The facet selectivity of inorganic ions on silver nanocrystals in etching reactions

The facet selectivity of the halide ions and chlorauric acid for several shaped silver nanocrystals is presented in this paper. Two inorganic ions show different representations when they are used for etching silver nanocrystals in the self-sacrificial template reaction. The morphological changes of the silver nanocrystals indicate that the halide ions prefer to etch the (110) facets of silver nanocrystals, while in the chlorauric acid etching reaction, gold first modifies the (110) facets and then lets chlorauric acid etch the (111) facets instead. The selective facet etching on individual nanoparticles in the solution phase has crucial significance in the control-synthesis of nanocrystals and the facet asymmetric reaction.

The thermal stability and structural site-distribution of Eu3+ ions in the red-emitting phosphors Ca9Eu2W4O24 and Sr9Eu2W4O24

The red-emitting phosphors Ca₉Eu₂W₄O₂₄ and Sr₉Eu₂W₄O₂₄ were synthesized by the solid-state reaction method. The crystal phases were characterized by X-ray powder diffraction. The photoluminescence excitation and emission spectra were investigated. The luminescence excitation and emission spectra confirm that the phosphors are efficiently excited by near UV light. The dependence of luminescence intensities on the heating temperatures was investigated. The Ca₉Eu₂W₄O₂₄ phosphor exhibits higher thermal stability than that of Sr₉Eu₂W₄O₂₄. The crystallographic sites for Eu³⁺ ions in Ca₉Eu₂W₄O₂₄ and Sr₉Eu₂W₄O₂₄ are investigated by the site-selective excitation spectra in the ⁵D₀ → ⁷F₀ wavelength region. It is identified that the Eu³⁺ ions occupy only M sites (statistically occupied by 0.5Eu and 0.5Ca) in Ca₉Eu₂W₄O₂₄ and, however, the Eu³⁺ ions can substitute both M sites (Eu³⁺ + Sr²⁺) and Sr²⁺ sites in Sr₉Eu₂W₄O₂₄. The luminescence spectra and the thermal stability are discussed on the basis of the crystal structure, Eu³⁺ site-distributions and the energy transfer.

The influence of water and metal ions on the transport properties of Trihexyl(tetradecyl)phosphonium chloride

A recent study indicated that the water-saturated ionic liquid (IL) trihexyl(tetradecyl)phosphonium chloride ([P_6,6,6,14][Cl]) provided a viable electrolyte for a Mg-air battery. However, there is limited literature on the properties of IL-water mixtures as battery electrolytes. The physical properties of [P_6,6,6,14][Cl] were studied with the addition of both water and metal salts (M_gCl₂ and LiCl) using conductivity and self-diffusion coefficient measurements. The conductivity of the samples at low water concentrations is surprisingly enhanced by the addition of the metal salt, contrary to lithium IL electrolytes. It was also found that the conductivity of the IL was increased by an order of magnitude by saturation with water. NMR diffusion measurements were used to probe the behaviour of both the cation and the water in the mixtures. It was found that the addition of metal salts to the water-saturated [P_6,6,6,14][Cl] did not affect the transport properties of the water or cation.

Facile synthesis of graphene oxide hybrids bridged by copper ions for increased conductivity

In this article, we report a facile method for preparing graphene oxide (GO) hybrid materials consisting of copper ions (Cu2+) complexed with GO, where Cu2+ acted as bridges connecting GO sheets. The method of film formation is based on cross-linking GO using Cu2+ followed by filtration onto nanoporous supports. This binding can be rationalized due to the chemical interaction between the functional groups on GO and the metal ion. We observed that there was a decrease in charge transfer resistance through electrochemical study. It suggests that the presence of metal ions in GO films could introduce new energy levels along the electron transport pathway and open up possible conduction channels. We also found that the hybrid graphene film assembled with Cu2+ dramatically decreases resistance through flash light reduction.

Reactions with oleum under harsh conditions : characterization of the unique [M(S2O7)3]2- ions (M=Si, Ge, Sn) in A2[M(S2O7)3] (A=NH4, Ag)

The reactions of group 14 tetrachlorides MCl4 (M=Si, Ge, Sn) with oleum (65 % SO3) at elevated temperatures lead to the unique complex ions [M(S2O7)3]2−, which show the central M atoms in coordination with three chelating S2O72− groups. The mean distances M[BOND]O within the anions increase from 175.6(2)–177.5(2) pm (M=Si) to 186.4(4)–187.7(4) pm (M=Ge) to 201.9(2)–203.5(2) pm (M=Sn). These distances are reproduced well by DFT calculations. The same calculations show an increasing positive charge for the central M atom in the row Si, Ge, Sn, which can be interpreted as the decreasing covalency of the M[BOND]O bonds. For the silicon compound (NH4)2[Si(S2O7)3], 29Si solid-state NMR measurements have been performed, with the results showing a signal at −215.5 ppm for (NH4)2[Si(S2O7)3], which is in very good agreement with theoretical estimations. In addition, the vibrational modes within the [MO6] skeleton have been monitored by Raman spectroscopy for selected examples, and are well reproduced by theory. The charge balance for the [M(S2O7)3]2− ions is achieved by monovalent A+ counter ions (A=NH4, Ag), which are implemented in the syntheses in the form of their sulfates. The sizes of the A+ ions, that is, their coordination requirements, cause the crystallographic differences in the crystal structures, although the complex [M(S2O7)3]2− ions remain essentially unaffected with the different A+ ions. Furthermore, the nature of the A+ ions influences the thermal behavior of the compounds, which has been monitored for selected examples by thermogravimetric differential thermal analysis (DTA/TG) and XRD measurements.

Studies on the interaction between malanin and metal ions by fluorescence spectra methods

A novel protein with anti-tumor activities named malanin was isolated and purified from an endemic plant in Yunnan and Guangxi provinces. Effects of copper ion, silver ion and calcium ion on malanin and apo-malanin fluorescence spectra were studied. The results showed that copper ion leads to obvious statistic quenching of malanin and apo-malanin fluorescence. The dissociation constant of them from malanin and apo-malanin were about 2.37×10-4 and 2.66×10-4 mol·L-1, respectively. The silver ion did not have quenching action on malanin fluorescence, but it had statistic quenching effect on apo-malanin fluorescence, and its dissociation constant was 2.37×10-4 mol·L-1. Calcium ion did not have quenching action on malanin and apo-malanin fluorescence. It plays an important role in keeping malanin natural conformation.

Insights into the transport of alkali metal ions doped into a plastic crystal electrolyte

The application of organic ionic plastic crystals (OIPCs) as a new class of solid electrolyte for energy storage devices such as lithium batteries and, more recently, sodium batteries is attracting increasing attention. Key to this is achieving sufficient target ion transport through the material. This requires fundamental understanding of the structure and dynamics of OIPCs that have been doped with the necessary lithium or sodium salts. Here we report, for the first time, the atomic level structure and transport of both lithium and sodium ions in the plastic crystalline phases of an OIPC diethyl(methyl)(isobutyl)phosphonium hexafluorophosphate. These molecular dynamics simulations reveal two types of coordination geometries of the alkali metal ion first solvation shells, which cooperate closely with the metal ion hopping motion. The significantly different ion migration rates between two metal ion doped systems could also be related to the differences in solvation structures.

Tunnelling current recognition through core-satellite gold nanoparticles for ultrasensitive detection of copper ions

We report a new method for ultrasensitive detection of Cu(2+), which is based on changes in the tunnelling recognition current across self-assembled core-satellite gold nanoparticles (GNPs) networks functionalised with amino acids (l-cysteine). The addition of copper ions induces the formation of GNP/l-cysteine/Cu(2+)/l-cysteine/GNP molecular junctions and generates a significant decrease in the resistance through the networks. The networks are ultrasensitive to over ten orders range of copper ion concentrations.

Graphene nanodots-encaged porous gold electrode fabricated via ion beam sputtering deposition for electrochemical analysis of heavy metal ions

All rights reserved. A graphene nanodots-encaged porous gold electrode via ion beam sputtering deposition (IBSD) for electrochemical sensing is presented. The electrodes were fabricated using Au target, and a composite target of Al and graphene, which were simultaneously sputtered onto glass substrates by Ar ion beam, followed with hydrochloric acid corrosion. The as-prepared graphene nanodots-encaged porous gold electrodes were then used for the analysis of heavy metal ions, e.g. Cu2+ and Pb2+ by Osteryoung square wave voltammetry (OSWV). These porous electrodes exhibited enhanced detection range for the heavy metal ions due to the entrapped graphene nanodots in 3-D porous structure. In addition, it was also found that when the thickness of porous electrode reached 40 nm the detection sensitivity came into saturation. The linear detection range is 0.009-4 μM for Cu2+ and 0.006-2.5 μM for Pb2+. Good reusability and repeatability were also observed. The formation mechanism and 3-D structure of the porous electrode were also investigated using scanning electron microscope (SEM), transmission electron microscope (TEM) and X-ray photoelectron spectra (XPS). This graphene entrapped 3-D porous structure may envision promising applications in sensing devices.

Combination of calcium and magnesium ions prevents substrate inhibition and promotes biomass and lipid production in thraustochytrids under higher glycerol concentration

Effect of calcium and magnesium ions was studied in detail in batch mode in shake flask cultures of two fast growing strains of thraustochytrids (Aurantiochytrium sp. DBTIOC-18 and Schizochytrium sp. DBTIOC-1) for biomass and lipid production. These strains were previously isolated from Indian marine biodiversity. Screening of these two strains on different carbon and nitrogen sources revealed the suitability of glycerol over glucose and sodium nitrate over yeast extract for the cultivation of these strains. The presence of higher concentration of glycerol in the medium inhibited the glycerol utilization by the cell thus resulting in lower biomass and lipid production in both the strains. Supplementing media with calcium and magnesium ions promoted glycerol utilization thus resulted in a substantial rise in volumetric production of biomass (55.12 g L-1, 48.12 g L-1), fatty acid for biodiesel (27.14 g L-1, 22.15 g L-1) and docosahexaenoic acid (14.57 g L-1, 10.12 g L-1) with both strains Aurantiochytrium sp. DBTIOC-18 and Schizochytrium sp. DBTIOC-1, respectively. Growth profile study of these two strains showed further improvement in production of biomass, fatty acid for biodiesel and docosahexaenoic acid when cultures were extended up to 7 days. Finding of this work underlines the importance of calcium and magnesium salts in designing new fermentation strategies to prevent substrate inhibition and achieve high cell density culture under high nutrient concentration especially carbon sources.