Manganese oxides are of considerable importance in technological applications, including ion-exchange, molecular adsorption, catalysis, and electrochemical supercapacitors owing to their structural flexibility combined with novel chemical and physical properties. [1][2][3][4][5] Up to now, various nanostructures of MnO 2 , such as nanoparticles, [6] nanorods/-belts/-wires/-tubes/-fibers, [7][8][9][10][11] nanosheets, [12] mesoporous/molecular sieves and branched structures, [13,14] urchins/orchids, and other hierarchical structures [15] have been synthesized by different methods.Over the past years, fabrication of hierarchical hollow nanostructures has attracted significant interest because of their widespread potential applications in catalysis, drug delivery, acoustic insulation, photonic crystals, [16][17][18][19][20] and other areas. Until now, the general approach for preparation of hollow structures has involved the use of various removable or sacrificial templates, referred to as "hard", such as monodispersed silica, [21,22] polymer latex spheres [23] and reducing metal nanoparticles, [24] as well as "soft" ones, for example, emulsion droplets/ micelles [25] and gas bubbles. [26] Furthermore, lots of one-pot template-free methods for generating hollow inorganic microand nanostructures have been developed employing novel mechanisms, including the nanoscale corrosion-based insideout evacuation [27] and Kirkendall effect. [28] Recently, rhombododecahedral silver cages have been prepared by self-assembly coupled with the precursor crystal-templating approach. [29] By treating the external morphologies of hollow structures, unique properties can be obtained. [30] Thus, it is desirable to develop easy methods to control the morphologies of assembled systems with well-defined hierarchical structures. Herein, we report a simple controlled preparation of hierarchical hollow microspheres and microcubes of MnO 2 nanosheets through self-assembly with an intermediate crystaltemplating process. As shown in Figure 1, the synthesis is performed by a three-step process. Particularly, discrete spherical and cubic hollow MnO 2 nanostructures with controlled morphologies can be prepared by changing the morphologies of MnCO 3 precursors, which can be simply obtained by adding the (NH 4 ) 2 SO 4 solution in the reaction system, and the thicknesses of the shells of hierarchical hollow nanostructures can be adjusted easily by the relative quantities of KMnO 4 reacted followed by selective removal of MnCO 3 crystal template with HCl. When used as adsorbent in waste-water treatment, as-prepared MnO 2 with a hierarchical hollow nanostructure exhibited a good ability to remove organic pollutant.Some related chemical reactions are shown as follows. The main chemical reaction (1) can be formulated with two half reactions. On the basis of the value of E°, the standard Gibbs free energy change DG°of reaction (1) could be estimated as -99.0 kJ mol -1 , implying strong tendency for reaction (1) to progress toward the right-hand side. As ...
Covalent triazine frameworks (CTFs) are normally synthesized by ionothermal methods. The harsh synthetic conditions and associated limited structural diversity do not benefit for further development and practical large‐scale synthesis of CTFs. Herein we report a new strategy to construct CTFs (CTF‐HUSTs) via a polycondensation approach, which allows the synthesis of CTFs under mild conditions from a wide array of building blocks. Interestingly, these CTFs display a layered structure. The CTFs synthesized were also readily scaled up to gram quantities. The CTFs are potential candidates for separations, photocatalysis and for energy storage applications. In particular, CTF‐HUSTs are found to be promising photocatalysts for sacrificial photocatalytic hydrogen evolution with a maximum rate of 2647 μmol h−1 g−1 under visible light. We also applied a pyrolyzed form of CTF‐HUST‐4 as an anode material in a sodium‐ion battery achieving an excellent discharge capacity of 467 mAh g−1.
Olmsted syndrome (OS) is a rare congenital disorder characterized by palmoplantar and periorificial keratoderma, alopecia in most cases, and severe itching. The genetic basis for OS remained unidentified. Using whole-exome sequencing of case-parents trios, we have identified a de novo missense mutation in TRPV3 that produces p.Gly573Ser in an individual with OS. Nucleotide sequencing of five additional affected individuals also revealed missense mutations in TRPV3 (which produced p.Gly573Ser in three cases and p.Gly573Cys and p.Trp692Gly in one case each). Encoding a transient receptor potential vanilloid-3 cation channel, TRPV3 is primarily expressed in the skin, hair follicles, brain, and spinal cord. In transfected HEK293 cells expressing TRPV3 mutants, much larger inward currents were recorded, probably because of the constitutive opening of the mutants. These gain-of-function mutations might lead to elevated apoptosis of keratinocytes and consequent skin hyperkeratosis in the affected individuals. Our findings suggest that TRPV3 plays essential roles in skin keratinization, hair growth, and possibly itching sensation in humans and selectively targeting TRPV3 could provide therapeutic potential for keratinization or itching-related skin disorders.
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