A DFT+U study of the catalytic activity of lanthanum nickelate

A density functional theory + Hubbard U (DFT+U) method is implemented to investigate the catalytic activity of lanthanum nickelate (LaNiO₃) for oxygen reduction reaction. Comparison of the surface energies of different LaNiO₃ surfaces shows that {001} surface has the lowest surface energy and hence maximum stability. Two possible terminations of the {001} surface namely LaO and NiO₂ are considered to carry out all our DFT calculations. Calculation of bond lengths of the atoms near the surface and adsorption energies for the reaction intermediates revealed that LaO terminated {001} surface is unstable for the process of OOH adsorption and hence not preferred for the oxygen reduction reaction. However, NiO₂ terminated {001} surface shows excellent catalytic activity for adsorption of all the reaction intermediates and hence is a favourable surface for reactions to occur. Superiority of the NiO₂ terminated {001} surface as catalyst over the LaO terminated one, is also confirmed from the total and partial density of states of the surfaces in presence of the adsorbates, which also shows that the desorption rate of the reaction intermediates is low in case of LaO terminated {001} surface compared to the NiO₂ terminated one.     

Acoustic source localization

In this article different techniques for localizing acoustic sources are described and the advantages/disadvantages of these techniques are discussed. Some source localization techniques are restricted to isotropic structures while other methods can be applied to anisotropic structures as well. Some techniques require precise knowledge of the direction dependent velocity profiles in the anisotropic body while other techniques do not require that knowledge. Some methods require accurate values of the time of arrival of the acoustic waves at the receivers while other techniques can function without that information. Published papers introducing various techniques emphasize the advantages of the introduced techniques while ignoring and often not mentioning the limitations and weaknesses of the new techniques. What is lacking in the literature is a comprehensive review and comparison of the available techniques; this article attempts to do that. After reviewing various techniques the paper concludes which source localization technique should be most effective for what type of structure and what the current research needs are.     

Gold Nanocages as Effective Photothermal Transducers in Killing Highly Tumorigenic Cancer Cells

Numerous gold nanostructures have the potential for photothermal therapy in cancers. Here, gold nanocages and gold nanoshells are synthesized, the sizes of which are fine‐tuned for a response at 750 nm wavelength. Their photothermal therapeutic efficiency is compared at gold concentration of 100 lg mL^?1 using a near‐infrared laser (750 nm). The biocompatibility for varying concentrations of gold (1 to 100 lg mL^?1) is performed in a normal cell line and laser‐mediated cell cytotoxicity for varying time intervals (7.5 and 10 min) is carried out in breast cancer cells. This study shows that when analyzed under similar conditions, the gold nanocages show better biocompatibility and are more efficient in near‐infrared absorption and photothermal conversion in comparison with conventional gold nanoshells. When subjected to photothermal laser ablation of breast cancer cell line for 7.5 min and 10 min, the nanocages are able to induce 62.92 ± 3.25% and 96.41 ± 3.04% reduction in cell viability, respectively, in comparison to nanoshells, in which a 43.35 ± 1.91% and 79.89 ± 4.74% reduction in cell viability is observed. The current study shows that the gold nanocages can outperform gold nanoshells and effectively kill cancer cells without any significant cytotoxic effect on normal cells.     

Probing platinum degradation in polymer electrolyte membrane fuel cells by synchrotron X-ray microscopy

Synchrotron-based scanning transmission X-ray spectromicroscopy (STXM) was used to characterize the local chemical environment at and around the platinum particles in the membrane (PTIM) which form in operationally tested (end-of-life, EOL) catalyst coated membranes (CCMs) of polymer electrolyte membrane fuel cells (PEM-FC). The band of metallic Pt particles in operationally tested CCM membranes was imaged using transmission electron microscopy (TEM). The cathode catalyst layer in the beginning-of-life (BOL) CCMs was fabricated using commercially available catalysts created from Pt precursors with and without nitrogen containing ligands. The surface composition of these catalyst powders was measured by X-ray Photoelectron Spectroscopy (XPS). The local chemical environment of the PTIM in EOL CCMs was found to be directly related to the Pt precursor used in CCM fabrication. STXM chemical mapping at the N 1s edge revealed a characteristic spectrum at and around the dendritic Pt particles in CCMs fabricated with nitrogen containing Pt-precursors. This N 1s spectrum was identical to that of the cathode and different from the membrane. For CCM samples fabricated without nitrogen containing Pt-precursors the N 1s spectrum at the Pt particles was indistinguishable from that of the adjacent membrane. We interpret these observations to indicate that nitrogenous ligands in the nitrogen containing precursors, or decomposition product(s) from that source, are transported together with the dissolved Pt from the cathode into the membrane as a result of the catalyst degradation process. This places constraints on possible mechanisms for the PTIM band formation process.     

Selective recognition of fluoride and acetate by a newly designed ruthenium framework: experimental and theoretical investigations

An effective anion sensor, [Ru(II)(bpy)(2)(H(2)L(-))](+) (1(+)), based on a redox and photoactive {Ru(II)(bpy)(2)} moiety and a new ligand (H(3)L = 5-(1H-benzo[d]imidazol-2-yl)-1H-imidazole-4-carboxylic acid), has been developed for selective recognition of fluoride (F(-)) and acetate (OAc(-)) ions. Crystal structures of the free ligand, H(3)L and [1](ClO(4)) reveal the existence of strong intramolecular and intermolecular hydrogen bonding interactions. The structure of [1](ClO(4)) shows that the benzimidazole N-H of H(2)L(-) is hydrogen bonded with the pendant carboxylate oxygen while the imidazole N-H remains free for possible hydrogen bonding interaction with the anions. The potential anion sensing features of 1(+) have been studied by different experimental and theoretical (DFT) investigations using a wide variety of anions, such as F(-), Cl(-), Br(-), I(-), HSO(4)(-), H(2)PO(4)(-), OAc(-) and SCN(-). Cyclic voltammetry and differential pulse voltammetry established that 1(+) is an excellent electrochemical sensor for the selective recognition of F(-) and OAc(-) anions. 1(+) is also found to be a selective colorimetric sensor for F(-) or OAc(-) anions where the MLCT band of the receptor at 498 nm is red shifted to 538 nm in the presence of one equivalent of F(-) or OAc(-) with a distinct change in colour from reddish-orange to pink. The binding constant between 1(+) and F(-) or OAc(-) has been determined to be logK = 7.61 or 7.88, respectively, based on spectrophotometric titration in CH(3)CN. The quenching of the emission band of 1(+) at 716 nm (λ(ex) = 440 nm, Φ = 0.01 at 298 K in CH(3)CN) in the presence of one equivalent of F(-) or OAc(-), as well as two distinct lifetimes of the quenched and unquenched forms of the receptor 1(+), makes it also a suitable fluorescence-based sensor. All the above experiments, in combination with (1)H NMR, suggest the formation of a 1:1 adduct between the receptor (1(+)) and the anion (F(-) or OAc(-)). The formation of 1:1 adduct {[1(+)·F(-)] or [1(+)·OAc(-)]} has been further evidenced by in situ ESI-MS(+) in CH(3)CN. Though the receptor, 1(+), is comprised of two N-H protons associated with the coordinated H(2)L(-) ligand, only the free imidazole N-H proton participates in the hydrogen bonding interactions with the incoming anions, while the intramolecularly hydrogen bonded benzimidazole N-H proton remains intact as evidenced by the crystal structure of the final product (1). The hydrogen bond mediated anion sensing mechanism, over the direct deprotonation pathway, in 1(+) has been further justified by a DFT study and subsequent NBO analysis.     

Influence of Tb doping on the luminescence characteristics of ZnO nanoparticles

Structural and optical properties of the Tb-doped ZnO nanoparticles with average diameter ≈4 nm have been systematically investigated. Our X-ray diffraction studies show a contraction of the ZnO lattice with the increase of the Tb mole-fraction x for x ≤ 0.02 and an expansion beyond x ≈ 0.02. The photoluminescence spectra are found to be comprised of a near band edge ultra violet luminescence (UVL) and a broad green luminescence (GL) band. Under the atmospheric condition, the intensity of the GL band is found to increase with the Tb mole-fraction over the entire doping range. On the other hand, under the vacuum condition, it has been observed that the GL intensity decreases with the increase of x up to x ≈ 0.02 but further increase of x leads to a gradual revival of the GL emission. Our study suggests that for x ≤ 0.02, GL results due to the physisorption of certain groups on the surface of the nanoparticles (GL-groups). It is also found that in this Tb mole-fraction regime, Tb incorporates mostly on the surface of the nanoparticles and affects the UVL to GL intensity ratio by influencing the attachment of the GL-groups. However, for x > 0.02, GL originates not only from the GL-groups but also from certain point defects, which are likely to be generated due to the incorporation of Tb in the core of the nanoparticles. A simple rate equation model is introduced to get a quantitative understanding about the variation of the density of the centers responsible for the GL emission as a function of x under the atmospheric and the vacuum conditions.     

Self-assembled one dimensional functionalized metal-organic nanotubes (MONTs) for proton conduction

Two self-assembled isostructural functionalized metal-organic nanotubes have been synthesized using 5-triazole isophthalic acid (5-TIA) with In(III) and Cd(II). In- and Cd-5TIA possess one-dimensional (1D) nanotubular architecture and show proton conductivity along regular 1D channels, measured as 5.35 × 10(-5) and 3.61 × 10(-3) S cm(-1) respectively.     

Resonance propagation in heavy-ion scattering

The formalism developed earlier by us for the propagation of a resonance in the nuclear medium in proton-nucleus collisions has been modified to the case of vector boson production in heavy-ion collisions. The formalism includes coherently the contribution to the observed di-lepton production from the decay of a vector boson inside as well as outside the nuclear medium. The medium modification of the boson is incorporated through an energy dependent optical potential. The calculated invariant ρ mass distributions are presented for the ρ-meson production using optical potentials estimated within the VDM and the resonance model. The shift in the invariant mass distribution is found to be small. To achieve the mass shift (of about 200 MeV towards lower mass) as indicated in the high energy heavy-ion collision experiments, an unusually strong optical potential of about −120 MeV is required. We also observe that, for not so heavy nuclear systems and/or for fast moving resonances, the shape, magnitude and peak position of the invariant mass distribution is substantially different if the contributions from the resonance decay inside and outside are summed-up at the amplitude level (coherently) or at the cross section level (incoherently).     

Palladium-catalyzed heteroannulation leading to heterocyclic structures with two heteroatoms: a highly regio- and stereoselective synthesis of (Z)-4-alkyl-2-alkyl(aryl)idene-3,4-dihydro-2H-1,4-benzoxazines and (Z)-3-alkyl(aryl)idene-4-tosyl-3,4-dihydro-2H-1,4-benzoxazines.

A highly convenient method has been developed for the synthesis of (Z)-4-alkyl-2-alkyl(aryl)idene-3,4-dihydro-2H-1,4-benzoxazines 9 and (Z)-3-alkyl(aryl)idene-4-tosyl-3,4-dihydro-2H-1,4-benzoxazines 34-38 through palladium-copper-catalyzed reactions. Aryl halides 7 reacted with 2-[N-alkyl(benzyl)-N-prop-2'-ynyl]aminophenyl tosylate 6 in the presence of (PPh3)2PdCl2 (3 mol %), CuI(5 mol %) in triethylamine at room temperature to yield 2-[N-alkyl(benzyl)-N-(3-aryl-prop-2'-ynyl)]-aminophenyl tosylates 8 in extremely good yields (72-96%). The latter could then be cyclized with KOH in ethanol-water to Z-9 in a highly regio- and stereoselective manner. Similarly, palladium-copper-catalyzed reaction of 2-(prop-2'-ynyloxy)aniline (21) with aryl iodides 7 led to 22-26 which after tosylation and cyclization with cuprous iodide in CH3CN in the presence of K2CO3 and Bu4-NBr led to the (Z)-3-alkyl(aryl)idene-4-tosyl 3,4-dihydro-2H-1,4-benzoxazines 34-38 in good overall yields. The Z-stereochemistry of the products was established from 1H NMR spectra, 3JCH values (between vinylic proton and methylenic carbon of the heterocyclic ring), NOE experiments, and X-ray analysis. The method was also found to be suitable for the synthesis of bis(benzoxazinylated) derivatives 17, 39, and 2-alkyl-3,4-dihydro-2H-1,4-benzoxazines 18. Our method for the synthesis of 3,4-dihydro-2H-1,4-benzoxazines is highly efficacious, using easily available starting materials under very mild conditions. Also the synthesis of some novel 5-substituted uracil derivatives 40 and 41 containing the benzoxazinyl moiety and of potential biological interest is being reported.