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Ultrathin nanoplates of metastable 1T-MoS2 have been successfully stabilized and uniformly distributed on the surface of n-butyl triethyl ammonium bromide functionalized polypyrrole/graphene oxide (BTAB/PPy/GO) by a very simple hydrothermal method. BTAB as a typical kind of quaternary ammonium-type ionic liquids (ILs) played a crucial role in the formation of the obtained 1T-MoS2/BTAB/PPy/GO. It was covalently linked with PPy/GO and arranged in a highly ordered order at the solid-liquid interface of PPy/GO and H2O due to Coulombic interactions and other intermolecular interactions, which would induce and stabilize ultrathin 1T-MoS2 nanoplates by morphosynthesis. The good electrocatalytic activity toward nitrogen reduction reaction (NRR) with strong durability and good stability can be achieved by 1T-MoS2/BTAB/PPy/GO due to their excellent inorganic/organic hierarchical lamellar micro-/nanostructures. Especially, after the long-term electrocatalysis for NRR at a negative potential, metastable 1T-MoS2 as the catalytic center undergoes two types of irreversible crystal phase transition, which was converted to 1T'-MoS2 and Mo2N, caused by the competitive hydrogen evolution reaction (HER) process and the electrochemical reaction between the electroactive 1T-MoS2 and N2, respectively. The new N-Mo bonding prevents Mo atoms from binding to other N atoms in N2, resulting in the deactivation of the electrocatalysts to NRR after being used for 18 h. Even so, quaternary ammonium-type ILs would induce the crystal structures of transition-metal dichalcogenides (TMDCs), which might provide a new thought for the reasonable design of electrocatalysts based on TMDCs for electrocatalysis.Toxicity concerns related to Gd(III)-based MRI agents prompted an intensive research towards their replacement by complexes of essential Mn(II) ion. Here, we report a macrocyclic chelate, [Mn(PC2A-BP)], which possesses high thermodynamic stability and kinetic inertness as well as remarkable relaxivity (r1p = 23.5 mM-1s-1, 20 MHz, 37 °C) in the presence of human serum albumin allowing a significant MRI signal intensity increase in the vasculature even at low dose (25 μmol/kg) of the complex.Citrus sinensis and Citrus limonia were obtained by germination from seeds, and isotopic-labeling experiments using d-[1-13C]glucose were performed with the seedlings. After 60 days, the seedlings were analyzed by high-performance liquid chromatography-ultraviolet-solid-phase extraction-nuclear magnetic resonance, data and the 13C enrichment patterns of xanthyletin and seselin indicated that the pyran ring was formed by the methylerythritol phosphate pathway and that the coumarin moiety was derived from the shikimate pathway in both compounds. This information regarding the biosynthetic pathway can be used to increase resistance against phytopathogens, because xanthyletin and seselin are reported to have antimicrobial activity on the growth of Xylella fastidiosa, which causes citrus variegated chlorosis in orange.In contrast to classical ion mobility spectrometers (IMS) operating at ambient pressure, the High Kinetic Energy Ion Mobility Spectrometer (HiKE-IMS) is operated at reduced pressures between 10 - 40 mbar and higher reduced electric field strengths of up to 120 Td. Thus, the ion-molecule reactions occurring in the HiKE-IMS can significantly differ from those in classical ambient pressure IMS. In order to predict the ionization pathways of specific analyte molecules, a profound knowledge about the reactant ion species generated in HiKE-IMS and their dependence on the ionization conditions are essential. In this work, the formation of positive reactant ions in HiKE-IMS is investigated in detail. Based on kinetic and thermodynamic data from literature, the ion-molecule reactions are kinetically modeled. To verify the model, we present measurements of the reactant ion population and its dependence on the reduced electric field strength, the operating pressure and the water concentration in the sample gas. All of these parameters significantly affect the reactant ion population formed in HiKE-IMS.A practical and atom-economic protocol for the stereoselective preparation of various 1,4- and 1,3-diene skeletons through iridium-catalyzed directed olefinic C-H allylation and alkenylation of NH-Ts acrylamides in water was developed. This reaction tolerated a wide scope of substrates under simple reaction conditions and enabled successful gram-scale preparation. Furthermore, an asymmetric variant of this reaction giving enantioenriched 1,4-dienes was achieved employing a chiral diene-iridium complex as the catalyst.The quinoid structure, a resonance structure of benzenoid, gives rise to peculiar chemical reactivity and physical properties. A complete characterization of its geometric and electronic properties on the atomic scale is of vital importance to understand and engineer the chemical and physical properties of quinoid molecules. Here, we report a real-space structural and electronic characterization of quinoid poly(para-phenylene) (PPP) chains by using noncontact atomic force microscopy and scanning tunneling microscopy. Our results reveal that quinoid PPP chains adopt a coplanar adsorption configuration on Cu(111) and host in-gap states near Fermi level. In addition, intra- and interchain hopping of quinoid structure are observed, indicative of a quasiparticle behavior originating from charge-lattice interactions. The experimental results are nicely reproduced by tight-binding calculations. Our study provides a comprehensive understanding of the structural and electronic properties of quinoid PPP chains in real space and may be further extended to address the dynamics of nonlinear excitations in quinoid molecules.Activation of G-protein-gated inward rectifying potassium channels (Kir3.x) require the direct binding of phosphorylated phosphatidylinositides (PIPs). Previous studies have established that PIP isoforms activate Kir channels to varying degrees and the binding affinity between PIPs and Kir3.2 appears to be correlated with the level of activation. However, how individual residues contribute to the selectivity of Kir channels toward PIP isoforms is poorly understood. buy BGB-8035 Here, we employ native mass spectrometry (MS) and fluorescent-lipid binding assays to gain insight into the contribution of specific Kir3.2 residues binding to phospholipids. For the wild-type channel, we demonstrate the importance of membrane protein samples devoid of co-purified contaminants for protein-lipid binding studies and show that PIP(4,5)P2 cooperatively binds Kir3.2 with a Hill coefficient of 2.7. We also find lipid binding profiles determined from native MS and solution binding assays are in direct agreement. Point mutations of Kir3.2 residues that interact with PIPs distinctly alter selective lipid binding.
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