Synthesis of spongy gold nanocrystals with pronounced catalytic activities

A simple and easier chemical method for preparing spongy gold nanocrystals has been developed on the basis of a modified-citrate reduction technique of the corresponding gold salt at 25 degrees C in the absence of template. These nanocrystals possessed autocatalytic behavior and exhibited pronounced catalytic activity in the borohydride reduction of 4-nitrophenol due to their unique spongy morphology.     

UV-vis-NIR and EPR characterisation of the redox series [MQ(3)](2+,+,0,-,2-), M = Ru or Os, and Q = o-quinone derivative

The neutral title compounds with Q = 3,5-di-tert-butyl-o-quinone or 4,6-di-tert-butyl-N-phenyl-o-iminobenzoquinone (Q(x)) were studied by UV-vis-NIR spectroelectrochemistry and by EPR spectroscopy in the case of the odd-electron monocation and monoanion intermediates. Supported by DFT and TD-DFT calculations, the results indicate stepwise electron removal from predominantly ligand-based delocalised MOs on oxidation whereas the stepwise electron uptake on reduction involves unoccupied MOs with considerably metal-ligand mixed character. In both cases, the strong near-infrared absorption of the neutral precursors diminishes. In comparison to the ruthenium series, the osmium analogues exhibit larger transition energies from enhanced MO splitting and a different EPR response due to the higher spin-orbit coupling. The main difference between the quinone (1(n), 2(n)) and corresponding monoiminoquinone systems (3(n), 4(n)) is the shift of about 0.6 V to lower potentials for the monoimino analogues. While the absorption features do not differ markedly, the EPR data reflect a higher degree of covalent bonding for the complexes with monoimino ligands.     

Lower rim 1,3-di{4-antipyrine}amide conjugate of calix[4]arene: synthesis, characterization, and selective recognition of Hg2+ and its sensitivity toward pyrimidine bases

The structurally characterized lower rim 1,3-di{4-antipyrine}amide conjugate of calix[4]arene (L) exhibits high selectivity toward Hg(2+) among other biologically important metal ions, viz., Na(+), K(+), Ca(2+), Mg(2+), Mn(2+), Fe(2+), Co(2+), Ni(2+), Cu(2+), Zn(2+), Cd(2+), Hg(2+), Pb(2+), and Ag(+) as studied by fluorescence, absorption, and ESI MS. L acts as a sensor for Hg(2+) by switch-off fluorescence and exhibits a lowest detectable concentration of 1.87 ± 0.1 ppm. The complex formed between L and Hg(2+) is found to be 1:1 on the basis of absorption and fluorescence titrations and was confirmed by ESI MS. The coordination features of the mercury complex of L were derived on the basis of DFT computations and found that the Hg(2+) is bound through an N(2)O(2) extending from both the arms to result in a distorted octahedral geometry with two vacant sites. The nanostructural features such as shape and size obtained using AFM and TEM distinguishes L from its Hg(2+) complex and were different from those of the simple mercuric perchlorate. L is also suited to sense pyrimidine bases by fluorescence quenching with a minimum detection limit of 1.15 ± 0.1 ppm in the case of cytosine. The nature of interaction of pyrimidine bases with L has been further studied by DFT computational calculations and found to have interactions through a hydrogen bonding and NH-π interaction between the host and the guest.     

Imaging of a convective field in a rectangular cavity using interferometry, schlieren and shadowgraph

The present study is concerned with the quantitative imaging of buoyancy-driven convection in a fluid medium that is confined in a horizontal differentially heated rectangular cavity. The horizontal surfaces of the cavity provide a temperature difference, for initiating convection in the fluid. The vertical side walls are thermally insulated. Three imaging techniques, namely laser interferometry, schlieren, and shadowgraph have been utilized. Experiments have been conducted in a cavity of length 447 mm and 32 mm vertical height. The cavity is square in cross-section, and the imaging direction is parallel to its longer side. Convection in air and water have been investigated. Temperature differences in the range of 5–50 K for air and 3–10 K for water have been employed in the experiments. Quantities of interest are the temperature profiles in unsteadiness in the thermal field. At lower temperature differences across the fluid region, temperatures as recorded by interferometry and schlieren are in good agreement with each other. Further, they match the numerical predictions, as well as correlations available in the literature. Imaging based on shadowgraph is not as satisfactory at lower temperature differences. At larger cavity temperature differences, the shadowgraph images become clear enough for quantitative analysis, but the flow becomes time-dependent. The three techniques reveal similar trends in terms of the spatial distribution of temperature gradients and the time scales of unsteadiness. The schlieren and shadowgraph are more suitable for high gradients and interferometry is suitable for low gradients and all these three techniques are not flow visualization tools alone but are appropriate for quantitative imaging of thermal field.     

Non-unicity of Gibbs states of Czech models in a half-space

A classical lattice model is studied, with the property that, while yielding a unique state in the bulk, there exist at least two equilibrium states once considered in a half-space. The properties of those two states are discussed. In particular, the cluster expansion method is used to evaluate their difference deep in the bulk away from the boundary of the half-space.     

One pot low temperature synthesis of graphene coupled Gd-doped ZnFe<Subscript>2</Subscript>O<Subscript>4</Subscript> nanocomposite for effective removal of antibiotic levofloxacin drug

Nanocomposites of reduced graphene oxide (rGO) coupled gadolinium doped ZnFe₂O₄ (GZFG) have been successfully one pot in-situ synthesized adopting low temperature solution process from zinc nitrate, iron nitrate, gadolinium acetate and graphene oxide with varying concentrations of gadolinium (upto 10% Gd with respect to Zn) in the precursor medium. X-ray diffraction and transmission electron microscopy studies confirm the presence of single phase cubic spinel structure of ZnFe₂O₄ that uniformly distributed over the rGO layers. With increasing Gd doping concentration in precursor medium, the average crystallite size of ZnFe₂O₄ diminishes gradually from ~11 to ~5.5?nm. Raman and X-ray photoelectron spectral analyses confirm an existence of interaction between rGO and ZnFe₂O₄ in GZFG samples. Using antibiotic levofloxacin in water, the drug removal capacity (DRC) of GZFG has been performed by optimization of parameters such as gadolinium doping concentration in precursor medium, solution pH, etc. However, the gadolinium doping leads to an improvement in DRC of the nanocomposite and the 5% Gd doped sample shows about 86% DRC at the optimized condition. This simple strategy can be utilized in the synthesis of rGO coupled Gd doped other metal oxide nanocomposites for DRC application.

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Controlled trapping of single particle states on a periodic substrate by deterministic stubbing

A periodic array of atomic sites, described within a tight binding formalism is shown to be capable of trapping electronic states as it grows in size and gets stubbed by an ‘atom’ or an ‘atomic’ clusters from a side in a deterministic way. We prescribe a method based on a real space renormalization group method, that unravels a subtle correlation between the positions of the side coupled atoms and the energy eigenvalues for which the incoming particle finally gets trapped. We discuss how, in such conditions, the periodic backbone gets transformed into an array of infinite quantum wells in the thermodynamic limit. We present a case here, where the wells have a hierarchically distribution of widths, hosting standing wave solutions in the thermodynamic limit.     

Off-axis field approximations for ion traps with apertures

In recent work (Int. J. Mass Spec., vol. 282, pp. 112–122) we have considered the effect of apertures on the fields inside rf traps at points on the trap axis. We now complement and complete that work by considering off-axis fields in axially symmetric (referred to as “3D”) and in two dimensional (“2D”) ion traps whose electrodes have apertures, i.e., holes in 3D and slits in 2D. Our approximation has two parts. The first, E_noAperture, is the field obtained numerically for the trap under study with apertures artificially closed. We have used the boundary element method (BEM) for obtaining this field. The second part, E_{dueToAperture}, is an analytical expression for the field contribution of the aperture.In E_{dueToAperture}, aperture size is a free parameter. A key element in our approximation is the electrostatic field near an infinite thin plate with an aperture, and with different constant-valued far field intensities on either side. Compact expressions for this field can be found using separation of variables, wherein the choice of coordinate system is crucial. This field is, in turn, used four times within our trap-specific approximation.The off-axis field expressions for the 3D geometries were tested on the quadrupole ion trap (QIT) and the cylindrical ion trap (CIT), and the corresponding expressions for the 2D geometries were tested on the linear ion trap (LIT) and the rectilinear ion trap (RIT). For each geometry, we have considered apertures which are 10%, 30%, and 50% of the trap dimension. We have found that our analytical correction term E_{dueToAperture}, though based on a classical small-aperture approximation, gives good results even for relatively large apertures.     

1-(d-Glucopyranosyl-2′-deoxy-2′-iminomethyl)-2-hydroxybenzene as chemosensor for aromatic amino acids by switch-on fluorescence

A glucose based C2-glyco-conjugate, that is, 1-(d-glucopyranosyl-2′-deoxy-2′-iminomethyl)-2-hydroxybenzene (L), has been synthesized in a high yield and characterized. Titration of L with all the 20 naturally occurring amino acids resulted in a large fluorescence intensity enhancement only in case of aromatic amino acids, that is, Phe, Trp, His, and Tyr and not with the others. This has been attributed to the initial formation of 1:1 hydrogen bonded complex followed by π-π interactions present between the aromatic moieties of such complexes as demonstrated by absorption and computational methods. Thus L has been able to recognize aromatic amino acids down to 1.5-3 ppm through switch-on fluorescence behavior.