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BACKGROUND: Phosphorus (P) deficiency, a major nutrient stress, greatly hinders plant growth. Phosphate (Pi) uptake in plant roots relies on PHT1 family transporters. However, melon (Cucumis melo L.) lacks comprehensive identification and characterization of PHT1 genes, particularly their response patterns under diverse stresses. RESULTS: This study identified and analyzed seven putative CmPHT1 genes on chromosomes 3, 4, 5, 6, and 7 using the melon genome. Phylogenetic analysis revealed shared motifs, domain compositions, and evolutionary relationships among genes with close histories. Exon number varied from 1 to 3. Collinearity analysis suggested segmental and tandem duplications as the primary mechanisms for CmPHT1 gene family expansion. CmPHT1;4 and CmPHT1;5 emerged as a tandemly duplicated pair. Analysis of cis-elements in CmPHT1 promoters identified 14 functional categories, including putative PHR1-binding sites (P1BS) in CmPHT1;4, CmPHT1;6, and CmPHT1;7. We identified that three WRKY transcription factors regulated CmPHT1;5 expression by binding to its W-box element. Notably, CmPHT1 promoters harbored cis-elements responsive to hormones and abiotic factors. Different stresses regulated CmPHT1 expression differently, suggesting that the adjusted expression patterns might contribute to plant adaptation. CONCLUSIONS: This study unveils the characteristics, evolutionary diversity, and stress responsiveness of CmPHT1 genes in melon. These findings lay the foundation for in-depth investigations into their functional mechanisms in Cucurbitaceae crops.
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Cucumis melo , Regulação da Expressão Gênica de Plantas , Fosfatos , Filogenia , Proteínas de Plantas , Estresse Fisiológico , Cucumis melo/genética , Cucumis melo/metabolismo , Fosfatos/metabolismo , Proteínas de Plantas/genética , Proteínas de Plantas/metabolismo , Estresse Fisiológico/genética , Genes de Plantas , Proteínas de Transporte de Fosfato/genética , Proteínas de Transporte de Fosfato/metabolismo , Transporte Biológico/genéticaRESUMO
The exploitation of multicomponent composites (MCCs) has become the main pathway for obtaining advanced microwave absorption materials (MAMs). Herein, a metal valence state modulation strategy is proposed to tune the electromagnetic (EM) parameters and improve microwave absorption performances. Core@shell hollow carbon microspheres@MoSe2 and hollow carbon microspheres@MoSe2/MoOx MCCs with various mixed-valence states content are well-designed and produced by a simple hydrothermal reaction or/and heat treatment process. The results reveal that the thermal treatment of hollow carbon microspheres@MoSe2 in Ar and Ar/H2 leads to the in situ formation of MoOx and multivalence state, respectively, and the enhanced content of Mo4+ in the designed MCCs greatly boosts their impedance matching characteristics, polarization, and conduction loss capacities, which lead to their evidently improved EM wave absorption properties. Amongst, the as-prepared hollow carbon microspheres@MoSe2/MoOx MCCs achieve an effective absorption bandwidth of 5.80 GHz under a matching thickness of 1.97 mm and minimum reflection loss of -21.49 dB. Therefore, this work offers a simple and universal method to fabricate core@shell hollow carbon microspheres@MoSe2/MoOx MCCs, and a novel and feasible metal valence state modulation strategy is proposed to develop high-efficiency MAMs.
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Highly efficient synthesis of axially chiral biaryl amines through cobalt-catalyzed atroposelective C-H arylation using easily accessible cobalt(II) salt and salicyloxazoline ligand has been reported. This methodology provides a straightforward and sustainable access to a broad range of enantioenriched biaryl-2-amines in good yields (up to 99 %) with excellent enantioselectivities (up to 99 % ee). The synthetic utility of the unprecedented method is highlighted by its scalability and diverse transformations.
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Substituted naphthalimide (NI) moieties are highly versatile and newly recognized aggregation-induced emission (AIE) building blocks for many potentially useful smart molecules, polymers, and nanoparticles. However, the introduction of NI fluorophore into cross-linked polymeric networks to prepare AIE-active hydrogels still remains underdeveloped. Herein, a novel naphthalimide-based aggregation-induced emissive polymeric hydrogel is reported, followed by its proof-of-concept applications as fluorescence pattern switch and biomimetic actuator. The hydrogel, bearing semi-interpenetrating polymer networks, is synthesized starting from N-isopropylacrylamide, hydroxyethyl methacrylate, and a newly designed NI monomer (4-phenoxy-N-allyl-1,8-naphthalimide, PhAN). Rational molecular design for AIE-active PhAN monomer lies in modification of the NI core with rigid and bulky phenoxy group to break its planarity to produce desirable propeller-shaped molecular conformation. The as-prepared hydrogel is proved to be a aggregation-induced blue-light-emitting hydrogel. It also shows volume phase transition behavior and is endowed with thermally responsive synergistic emission and transmittance change, thus enabling simultaneous regulation of two optical properties merely by one single stimulus. These useful advantages further encourage fabrication of several proto-type fluorescence pattern switching and biomimetic actuating devices. This study may not only enlarge the list of fluorescent hydrogels but also serve as a novel smart optical platform for potential anticounterfeiting, sensing, displaying, or actuating applications.
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Hidrogéis , Naftalimidas , Biomimética , Fluorescência , PolímerosRESUMO
A simple and ubiquitously present group, free amine, is used as a directing group to synthesize axially chiral biaryl compounds by PdII -catalyzed atroposelective C-H olefination. A broad range of axially chiral biaryl-2-amines can be obtained in good yields with high enantioselectivities (up to 97 % ee). Chiral spiro phosphoric acid (SPA) proved to be an efficient ligand and the loading could be reduced to 1â mol % without erosion of enantiocontrol in gram-scale synthesis. The resulting axially chiral biaryl-2-amines also provide a platform for the synthesis of a set of chiral ligands.
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The discovery of proper ligands to simultaneously modulate the reactivity and effectively control the stereoselectivity is a central topic in the field of enantioselective C-H activation. Herein, we reported the synthesis of axially chiral biaryls by Pd-catalyzed atroposelective C-H olefination. A novel chiral spiro phosphoric acid, STRIP, was identified as a superior ligand for this transformation. A broad range of axially chiral quinoline derivatives were synthesized in good yields with excellent enantioselectivities (up to 98 % ee). Density functional theory was used to gain a theoretical understanding of the enantioselectivities in this reaction.
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The site-selective functionalization of unactivated C(sp3 )-H bonds remains one of the greatest challenges in organic synthesis. Herein, we report on the site-selective δ-C(sp3 )-H alkylation of amino acids and peptides with maleimides via a kinetically less favored six-membered palladacycle in the presence of more accessible γ-C(sp3 )-H bonds. Experimental studies revealed that C-H bond cleavage occurs reversibly and preferentially at γ-methyl over δ-methyl C-H bonds while the subsequent alkylation proceeds exclusively at the six-membered palladacycle that is generated by δ-C-H activation. The selectivity can be explained by the Curtin-Hammett principle. The exceptional compatibility of this alkylation with various oligopeptides renders this procedure valuable for late-stage peptide modifications. Notably, this process is also the first palladium(II)-catalyzed Michael-type alkylation reaction that proceeds through C(sp3 )-H activation.
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Atroposelective synthesis of axially chiral biaryls by palladium-catalyzed C-H olefination, using tert-leucine as an inexpensive, catalytic, and transient chiral auxiliary, has been realized. This strategy provides a highly efficient and straightforward access to a broad range of enantioenriched biaryls in good yields (up to 98 %) with excellent enantioselectivities (95 to >99 % ee). Kinetic resolution of trisubstituted biaryls bearing sterically more demanding substituents is also operative, thus furnishing the optically active olefinated products with excellent selectivity (95 to >99 % ee, s-factor up to 600).
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A cobalt-catalyzed dual C(sp3 )-H activation strategy has been developed and it provides a novel strategy for the synthesis of bicyclo[4.1.0]heptanes and bicyclo[3.1.0]hexanes. A key to the success of this reaction is the conformation-induced methylene C(sp3 )-H activation of the resulting cobaltabicyclo[4.n.1] intermediate. In addition, the synthesis of bicyclo[3.1.0]hexane from pivalamide, by a triple C(sp3 )-H activation, has also been demonstrated.
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Graphene, because of its excellent mechanical, electrical, chemical, physical properties, sparked great interest to develop and extend its applications. Particularly, graphene based field-effect transistors (GFETs) present exciting and bright prospects for sensing applications due to their greatly higher sensitivity and stronger selectivity. This Review highlights a selection of important topics pertinent to GFETs and their application in electronic sensors. This article begins with a description of the fabrications and characterizations of GFETs, and then introduces the new developments in physical, chemical, and biological electronic detection using GFETs. Finally, several perspective and current challenges of GFETs development are presented, and some proposals are suggested for further development and exploration.
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Eletrônica , Grafite/química , Microscopia Eletrônica de VarreduraRESUMO
Ketones are ubiquitous in bioactive natural products, pharmaceuticals, chemical feedstocks, and synthetic intermediates. Hence, deacylative coupling reactions enable the versatile elaboration of a plethora of chemicals to access complex drug candidates and natural products. Here, we present deacylative arylation and alkynylation strategies for the synthesis of a wide range of alkyl-tethered arenes and alkynes from cyclic ketones and methyl ketones under dual nickel/photoredox catalysis. This reaction begins by generating a pre-aromatic intermediate (PAI) through the condensation of the ketone and N'-methylpicolino-hydrazonamide (MPHA), followed by the oxidative cleavage of the PAI α-CâC bond to form an alkyl radical, which is subsequently intercepted by a Ni complex, facilitating the formation of diverse C(sp3)-C(sp2)/C(sp) bonds with remarkable generality. This protocol features a one-pot reaction capability, high regioselectivity and ring-opening efficiency, mild reaction conditions, and a broad substrate scope with excellent functional group compatibility.
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Considering the serious electromagnetic wave (EMW) pollution problems and complex application condition, there is a pressing need to amalgamate multiple functionalities within a single substance. However, the effective integration of diverse functions into designed EMW absorption materials still faces the huge challenges. Herein, reduced graphene oxide/carbon foams (RGO/CFs) with two-dimensional/three-dimensional (2D/3D) van der Waals (vdWs) heterostructures were meticulously engineered and synthesized utilizing an efficient methodology involving freeze-drying, immersing absorption, secondary freeze-drying, followed by carbonization treatment. Thanks to their excellent linkage effect of amplified dielectric loss and optimized impedance matching, the designed 2D/3D RGO/CFs vdWs heterostructures demonstrated commendable EMW absorption performances, achieving a broad absorption bandwidth of 6.2 GHz and a reflection loss of - 50.58 dB with the low matching thicknesses. Furthermore, the obtained 2D/3D RGO/CFs vdWs heterostructures also displayed the significant radar stealth properties, good corrosion resistance performances as well as outstanding thermal insulation capabilities, displaying the great potential in complex and variable environments. Accordingly, this work not only demonstrated a straightforward method for fabricating 2D/3D vdWs heterostructures, but also outlined a powerful mixed-dimensional assembly strategy for engineering multifunctional foams for electromagnetic protection, aerospace and other complex conditions.
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A Cu(OTf)2-catalyzed glycosylation protocol using glycosyl ortho-N-phthalimidoylpropynyl benzoates (NPPBs) as donors was disclosed, which features an inexpensive copper catalyst, operationally convenient conditions, high to excellent yields, and a broad substrate scope. Mechanistic studies indicated an isochromen-4-yl copper(II) intermediate arising from the departure of the leaving group.
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Peptides hold great promise in proteomics, diagnostics and drug discovery. While natural peptides continue to be of key importance, chemically modified unnatural peptides have been found to show enhanced biological activities and improved therapeutic capabilities compared to their natural counterparts. Therefore, the development of efficient and versatile strategies to enable easy access to unnatural peptides is in high demand. In recent years, palladium-catalyzed direct functionalization of inert C(sp3)-H bonds has emerged as a powerful and straightforward synthetic strategy for late-stage modification of peptides. In this review, we summarize recent progress in this emerging field. For clarity, this review is organized into three sections according to the functionalization of the peptide side-chains at ß-, γ-, and δ-positions.
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Paládio/química , Peptídeos/química , CatáliseRESUMO
Transition-metal-catalyzed dehydrogenative C-H allylation with 1,1-disubstituted alkenes via ß-H elimination remains challenging, because of the low reactivity and difficulty of controlling selectivity. Herein, the development of a Pd(II)-catalyzed directed atroposelective C-H allylation with methacrylates is described. Exclusive allylic selectivity was achieved. A vast array of axially chiral biaryl-2-amines are efficiently synthesized with excellent enantioselectivities (up to >99% enantiomeric excess).
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The first example of Ni-catalyzed halogenation of (hetero)aryl C-H bonds with lithium halides (LiX, X = Br, I, Cl) using PIP as a removable directing group is reported. This protocol provides an efficient access to ortho-halogenated (hetero)arenes with operational simplicity, good functional group tolerance, and large-scale synthesis.
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Ni(II)-catalyzed ortho-arylation of aromatic and heteroaromatic carboxamides with triethoxy(aryl)silanes assisted by a removable bidentate auxiliary is reported. This transformation features a broad substrate scope, good functional group tolerance, and compatibility with heterocyclic substrates. Compared to the well-established Ni(II)-catalyzed C-H arylation with ArX or aryliodonium salts via oxidative addition, this reaction proceeded via a fluoride-promoted transmetalation.
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A Pd(II)-catalyzed sulfonylation of unactivated C(sp(3))-H bonds with sodium arylsulfinates using an 8-aminoquinoline auxiliary is described. This reaction demonstrates excellent functional group tolerance with respect to both the caboxamide starting material and the sodium arylsulfinate coupling partner, affording a broad range of aryl alkyl sulfones. Moreover, the late-stage modification of complex molecules was achieved via this sulfonylation protocol.
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Aminoquinolinas/química , Paládio/química , Sódio/química , Ácidos Sulfínicos/química , Catálise , Ligação de Hidrogênio , Estrutura MolecularRESUMO
Three-dimensional graphene foam (3DGF) is a superior sensing material because of its high conductivity, large specific surface area and wide electrochemical potential windows. In this work, hexagonal Ni(OH)2 nanosheets are deposited on the surface of chemical vapor deposition-grown 3DGF through a facial hydrothermal process without any auxiliary reagents. The morphology and structure of the composite are characterized by scanning electron microscopy (SEM), transmission electron microscope (TEM), Raman spectroscopy, and X-ray diffraction (XRD). Based on the Ni(OH)2/3DGF composite, a free-standing electrochemical electrode is fabricated. Being employed as a nonenzymatic glucose detection electrochemical electrode, it exhibits a high sensitivity (â¼2.65 mA mM(-1) cm(-2)), low detection limit (0.34 µM) and excellent selectivity with a linear response from 1 µM to 1.17 mM. The excellent sensing properties of the Ni(OH)2/3DGF electrode may be attributed to the synergistic effect of the high electrocatalytic activity of Ni(OH)2 nanosheets and the high conductivity and large surface area of 3DGF.
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Técnicas Eletroquímicas , Glucose/análise , Grafite/química , Hidróxidos/química , Níquel/química , Eletrodos , Nanoestruturas/química , Nanoestruturas/ultraestrutura , Análise Espectral RamanRESUMO
Nanostructured Co3O4 materials attracted significant attention due to their exceptional electrochemical (pseudo-capacitive) properties. However, rigorous preparation conditions are needed to control the size (especially nanosize), morphology and size distribution of the products obtained by conventional methods. Herein, we describe a novel one step shape-controlled synthesis of uniform Co3O4 nanocubes with a size of 50 nm with the existence of mesoporous carbon nanorods (meso-CNRs). In this synthesis process, meso-CNRs not only act as a heat receiver to directly obtain Co3O4 eliminating the high-temperature post-calcination, but also control the morphology of the resulting Co3O4 to form nanocubes with uniform distribution. More strikingly, mesoporous Co3O4 nanocubes are obtained by further thermal treatment. The structure and morphology of the samples were characterized by scanning electron microscopy, transmission electron microscopy and X-ray diffraction. A possible formation mechanism of mesoporous Co3O4 nanocubes is proposed here. Electrochemical tests have revealed that the prepared mesoporous Co3O4 nanocubes demonstrate a remarkable performance in supercapacitor applications due to the porous structure, which endows fast ion and electron transfer.