Elemental analysis in bed sediment samples of Karnafuli estuarine zone in the Bay of Bengal by instrumental neutron activation analysis

The concentration of rare earths and other elements have been determined in the bed sediment samples of Karnafuli estuarine zone in the Bay of Bengal by instrumental neutron activation analysis (INAA). The samples and the standards soil-5, soil-7, coal fly ash and pond sediment were prepared and simultaneously irradiated for short and long time at the TRIGA Mark-II research reactor facility of Atomic Energy Research Establishment, Savar, Dhaka. The maximum themal neutron flux was of the order of 10¹³ n·cm^–2·s^–1. After irradiation the radioactivity of the product nuclides was measured by using a high resolution high purity germanium detector system. Analysis of -ray spectra and quantitative analysis of the elemental concentration were done via the software GANAAS, it has been possible to determine the concentration level of 27 elements including the rare earths La, Ce, Sm, Eu, Tb, Dy and Yb and uranium and thorium.     

Microbial transformation of cortisol and prolyl endopeptidase inhibitory activity of its transformed products

Incubation of cortisol (1) with Gibberella fujikuruoi for 12 days yielded an oxidatively cleaved product, 11beta-hydroxyandrost-4-en-3,17-dione (2), while incubation with Bacillus subtilis and Rhizopus stolonifer yielded the reduced product, 11beta, 17alpha,20,21-tetrahydroxy-(20S)-pregn-4-en-3-one (3). Other reduced products, 11beta, 17alpha, 21-trihydroxy-5alpha-pregnan-3, 20-dione (4) and 3beta, 11beta, 17alpha, 21-tetrahydroxy-5alpha-pregnan-20-one (5) were obtained by incubation of compound 1 with Bacillus cerus. The inhibitory activity of compounds 1-5 against prolyl endopeptidase enzyme (PEP) was also assayed. Compounds 2 (IC50 162.8 microM) and 4 (IC50 157 microM) have shown significant inhibitory activity against PEP.     

Optical power limiting and transmitting properties of cadmium iodide single crystals: Temperature dependence

Optical limiting properties of the single crystals of cadmium iodide are investigated using ns laser pulses. It is found that the transmissions in the crystals increase with increasing temperature. However, they limit the transmissions at high input powers. The limiting power is found to be higher at higher temperature. From the measured transmission data, the photon absorption coefficients are estimated. The temperature dependence of the coefficients shows a decrease in magnitude with increasing temperature. This might be due to the temperature-dependent bandgap shift of the material. The results demonstrate that the cadmium iodide single crystals are promising materials for applications in optical power limiting devices.     

Vitamin C induced decomposition of lipid hydroperoxides: direct evidence of genotoxin-DNA binding detected by QCRS

We report direct evidence for human DNA-binding to precursors of mutagenic lesion-inducing compounds, produced form the vitamin C induced decomposition of lipid hydroperoxides, using a quartz crystal resonant sensor assay.     

Comparison of four C18 columns for the liquid chromatographic determination of deoxynivalenol in naturally contaminated wheat

Three long and 1 short reversed-phase C18 columns were compared for separation of deoxynivalenol (DON) in extracts of naturally contaminated wheat samples using liquid chromatography with ultraviolet detection and liquid chromatography/mass spectrometry (LC/MS). Among the 3 long columns used, a Symmetry C18 column with an isocratic solvent mixture of water-acetonitrile-methanol (90 + 5 + 5, v/v/v) gave the best separation for DON without interferences from other compounds in the wheat extracts. The Symmetry short (75 mm) column was comparable with the long column (250 mm) in resolving DON but significantly reduced retention time (i.e., 5.8 versus 16.3 min). Increasing the column temperature from 25 to 45 degrees C resulted in a further reduction in retention time. Identity of DON in the wheat extracts and standard solutions was confirmed by LC/MS in the positive ion mode, whereby DON appeared with an (M+1)+ ion at a mass-to-charge ratio of 297 plus fragment ions associated with loss of water and/or a 30 atomic mass unit (amu) CH2O fragment. The Symmetry short column was also capable of separating a mixture of the mycotoxins DON, 15-acetyl-DON, nivalenol, and zearalenone by use of a combination of an isocratic and gradient solvent system. The overall method showed high precision, exhibiting a relative standard deviation of 4.8%, limit of detection of 50 ng/g, and limit of quantitation of 165 ng/g. It was significantly correlated with enzyme-linked immunosorbent assay analysis, indicating its appropriateness for safety and quality assurance of wheat and related grains.     

Reactivity of triruthenium thiophyne and furyne clusters: competitive S-C and P-C bond cleavage reactions and the generation of highly unsymmetrical alkyne ligands

The synthesis and reactivity of the thiophyne and furyne clusters [Ru3(CO)7(mu-dppm)(mu3-eta2-C4H2E)(mu-P(C4H3E)2)(mu-H)] (E = S, O) is reported. Addition of P(C4H3E)3 to [Ru3(CO)10(mu-dppm)] (1) at room temperature in the presence of Me3NO gives simple substitution products [Ru3(CO)9(mu-dppm)(P(C4H3E)3)] (E = S, 2; E = O, 3). Mild thermolysis in the presence of further Me3NO affords the thiophyne and furyne complexes [Ru3(CO)7(mu-dppm)(mu3-eta2-C4H2E)(mu-P(C4H3E)2)(mu-H)] (E = S, 4; E = O, 6) resulting from both carbon-hydrogen and carbon-phosphorus bond activation. In each the C4H2E (E = S, O) ligand donates 4-electrons to the cluster and the rings are tilted with respect to the mu-dppm and the phosphido-bridged open triruthenium unit. Heating 4 at 80 degrees C leads to the formation of the ring-opened cluster [Ru3(CO)5(mu-CO)(mu-dppm)(mu3-eta3-SC4H3)(mu-P(C4H3S)2)] (5) resulting from carbon-sulfur bond scission and carbon-hydrogen bond formation and containing a ring-opened mu3-eta3-1-thia-1,3-butadiene ligand. In contrast, a similar thermolysis of 3 affords the phosphinidene cluster [Ru3(CO)7(mu-dppm)(mu3-eta2-C4H2O)(mu3-P(C4H3O))] (7) resulting from a second phosphorus-carbon bond cleavage and (presumably) elimination of furan. Treatment of 4 and 6 with PPh3 affords the simple phosphine-substituted products [Ru3(CO)6(PPh3)(mu-dppm)(mu3-eta2-C4H2E)(mu-P(C4H3E)2)(mu-H)] (E = S, 8; E = O, 9). Both thiophyne and furyne clusters 4 and 6 readily react with hydrogen bromide to give [Ru3(CO)6Br(mu-Br)(mu-dppm)(mu3-eta2-eta1-C4H2E)(mu-P(C4H3E)2)(mu-H)] (E = S, 10; E = O, 11) containing both terminal and bridging bromides. Here the alkynes bind in a highly unsymmetrical manner with one carbon acting as a bridging alkylidene and the second as a terminally bonded Fisher carbene. As far as we are aware, this binding mode has only previously been noted in ynamine complexes or those with metals in different oxidation states. The crystal structures of seven of these new triruthenium clusters have been carried out, allowing a detailed analysis of the relative orientations of coordinated ligands.     

Nanosized nickel oxide particles and modification with poly(methyl methacrylate)

In recent years, there is an increasing interest in the fabrication of inorganic–organic materials considering the remarkable change and improvement in properties. In this investigation, nanosized nickel oxide (NiO) particles were first prepared by calcination of nickel hydroxide precursor obtained by a simple liquid‐phase process. Mixed phases of NiO and nickel hydroxide were present as the calcination temperature was lower than 250°C. Non‐stoichiometric NiO was formed between 250°C and 350°C, and a pure NiO was obtained as the temperature reached 500°C. The surface characteristics of NiO particles were evaluated by measuring the adsorption behavior of anionic and cationic surfactants and some biomolecules. NiO/poly(methyl methacrylate) composite particles were then prepared using variable NiO/methyl methacrylate (MMA) ratio by seeded emulsion polymerization. The efficiency of NiO incorporation in the composite increased as the MMA content was increased in the recipe. The composite particles were colloidally stable, and the obtained particles were characterized by Fourier transform infrared, scanning electron microscopy, X‐ray diffraction, and X‐ray photoelectron spectra. Copyright © 2011 John Wiley & Sons, Ltd.     

Synthetic, electrochemical, and theoretical studies of tetrairidium clusters bearing mono- and bis[60]fullerene ligands

Heating a mixture of Ir(4)(CO)(9)(PPh(3))(3) (1) and 2 equiv of C(60) in refluxing chlorobenzene (CB) affords a "butterfly" tetrairidium-C(60) complex Ir(4)(CO)(6){mu(3)-kappa(3)-PPh(2)(o-C(6)H(4))P(o-C(6)H(4))PPh(eta(1)-o-C(6)H(4))}(mu(3)-eta(2):eta(2):eta(2)-C(60)) (3, 36%). Brief thermolysis of 1 in refluxing chlorobenzene (CB) gives a "butterfly" complex Ir(4)(CO)(8){mu-k(2)-PPh(2)(o-C(6)H(4))PPh}{mu(3)-PPh(2)(eta(1):eta(2)-o-C(6)H(4))} (2, 64%) that is both ortho-phosphorylated and ortho-metalated. Interestingly, reaction of 2 with 2 equiv of C(60) in refluxing CB produces 3 (41%) by C(60)-assisted ortho-phosphorylation, indicating that 2 is the reaction intermediate for the final product 3. On the other hand, reaction of Ir(4)(CO)(8)(PMe(3))(4) (4) with excess (4 equiv) C(60) in refluxing 1,2-dichlorobenzene, followed by treatment with CNCH(2)Ph at 70 degrees C, affords a square-planar complex with two C(60) ligands and a face-capping methylidyne ligand, Ir(4)(CO)(3)(mu(4)-CH)(PMe(3))(2)(mu-PMe(2))(CNCH(2)Ph)(mu-eta(2):eta(2)-C(60))(mu(4)-eta(1):eta(1):eta(2):eta(2)-C(60)) (5, 13%) as the major product. Compounds 2, 3, and 5 have been characterized by spectroscopic and microanalytical methods, as well as by single-crystal X-ray diffraction studies. Cyclic voltammetry has been used to examine the electrochemical properties of 2, 3, 5, and a related known "butterfly" complex Ir(4)(CO)(6)(mu-CO){mu(3)-k(2)-PPh(2)(o-C(6)H(4))P(eta(1)-o-C(6)H(4))}(mu(3)-eta(2):eta(2):eta(2)-C(60)) (6). These cyclic voltammetry data suggest that a C(60)-mediated electron transfer to the iridium cluster center takes place for the species 3(3)(-) and 6(2)(-) in compounds 3 and 6. The cyclic voltammogram of 5 exhibits six well-separated reversible, one-electron redox waves due to the strong electronic communication between two C(60) cages through a tetrairidium metal cluster spacer. The electrochemical properties of 3, 5, and 6 have been rationalized by molecular orbital calculations using density functional theory and by charge distribution studies employing the Mulliken and Hirshfeld population analyses.     

Orange Peel Biomass-derived Carbon Supported Cu Electrocatalysts Active in the CO2-Reduction to Formic Acid

We report a green, wet chemistry approach towards the production of C-supported Cu electrocatalysts active in the CO₂ reduction to formic acid. We use citrus peels as a C support precursor and as a source of reducing agents for the Cu cations. We show that orange peel is a suitable starting material compared to lemon peel for the one-pot hydrothermal synthesis of Cu nanostructures affording better Cu dispersion as well as productivity and selectivity towards formic acid. We rationalize this finding in terms of the beneficial chemical composition of the orange peel, which favors both the reduction of the Cu precursor as well as the carbon matrix. This work demonstrates new viable opportunities for the reuse of citrus waste on a rational basis.     

Thermo-Kinetic Study of Piperazine Immobilized Silica Surface

In the present study, the degradation process of piperazine (PP) immobilized silica gel (SiPP) is investigated under dynamic conditions. The degradation of SiPP is studied with thermogravimetric analyzer (TGA). The kinetics of degradation process is analyzed by Kissinger method, Flynn–Wall–Ozawa's (FWO) method, and Deconvolution method. It is found that degradation of SiPP can be described by parallel independent two-portion process model, which includes two processing state of the system (marked by processes 1 and 2), where process 1 and 2 can be attributed to decomposition processes of organic moiety attached on silica surface. The apparent activation energy (E_a) is calculated by Flynn–Wall–Ozawa's (FWO) method and deconvolution method.