic potential. The system is modeled by the Gross-Pitaevskii equations with the Lee-Huang-Yang terms, which represent the higher-order self-repulsion induced by quantum fluctuations around the mean-field state, and a potential which is a periodic function of the radial coordinate. Ring-shaped QDs with high winding numbers (WNs) of the HV type, which are trapped in particular circular troughs of the radial potential, are produced by means of the imaginary-time-integration method. Effects of the depth and period of the potential on these QD states are studied. The trapping capacity of individual circular troughs is identified. Stable compound states in the form of nested multiring patterns are constructed too, including ones with WNs of opposite signs. The stably coexisting ring-shaped QDs with different WNs can be used for the design of BEC-based data-storage schemes.
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Monoterpene indole alkaloids (MIAs) are endowed with high structural and spatial complexity and characterized by diverse biological activities. Given this complexity-activity combination in MIAs, rapid and efficient access to chemical matter related to and with complexity similar to these alkaloids would be highly desirable, since such compound classes might display novel bioactivity. We describe the design and synthesis of a pseudo-natural product (pseudo-NP) collection obtained by the unprecedented combination of MIA fragments through complexity-generating transformations, resulting in arrangements not currently accessible by biosynthetic pathways. Cheminformatic analyses revealed that both the pseudo-NPs and the MIAs reside in a unique and common area of chemical space with high spatial complexity-density that is only sparsely populated by other natural products and drugs. Investigation of bioactivity guided by morphological profiling identified pseudo-NPs that inhibit DNA synthesis and modulate tubulin. These results demonstrate that the pseudo-NP collection occupies similar biologically relevant chemical space that Nature has endowed MIAs with.
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Alcaloides , Monoterpenos , Alcaloides IndólicosRESUMO
Pure-red perovskite LEDs (PeLEDs) based on CsPb(Br/I)3 nanocrystals (NCs) usually suffer from a compromise in emission efficiency and spectral stability on account of the surface halide vacancies-induced nonradiative recombination loss, halide phase segregation, and self-doping effect. Herein, a "halide-equivalent" anion of benzenesulfonate (BS- ) is introduced into CsPb(Br/I)3 NCs as multifunctional additive to simultaneously address the above challenging issues. Joint experiment-theory characterizations reveal that the BS- can not only passivate the uncoordinated Pb2+ -related defects at the surface of NCs, but also increase the formation energy of halide vacancies. Moreover, because of the strong electron-withdrawing property of sulfonate group, electrons are expected to transfer from the CsPb(Br/I)3 NC to BS- for reducing the self-doping effect and altering the n-type behavior of CsPb(Br/I)3 NCs to near ambipolarity. Eventually, synergistic boost in device performance is achieved for pure-red PeLEDs with CIE coordinates of (0.70, 0.30) and a champion external quantum efficiency of 23.5%, which is one of the best value among the ever-reported red PeLEDs approaching to the Rec. 2020 red primary color. Moreover, the BS- -modified PeLED exhibits negligible wavelength shift under different operating voltages. This strategy paves an efficient way for improving the efficiency and stability of pure-red PeLEDs.
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Organic solar cells (OSCs) have been widely studied due to the advantages of easy fabrication, low cost, light weight, good flexibility and sufficient transparency. In this work, flexible and semitransparent OSCs were successfully fabricated with the adoption of both polyimide/silver nanowires (PI/AgNW) and a conducting polymer PEDOT:PSS named PH1000 as the transparent conductive electrodes (TCEs). It is demonstrated that PI/AgNW is more suitable as a cathode rather than an anode in the viewpoint of its work function, photovoltaic performance, and simulations of optical properties. It is also found that the light incidence from PH1000 TCE can produce more plasmonic-enhanced photon absorption than the PI/AgNW electrode does, resulting in more high power conversion efficiency. Moreover, a high light transmittance of 33.8% and a decent efficiency of 3.88% are achieved for the whole all-flexible semitransparent device with only 9% decrease of resistance in PI/AgNW after 3000 bending cycles. This work illustrates that PI/AgNW has great potential and bright prospect in large-area OSC applications in the future.
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Although tremendous progress has recently been made in quasi-2D perovskite light-emitting diodes (PeLEDs), the performance of red PeLEDs emitting at ≈650-660 nm, which have wide prospects for application in photodynamic therapy, is still limited by an inefficient energy transfer process between the quasi-2D perovskite layers. Herein, a symmetric molecule of 3,3'-(9H-fluorene-9,9-diyl)dipropanamide (FDPA) is designed and developed with two functional acylamino groups and incorporated into the quasi-2D perovskites as the additive for achieving high-performance red PeLEDs. It is demonstrated that the agent can simultaneously diminish the van der Waals gaps between individual perovskite layers and passivate uncoordinated Pb2+ related defects at the surface and grain boundaries of the quasi-2D perovskites, which truly results in an efficient energy transfer in the quasi-2D perovskite films. Consequently, the red PeLEDs emitting at 653 nm with a peak external quantum efficiency of 18.5% and a maximum luminance of 2545 cd m-2 are achieved, which is among the best performing red quasi-2D PeLEDs emitting at ≈650-660 nm. This work opens a way to further improve the electroluminescence performance of red PeLEDs.
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Pseudo-natural products (pseudo-NPs) are de novo combinations of natural product (NP) fragments that define novel bioactive chemotypes. For their discovery, new design principles are being sought. Previously, pseudo-NPs were synthesized by the combination of fragments originating from biosynthetically unrelated NPs to guarantee structural novelty and novel bioactivity. We report the combination of fragments from biosynthetically related NPs in novel arrangements to yield a novel chemotype with activity not shared by the guiding fragments. We describe the synthesis of the polyketide pseudo-NP grismonone and identify it as a structurally novel and potent inhibitor of Hedgehog signaling. The insight that the de novo combination of fragments derived from biosynthetically related NPs may also yield new biologically relevant compound classes with unexpected bioactivity may be considered a chemical extension or diversion of existing biosynthetic pathways and greatly expands the opportunities for exploration of biologically relevant chemical space by means of the pseudo-NP principle.
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Antineoplásicos , Produtos Biológicos , Policetídeos , Produtos Biológicos/química , Proteínas Hedgehog/metabolismo , Vias BiossintéticasRESUMO
A stereoselective amination/cyclization cascade process has been developed that allows for the preparation of a series of unsaturated and substituted caprolactam derivatives in good yields. This conceptually novel protocol takes advantage of the easy access and modular character of vinyl γ-lactones that can be prepared from simple precursors. Activation of the lactone substrate in the presence of a suitable Pd precursor and newly developed phosphoramidite ligand offers a stereocontrolled ring-opening/allylic amination manifold under ambient conditions. The intermediate (E)-configured ε-amino acid can be cyclized using a suitable dehydrating agent in an efficient one-pot, two-step sequence. This overall highly chemo-, stereo- and regio-selective transformation streamlines the production of a wide variety of modifiable and valuable caprolactam building blocks in an operationally attractive way.
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Tertiary allylic alcohols were conveniently converted into either (Z)- or (E)-configured α,ß-unsaturated γ-amino acids by treatment with secondary amines under Pd catalysis at ambient conditions. The key to control the stereochemical course of these formal allylic aminations was the presence of a suitable diphosphine ligand, with dppp [1,3-bis(diphenylphosphino)propane, L12] providing high yields and selectivities for the (Z) isomers, whereas the bis[(2-diphenylphosphino)phenyl]ether (DPEPhos) derivative L1' allowed for selective formation of the corresponding (E) isomeric products. This ligand-controlled, stereodivergent protocol thus shows promise for the stereoselective preparation of allylic amine products from a common substrate precursor.
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Aminoácidos/química , Paládio/química , Propanóis/química , Aminação , Catálise , Éteres/química , Ligantes , Fosfinas/química , EstereoisomerismoRESUMO
Tertiary allylic alcohols equipped with a carboxyl group can be smoothly aminated under ambient conditions by a conceptually new and stereoselective protocol under palladium catalysis. The in situ formed Z-configured γ-amino acid cyclizes to afford an α,ß-unsaturated γ-lactam, releasing water as the only byproduct. This practical catalytic transformation highlights the use of a carboxyl group acting as an activating and stereodirecting functional group to provide a wide series of pharma-relevant building blocks. Various control reactions support the crucial role of the carboxyl group in the substrate to mediate these transformations.
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Lactamas/síntese química , Propanóis/química , Aminação , Lactamas/química , Estrutura Molecular , EstereoisomerismoRESUMO
Functionalized cyclic organic carbonates and related heterocycles have emerged as highly versatile heterocyclic substrates for ring-opening and decarboxylative catalytic transformations allowing for the development of new stereo- and enantioselective C-N, C-O, C-C, C-S and C-B bond formation reactions. Transition-metal-mediated conversions have only recently been rejuvenated as powerful approaches towards the preparation of more complex molecules. This minireview will highlight the potential of cyclic carbonates and structurally related heterocycles with a focus on their synthetic value and the mechanistic manifolds that are involved upon their conversion.
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For the first time, compounds with lanthanum from the main family element Boron (LaBx) were investigated as an active layer for thin-film transistors (TFTs). Detailed studies showed that the room-temperature fabricated LaBx thin film was in the crystalline state with a relatively narrow optical band gap of 2.28 eV. The atom ration of La/B was related to the working pressure during the sputtering process and the atom ration of La/B increased with the increase of the working pressure, which will result in the freer electrons in the LaBx thin film. LaBx-TFT without any intentionally annealing steps exhibited a saturation mobility of 0.44 cm²·V−1·s−1, which is a subthreshold swing (SS) of 0.26 V/decade and a Ion/Ioff ratio larger than 104. The room-temperature process is attractive for its compatibility with almost all kinds of flexible substrates and the LaBx semiconductor may be a new choice for the channel materials in TFTs.
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Boro/química , Eletrônica , Lantânio/química , Temperatura , Cristalografia por Raios X , Espectroscopia Fotoeletrônica , Espectrofotometria UltravioletaRESUMO
We numerically show the generation of robust vortex clusters embedded in a two-dimensional beam propagating in a dissipative medium described by the generic cubic-quintic complex Ginzburg-Landau equation with an inhomogeneous effective diffusion term, which is asymmetrical in the two transverse directions and periodically modulated in the longitudinal direction. We show the generation of stable optical vortex clusters for different values of the winding number (topological charge) of the input optical beam. We have found that the number of individual vortex solitons that form the robust vortex cluster is equal to the winding number of the input beam. We have obtained the relationships between the amplitudes and oscillation periods of the inhomogeneous effective diffusion and the cubic gain and diffusion (viscosity) parameters, which depict the regions of existence and stability of vortex clusters. The obtained results offer a method to form robust vortex clusters embedded in two-dimensional optical beams, and we envisage potential applications in the area of structured light.
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A general methodology for the synthesis of enantioenriched tertiary allylic aryl ethers through Pd-catalyzed decarboxylative reactions of vinyl cyclic carbonates and phenols is presented. Switching of the regioselectivity toward the formation of linear products by a judicious choice of the ligand is also reported.
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The first asymmetric synthesis of important α,α-disubstituted N-alkyl allyl amine scaffolds through allylic substitution is reported. This approach is based on palladium catalysis and features ample scope with respect to both the allylic precursor and amine reagent, and high asymmetric induction with enantiomeric ratios (e.r.) up to 98.5:1.5. The use of less-reactive anilines is also feasible, providing enantioenriched α,α-disubstituted N-aryl allylic amines.
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A silver(I)-catalyzed three-component reaction of propargylic alcohols, CO2 , and monohydric alcohols was successfully developed for the synthesis of ß-oxopropyl carbonates. As such, a series of ß-oxopropyl carbonates were exclusively produced in excellent yields (up to 98 %), even under atmospheric pressure of CO2 . The silver catalyst works efficiently for both the carboxylative cyclization of propargylic alcohols with CO2 and subsequent transesterification of α-alkylidene cyclic carbonates with monohydric alcohols; thus this tandem process performs smoothly under mild conditions. This work provides a versatile and thermodynamically favorable approach to dissymmetric dialkyl carbonates.
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Based on a molecular-orbital theory for H2(+), we have proposed and tested a pair potential function form for the diatomic systems. The new form has included the Pauli repulsive term, Rydberg potential, and London inverse-sixth-power energy, and is accurate at all relevant distances and simple enough for practical application in all-atom computer simulations. We find that an "approximate" universal reduced potential curve for strongly and weakly bound diatomic molecules may exist.