Molecular dynamics simulations on the local order of liquid and amorphous ZnTe

Molecular dynamics studies of structural and dynamical correlations of molten and vitreous states under several conditions of density and temperature were performed. We use an effective recently proposed interatomic potential, consisting of two- and three-body covalent interactions which has successfully described the structural, dynamical, and structural phase transformation induced by pressure in ZnTe [D. S. Borges and J. P. Rino, Phys. Rev. B 72, 014107 (2005)]. The two-body term of the interaction potential consists of Coulomb interaction resulting from charge transfer, steric repulsion due to atomic sizes, charge-dipole interaction to include the effect of electronic polarizability of anions, and dipole-dipole (van der Waals) interactions. The three-body covalent term is a modification of the Stillinger-Weber potential. Molecular dynamics simulations in isobaric-isenthalpic ensemble have been performed for systems amounting to 4096 and 64 000 particles. Starting from a crystalline zinc-blende (ZB) structure, the system is initially heated until a very homogeneous liquid is obtained. The vitreous zinc telluride phase is attained by cooling the liquid at sufficiently fast cooling rates, while slower cooling rates lead to a disordered ZB crystalline structure. Two- and three-body correlations for the liquid and vitreous phases are analyzed through pair distribution functions, static structure factors, and bond angle distributions. In particular, the neutron static structure factor for the liquid phase is in very good agreement with both the reported experimental data and first-principles simulations.     

Super-Oxidizing Covalent Triazine Framework Electrocatalyst for Two-Electron Water Oxidation to H2O2

Electrochemical two-electron water oxidation (2e WOR) is gaining surging research traction for sustainable hydrogen peroxide production. However, the strong oxidizing environment and thermodynamically competitive side-reaction (4e WOR) posit as thresholds for the 2e WOR. We herein report a custom-crafted covalent triazine network possessing strong oxidizing properties as a proof-of-concept metal-free functional organic network electrocatalyst for catalyzing 2e WOR. As the first-of-its-kind, the material shows a maximum of 89.9 % Faradaic Efficiency and 1428 μmol/h/cm² H₂O₂ production rate at 3.0 V bias potential (vs reversible hydrogen electrode, RHE), which are either better or comparable to the state-of-the-art electrocatalysts. We have experimentally confirmed a stepwise 2e WOR mechanism which was further computationally endorsed by density functional theory studies.     

An Application of a Theorem of Sheila Brenner for Hochschild Extension Algebras of a Truncated Quiver Algebra

Let A be a truncated quiver algebra over an algebraically closed field such that any oriented cycle in the ordinary quiver of A is zero in A. We give the number of the indecomposable direct summands of the middle term of an almost split sequence for a class of Hochschild extension algebras of A by the standard duality module D(A).

     

|\epsilon|-Near-zero materials in the near-infrared

We consider a mixture of metal-coated quantum dots dispersed in a polymer matrix and, using a modified version of the standard Maxwell-Garnett mixing rule, we prove that the mixture parameters (particles radius, quantum dots gain, etc.) can be chosen so that the effective medium permittivity has an absolute value very close to zero in the near-infrared, i.e. $|{\rm Re}(\epsilon)| \ll 1$ and $|{\rm Im}(\epsilon)| \ll 1$ at the same near-infrared wavelength. Resorting to full-wave simulations, we investigate the accuracy of the effective medium predictions and we relate their discrepancy with rigorous numerical results to the fact that $|\epsilon| \ll 1$ is a critical requirement. We show that a simple method for reducing this discrepancy, and hence for achieving a prescribed and very small value of $|\epsilon|, $ consists in a subsequent fine-tuning of the nanoparticles volume filling fraction.     

Wave scattering functions and their application to multiple scattering problems

Scattering functions arise naturally in standard treatments of the effects of a material object or surface embedded in a uniform field. The most commonly used scattering function describes the far-field modulation imparted at large distances to a spherical wavefront eminating from the scatterer. The purpose of this is to develop the properties of the spectrum of scattered plane waves as an exact generalized scattering function. The linearity of the wave equations guarantees that such a representation exists; moreover, it is possible to derive the generalized scattering function from the far-field scattering function by analytic continuation. Although these properties are known, recent theoretical developments have motivated us to reexplore the interrelations among the far-field scattering function, the Green's function and various forms of the generalized scattering function as well as the symmetry properties of the generalized scattering function imposed by reciprocity. For multiple-scattering objects that can be separated by parallel planes, a system of difference equations is developed that fully accommodates the mutual interaction among the scatterers. The mutual interaction equations were developed earlier, but we show here that they can be transformed into the form that would be obtained by using the Foldy-Lax-Twersky formalism. This reinforces the equivalence between wave-space and configuration space formulations of the scattering problems.     

Tin-free generation of alkyl radicals from alkyl 4-pentynyl sulfides via homolytic substitution at the sulfur atom

Homolytic substitution at the sulfur atom of beta-(phenylsulfanyl)vinyl radicals, obtained by radical reaction of benzenethiol with easily accessible alkyl 4-pentynyl sulfides, is a mild, effective, tin-free route for the generation of all types of alkyl radicals. This protocol can be employed in reductive defunctionalizations as well as cyclizations onto both electron-rich and electron-poor C-C double bonds.     

Radical reduction of aromatic azides to amines with triethylsilane

Aromatic azides are inert toward triethylsilane under thermal conditions in the presence of a radical initiator, but in the presence of additional catalytic amounts of tert-dodecanethiol, they afford anilinosilanes and thence the corresponding anilines in virtually quantitative yields.     

Pinus mugo Essential Oil Impairs STAT3 Activation through Oxidative Stress and Induces Apoptosis in Prostate Cancer Cells

Essential oils (EOs) and their components have been reported to possess anticancer properties and to increase the sensitivity of cancer cells to chemotherapy. The aim of this work was to select EOs able to downregulate STAT3 signaling using Western blot and RT-PCR analyses. The molecular mechanism of anti-STAT3 activity was evaluated through spectrophotometric and fluorometric analyses, and the biological effect of STAT3 inhibition was analyzed by flow cytometry and wound healing assay. Herein, Pinus mugo EO (PMEO) is identified as an inhibitor of constitutive STAT3 phosphorylation in human prostate cancer cells, DU145. The down-modulation of the STAT3 signaling cascade decreased the expression of anti-proliferative as well as anti-apoptotic genes and proteins, leading to the inhibition of cell migration and apoptotic cell death. PMEO treatment induced a rapid drop in glutathione (GSH) levels and an increase in reactive oxygen species (ROS) concentration, resulting in mild oxidative stress. Pretreatment of cells with N-acetyl-cysteine (NAC), a cell-permeable ROS scavenger, reverted the inhibitory action of PMEO on STAT3 phosphorylation. Moreover, combination therapy revealed that PMEO treatment displayed synergism with cisplatin in inducing the cytotoxic effect. Overall, our data highlight the importance of STAT3 signaling in PMEO cytotoxic activity, as well as the possibility of developing adjuvant therapy or sensitizing cancer cells to conventional chemotherapy.     

Photocatalytic Degradation of Palm Oil Mill Effluent (POME) Waste Using BiVO4 Based Catalysts

Disposal of palm oil mill effluent (POME), which is highly polluting from the palm oil industry, needs to be handled properly to minimize the harmful impact on the surrounding environment. Photocatalytic technology is one of the advanced technologies that can be developed due to its low operating costs, as well as being sustainable, renewable, and environmentally friendly. This paper reports on the photocatalytic degradation of palm oil mill effluent (POME) using a BiVO₄ photocatalyst under UV-visible light irradiation. BiVO₄ photocatalysts were synthesized via sol-gel method and their physical and chemical properties were characterized using several characterization tools including X-ray diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM), surface area analysis using the BET method, Raman spectroscopy, electron paramagnetic resonance (EPR), and UV-Vis diffuse reflectance spectroscopy (UV-Vis DRS). The effect of calcination temperature on the properties and photocatalytic performance for POME degradation using BiVO₄ photocatalyst was also studied. XRD characterization data show a phase transformation of BiVO₄ from tetragonal to monoclinic phase at a temperature of 450 °C (BV-450). The defect site comprising of vanadium vacancy (V_v) was generated through calcination under air and maxima at the BV-450 sample and proposed as the origin of the highest reaction rate constant (k) of photocatalytic POME removal among various calcination temperature treatments with a k value of 1.04 × 10⁻³ min⁻¹. These findings provide design guidelines to develop efficient BiVO₄-based photocatalyst through defect engineering for potential scalable photocatalytic organic pollutant degradation.