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We investigated the ligand dependence of the proton conduction of hydronium solvate ionic liquids (ILs), consisting of a hydronium ion (H3O+), polyether ligands, and a bis[(trifluoromethyl)sulfonyl]amide anion (Tf2N-; Tf = CF3SO2). The ligands were changed from previously reported 18-crown-6 (18C6) to other cyclic or acyclic polyethers, namely, dicyclohexano-18-crown-6 (Dh18C6), benzo-18-crown-6 (B18C6) and pentaethylene glycol dimethyl ether (G5). Pulsed-field gradient spin echo nuclear magnetic resonance results revealed that the protons of H3O+ move faster than those of cyclic 18C6-based ligands but as fast as those of acyclic G5 ligands. Based on these results and density functional theory calculations, we propose that the coordination of a cyclic ether ligand to the H3O+ ion is essential for fast proton conduction in hydronium solvate ILs. Our results attract special interest for many electro- and bio-chemical applications such as electrolyte systems for fuel cells and artificial ion channels for biological cells.Correction for 'Stability of Cu(ii) complexes with FomA protein fragments containing two His residues in the peptide chain' by Monika Katarzyna Lesiów et al., Metallomics, 2019, 11, 1518-1531, DOI 10.1039/C9MT00131J.Iron is an essential nutrient but is toxic in excess mainly under acidic conditions. Yeasts have emerged as low cost, highly efficient soil inoculants for the decontamination of metal-polluted areas, harnessing an increasing understanding of their metal tolerance mechanisms. Here, we investigated the effects of extracellular iron and acid pH stress on the dimorphism of Yarrowia lipolytica. Its growth was unaffected by 1 or 2 mM FeSO4, while a strong cellular iron accumulation was detected. However, the iron treatments decreased the hyphal length and number, mainly at 2 mM FeSO4 and pH 4.5. Inward cell membrane H+ fluxes were found at pH 4.5 and 6.0 correlated with a pH increase at the cell surface and a conspicuous yeast-to-hypha transition activity. Conversely, a remarkable H+ efflux was detected at pH 3.0, related to the extracellular microenvironment acidification and inhibition of yeast-to-hypha transition. Iron treatments intensified H+ influxes at pH 4.5 and 6.0 and inhibited H+ efflux at pH 3.0. Moreover, iron treatments inhibited the expression and activities of the plasma membrane H+-ATPase, with the H+ transport inhibited to a greater extent than the ATP hydrolysis, suggesting an iron-induced uncoupling of the pump. Our data indicate that Y. lipolytica adaptations to high iron and acidic environments occur at the expense of remodelling the yeast morphogenesis through a cellular pH modulation by H+-ATPases and H+ coupled transporters, highlighting the capacity of this non-conventional yeast to accumulate high amounts of iron and its potential application for bioremediation.The construction of metal-carbon nanostructures with enhanced performances using traditional methods, such as pyrolysis, photolysis, impregnation-reduction, etc., generally requires additional energy input, reducing agents and capping ligands, which inevitably increase the manufacturing cost and environmental pollution. Herein, a novel one-step substrate-induced electroless deposition (SIED) strategy is developed to synthesize ligand-free Ag NPs supported on porous carbon (PC) (Ag/PC). The PC matrix enriched with oxygenated functional groups has a low work function and thus a low redox potential compared to that of Ag+ ions, which induces the auto-reduction of Ag+ ions to Ag NPs. The as-synthesized Ag/PC-6 modified electrode can be used as an excellent nonenzymatic H2O2 sensor with a broad linear range of 0.001-20 mM, a low detection limit of 0.729 μM (S/N = 3), and a high response sensitivity of 226.9 μA mM-1 cm-2, outperforming most of the reported sensor materials. Moreover, this electrode can be applied to detect trace amounts of H2O2 in juice and milk samples below the permitted residual level in food packaging and the recovery of H2O2 is 99.6% in blood serum (10%) with good reproducibility. This study proposes an efficient approach for synthesizing a highly active supported Ag electrocatalyst, which shows significant potential for practical applications.The hierarchical structural evolution of natural rubber (NR) filled with different contents of nanoscale carbon black (CB) (10 phr-CB10 and 50 phr-CB50) after first loading and recovering for different times was investigated by X-ray nano-CT, wide-angle X-ray scattering (WAXS) and solid state NMR techniques. The CB filler structures as captured by X-ray nano-CT recover gradually with increasing recovering time, but the filler network with different CB contents shows dramatically different structure evolution. For CB10, limited by the filling content, CB particles mainly induces a hydrodynamic effect in spite of deformation or recovering. For CB50, the CB filler forms a 3D connected network, partially destructed during deformation, and the destructed part can be partially recovered during recovery. https://www.selleckchem.com/products/ly3023414.html This suggests that the connected CB filler structure mainly acts as a network reinforcement, whereas the destructed part can induce a hydrodynamic effect. The different effects induced by different CB filling contents are also reflected by the NR matrix, which is reflected by the onset strains εc of strain-induced crystallization (SIC) of NR as captured by WAXS. For CB10, εc remains almost constant, i.e. εc = ca. 1.49, while that of NR with CB50 slightly decreases from initial ca. 1.12 to 0.96 with increasing recovering time up to 50 h. Also, the bound rubber fraction and entangled rubber network remain unchanged after deformation and under different recovery time as detected by the magic sandwich echo (MSE) FID and proton multiple quantum (MQ) NMR. These results demonstrate the key role of the CB filler network in determining the stress-softening behavior of reinforced rubber.Flat optics nanoarrays based on few-layer MoS2 are homogeneously fabricated over large-area (cm2) transparent templates, demonstrating effective tailoring of the photon absorption in two-dimensional (2D) transition-metal dichalcogenide (TMD) layers. The subwavelength subtractive re-shaping of the few-layer MoS2 film into a one-dimensional (1D) nanostripe array results in a pronounced photonic anomaly, tunable in a broadband spectral range by simply changing the illumination conditions (or the lattice periodicity). This scheme promotes efficient coupling of light to the 2D TMD layers via resonant interaction between the MoS2 excitons and the photonic lattice, with subsequent enhancement of absorption exceeding 400% relative to the flat layer. In parallel, an ultra-broadband absorption amplification in the whole visible spectrum is achieved, thanks to the non-resonant excitation of substrate guided modes promoted by MoS2 nanoarrays. These results highlight the potential of nanoscale re-shaped 2D TMD layers for large-area photon harvesting in layered nanophotonics, quantum technologies and new-generation photovoltaics.
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