Physical and photoelectrochemical characterizations of hematite α-Fe2O3: Application to photocatalytic oxygen evolution

The physical properties and photoelectrochemical characterization of α-Fe₂O₃, synthesized by co-precipitation, have been investigated in regard to solar energy conversion. The optical gap is found to be 1.94 eV and the transition is indirectly allowed. The chemical analysis reveals an oxygen deficiency and the oxide exhibits n-type conductivity, confirmed by a negative thermopower. The plot log σ vs 1/T shows linearity in the range (400-670 K) with the donor levels at 0.14 eV below the conduction band and a break at ∼590 K, attributed to the ionization of the donors. The conduction occurs by small polaron hopping through mixed valences Fe^2+/3+ with an electron mobility μ_400 K of 10⁻³ V cm² s⁻¹. α-Fe₂O₃ exhibits long term chemical stability in neutral solution and has been characterized photoelectrochemically to assess its activity as bias-free O₂-photoanode. The flat band potential V_fb (−0.45V_SCE) and the electron density N_D (1.63 × 10¹⁸ cm⁻³) were determined, respectively, by extrapolating the linear part to C⁻² = 0 and the slope of the Mott Schottky plot. At pH 6.5, the valence band (+1.35V_SCE) is suitably positioned with respect to the O₂/H₂O level (+0.62 V) and α-Fe₂O₃ has been evaluated for the chemical energy storage through the photocatalytic reaction: (, ΔG = 213.36 kJ mol⁻¹). The best photoactivity occurs in solution (0.025 M, pH 8) with an oxygen rate evolution of 7.8 cm³ (g catalyst)⁻¹ h⁻¹.     

Electrical and Seismic Tomography Used to Image the Structure of a Tailings Pond at the Abandoned Kettara Mine, Morocco

The Kettara site (Morocco) is an abandoned pyrrhotite ore mine in a semi-arid environment. The site contains more than 3 million tons of mine waste that were deposited on the surface without concern for environmental consequences. Tailings were stockpiled in a pond, in a dyke, and in piles over an area of approximately 16?ha and have generated acid mine drainage (AMD) for more than 29?years. Geophysical methods have been used at the Kettara mine site to determine the nature of the geological substrate of the tailings pond, the internal structure of the mine wastes, and to investigate the pollution zones associated with sulphide waste dumps. Electrical resistivity tomography (ERT) and seismic refraction data were acquired, processed, and interpreted; the results from ERT and seismic refraction were complementary. A topographical survey of the tailings disposal area was also undertaken to estimate the volume of wastes and quantify the AMD process. Two-dimensional inverse models were used to investigate the geophysical data and indicated alteration zones at depth. It was determined that the material could be classified into three categories: tailings, with low resistivity (5?C15??? m) and low velocity (500?C1,800?m/s); altered, black shales, with intermediate resistivity (20?C60??? m) and velocity (2,000?C3,500?m/s), and; materials with high resistivity and velocity (>60????m and >4,000?m/s, respectively), including unaltered shales associated with quartzite seams. The low-resistivity zone generates AMD, which migrates downward through fractures and micro-fractures. The substrate is composed of broken and altered shale, which facilitates AMD infiltration.     

Effect of microwave treatment on the cooking and macronutrient qualities of pulses

The effect of microwave treatment to reduce the cooking times of five pulses, namely red lentil, chickpea, pigeon pea, mung bean, and pinto bean, were determined in this study. Pulses from 10 to 18% moisture contents were treated using 400 to 600 W microwaves for 14 to 56 s. The cooking times of microwave-treated pulses were significantly lower than that of the control samples. The lowest cooking time was observed for 18% moisture content chickpea and pigeon pea treated with 600 W for 56 s. The Fourier transform mid-infrared spectra in both lipids and fingerprint regions showed the macronutrients differences among the five pulses. Major changes were observed in the amide I region of microwave treated pulses. This effect of microwave treatment was higher in red lentil, chickpea, and mung bean than in pigeon pea and pinto bean at 10% moisture content. At 18% moisture content, the change of β-sheets to aggregates was observed in all pulses due to microwave treatment.     

Three-Dimensional Natural Convection in the Horizontal Bridgman Configuration Under Various Wall Electrical Conductivity and Magnetic Field

A numerical investigation of the three-dimensional natural convection of a liquid metal contained in the horizontal Bridgman configuration, having an aspect ratio equal to 5 and submitted to an external magnetic field in either the longitudinal or vertical direction, is presented. The numerical approach is based on the finite-volume approximation. A computer program based on the SIMPLER algorithm is developed. The effect of a magnetic field provides a notable change on the flow and thermal structures. The strongest stabilization of the convection flow is found when the magnetic field is oriented vertically. Also, wall electrical conductivity has an effect on the average Nusselt number. A good agreement between our numerical simulations and experimental data found in the literature is obtained.     

Stability of Swirling Flows with Heat Transfer in a Cylindrical Enclosure with CO/Counter-Rotating End Disks Under an Axial Magnetic Field

In this article, a numerical study of swirling flows with heat transfer generated by two rotating end disks (co- and counter-rotating) inside a cylindrical enclosure having an aspect ratio equal to 2, filled with a liquid metal, and submitted to a vertical temperature gradient and an axial magnetic field is studied. The governing Navier-Stokes, energy, and potential equations along with appropriate boundary conditions are solved by using the finite-volume method. The flow and temperature fields are presented by stream function and isotherms, respectively. This flow is very unstable and reveals a great richness of structures. In an oscillatory regime, results are presented for various values of the Hartmann number, Ha = 5, 10, 20 and 30, and Richardson numbers, Ri = 0, 0.5, 1, 2 and 4, in order to see their effects on the value of the critical Reynolds number, Re_cr. Stability diagrams are established according to the numerical results of this investigation. These diagrams show the dependence of Re_cr with the increase of Ha for various values of Ri. The flow between co-rotating end disks is very different from the flow between counter-rotating end disks. Finally, this study confirms the possibility of stabilization of a liquid metal flow by application of an axial magnetic field.     

Hydrothermal Synthesis and Characterization of Europium-doped Barium Titanate Nanocrystallites

Nano-Micro Letters - Barium titanate nanocrystallites were synthesized by a hydrothermal technique from barium chloride and tetrabutyl titanate. Single-crystalline cubic perovskite BaTiO3...     

Hexahistidine‐Tagged Single‐Walled Carbon Nanotubes (His6‐tagSWNTs): A Multifunctional Hard Template for Hierarchical Directed Self‐Assembly and Nanocomposite Construction

While a hexahistidine affinity tag can be introduced at protein termini or internal sites by standard molecular biology procedures for purification, immobilization, or labeling of proteins, here the versatility of this concept is exploited for the chemical preparation of novel hexahistidine‐tagged single‐walled carbon nanotubes (His₆‐tagSWNTs), a novel hard template useful for solubilizing, assembling, processing, and interfacing SWNTs in aqueous conditions. Water‐soluble and exfoliated His₆‐tagSWNTs are prepared and fully characterized. This functional molecular module is able to interact via robust physisorption (π?π stacking) with the sidewall of SWNTs and combines the versatility of small, water‐soluble reporters (His₆) for hierarchical directed self‐assembly (HDSA) and construction of nanocomposites. It is demonstrated that metal coordination bonds with Ni(II) can be used for the supramolecular self assembly of His₆‐tagSWNTs, generating complex reticulated networks and architectures. The His₆‐tagSWNTs hard template nanohybrid is further utilized for directed self‐assembly with silica nanoparticles. The versatility of the novel hybrids opens a new era for the rational design, smart (bio)functionalization, processing, interfacing, and self assembling of carbon nanotubes for the construction of multicomposites and more complex systems with controllable spatial organization and programmable properties for a wide range of applications in biology, nanoelectronics, and catalysis.     

Mining the cinnabaramide biosynthetic pathway to generate novel proteasome inhibitors

The cinnabaramides and salinosporamides are mixed PKS/NRPS natural products isolated from a terrestrial streptomycete and a marine actinomycete, respectively. They interfere with the proteasome and thus potentially inhibit the growth of cancer cells. The compounds exhibit a γ-lactam-β-lactone bicyclic ring structure attached to a cyclohexenyl unit and a PKS side chain. As a first step towards improving anticancer activity and permitting genetic approaches to novel analogues, we have cloned and characterized the cinnabaramide biosynthetic genes from Streptomyces sp. JS360. In addition to the expected PKS and NRPS genes, the cluster encodes functionalities for the assembly of the hexyl side chain precursor. The corresponding enzymes exhibit relaxed substrate specificities towards a number of synthesized precursors, enabling production of novel chlorinated cinnabaramides. These were isolated and analyzed for activity, revealing that derivatives bearing a chlorine atom in the PKS side chain show higher inhibitory potentials towards the proteasome's proteolytic subunits (especially the trypsin and chymotrypsin units) and higher cytotoxicities towards human tumor cell lines than the parent cinnabaramide A. Although their activities towards the proteasome were weaker than that of salinosporamide A, the cinnabaramides were found to inhibit the growth of various fungi with greater potency.