Neutron activation analysis of wheat samples

The deficiency of essential micronutrients and excess of toxic metals in cereals, an important food items for human nutrition, can cause public health risk. Therefore, before their consumption and adoption of soil supplementation, concentrations of essential micronutrients and metals in cereals should be monitored. This study collected soil and two varieties of wheat samples–Triticum aestivum L. (Jordão/bread wheat), and Triticum durum L. (Marialva/durum wheat) from Elvas area, Portugal and analyzed concentrations of As, Cr, Co, Fe, K, Na, Rb and Zn using Instrumental Neutron Activation Analysis (INAA) to focus on the risk of adverse public health issues. The low variability and moderate concentrations of metals in soils indicated a lower significant effect of environmental input on metal concentrations in agricultural soils. The Cr and Fe concentrations in soils that ranged from 93–117 and 26,400–31,300 mg/kg, respectively, were relatively high, but Zn concentration was very low (below detection limit <22 mg/kg) indicating that soils should be supplemented with Zn during cultivation. The concentrations of metals in roots and straw of both varieties of wheat decreased in the order of K>Fe>Na>Zn>Cr>Rb>As>Co. Concentrations of As, Co and Cr in root, straw and spike of both varieties were higher than the permissible limits with exception of a few samples. The concentrations of Zn in root, straw and spike were relatively low (4–30 mg/kg) indicating the deficiency of an essential micronutrient Zn in wheat cultivated in Portugal. The elemental transfer from soil to plant decreases with increasing growth of the plant. The concentrations of various metals in different parts of wheat followed the order: Root>Straw>Spike. A few root, straw and spike samples showed enrichment of metals, but the majority of the samples showed no enrichment. Potassium is enriched in all samples of root, straw and spike for both varieties of wheat. Relatively to the seed used for cultivation, Jordão presented higher transfer coefficients than Marialva, in particular for Co, Fe, and Na. The Jordão and Marialva cultivars accumulated not statistically significant different concentrations of different metals. The advantages of using INAA are the multielementality, low detection limits and use of solid samples (no need of digestion).

Chromatographic behaviour of monoclonal antibodies against wild-type amidase from Pseudomonasaeruginosa on immobilized metal chelates

The aim of this work was to devise a one-step purification procedure for monoclonal antibodies (MAbs) of IgG class by immobilized metal affinity chromatography (IMAC). Therefore, several stationary phases were prepared containing immobilized metal chelates in order to study the chromatographic behaviour of MAbs against wild-type amidase from Pseudomonas aeruginosa. Such MAbs adsorbed to Cu(II), Ni(II), Zn(II) and Co(II)-IDA agarose columns. The increase in ligand concentration and the use of longer spacer arms and higher pH values resulted in higher adsorption of MAbs into immobilized metal chelates. The dynamic binding capacity and the maximum binding capacity were 1.33 +/- 0.015 and 3.214 +/- 0.021 mg IgG/mL of sedimented commercial matrix, respectively. A K(D) of 4.53 x 10(-7) M was obtained from batch isotherm measurements. The combination of tailor-made stationary phases of IMAC and the correct selection of adsorption conditions permitted a one-step purification procedure to be devised for MAbs of IgG class. Culture supernatants containing MAbs were purified by IMAC on commercial-Zn(II) and EPI-30-IDA-Zn(II) Sepharose 6B columns and by affinity chromatography on Protein A-Sepharose CL-4B. This MAb preparation revealed on SDS-PAGE two protein bands with M(r) of 50 and 22 kDa corresponding to the heavy and light chains, respectively. Copyright (C) 2011 John Wiley & Sons, Ltd.

Sensor element for a metal-insulator-semiconductor camera system (MISCam)

We discuss the operation of a new type of optical sensor (MISCam) based on a metal-insulator-semiconductor (MIS) structure. The operation principle relies on light-induced changes of the band bending and barrier height at the interface between semiconductor and insulator. An image is obtained from the quenching of the ac signal in analogy to the principle of the laser-scanned photodiode (LSP). Lateral resolution depends on the semiconductor material chosen. We have characterised the MIS structures by C-V, I-V, and spectral response measurements testing different types of insulators like a-Si3N4, SiO2, and AlN. The presence of slow interface charges allows for image memory. Colour sensors can be realised by controlling sign and magnitude of the electric fields in the base and the interface region.

Coexistence of Universal and Topological Anomalous Hall Effects in Metal CrO2 Thin Films in the Dirty Limit

The scaling exponent of 1.6 between anomalous Hall and longitudinal conductivity, characteristic of the universal Hall mechanism in dirty-metal ferromagnets, emerges from a series of CrO2 films as we systematically increase structural disorder. Magnetic disorder in CrO2 increases with temperature and this drives a separate topological Hall mechanism. We find that these terms are controlled discretely by structural and magnetic defect populations, and their coexistence leads to apparent divergence from exponent 1.6, suggesting that the universal term is more prevalent than previously realized.

Structural characterization and immunogenicity in wildtype and immune tolerant mice of degraded recombinant human interferon alpha2b

Purpose - To study the influence of protein structure on the immunogenicity in wildtype and immune tolerant mice of well-characterized degradation products of recombinant human interferon alpha2b (rhIFNα2b). Methods - RhIFNα2b was degraded by metal catalyzed oxidation (M), crosslinking with glutaraldehyde (G), oxidation with hydrogen peroxide (H) and incubation in a boiling water bath (B). The products were characterized with UV absorption, circular dichroism and fluorescence spectroscopy, gel permeation chromatography, reversed-phase HPLC, SDS-PAGE, Western blotting and mass spectrometry. The immunogenicity of the products was evaluated in wildtype mice and in transgenic mice immune tolerant for hIFNα2. Serum antibodies were detected by ELISA or surface plasmon resonance. Results - M-rhIFNα2b contained covalently aggregated rhIFNα2b with three methionines partly oxidized to methionine sulfoxides. G-rhIFNα2b contained covalent aggregates and did not show changes in secondary structure. H-rhIFNα2b was only chemically changed with four partly oxidized methionines. B-rhIFNα2b was largely unfolded and heavily aggregated. Native (N) rhIFNα2b was immunogenic in the wildtype mice but not in the transgenic mice, showing that the latter were immune tolerant for rhIFNα2b. The antirhIFNα2b antibody levels in the wildtype mice depended on the degradation product: M-rhIFNα2b > H-rhIFNα2b ~ N-rhIFNα2b >> B-rhIFNα2b; G-rhIFNα2b did not induce anti-rhIFNα2b antibodies. In the transgenic mice, only M-rhIFNα2b could break the immune tolerance. Conclusions - RhIFNα2b immunogenicity is related to its structural integrity. Moreover, the immunogenicity of aggregated rhIFNα2b depends on the structure and orientation of the constituent protein molecules and/or on the aggregate size.

Structural characterization and immunogenicity in wild-type and immune tolerant mice of degraded recombinant human interferon Alpha2b

Purpose: This study was conducted to study the influence of protein structure on the immunogenicity in wild-type and immune tolerant mice of well-characterized degradation products of recombinant human interferon alpha2b (rhIFNα2b). Methods: RhIFNα2b was degraded by metal-catalyzed oxidation (M), cross-linking with glutaraldehyde (G), oxidation with hydrogen peroxide (H), and incubation in a boiling water bath (B). The products were characterized with UV absorption, circular dichroism and fluorescence spectroscopy, gel permeation chromatography, reverse-phase high-pressure liquid chromatography, sodium dodecyl sulfate polyacrylamide gel electrophoresis, Western blotting, and mass spectrometry. The immunogenicity of the products was evaluated in wild-type mice and in transgenic mice immune tolerant for hIFNα2. Serum antibodies were detected by enzyme-linked immunosorbent assay or surface plasmon resonance. Results: M-rhIFNα2b contained covalently aggregated rhIFNα2b with three methionines partly oxidized to methionine sulfoxides. G-rhIFNα2b contained covalent aggregates and did not show changes in secondary structure. H-rhIFNα2b was only chemically changed with four partly oxidized methionines. B-rhIFNα2b was largely unfolded and heavily aggregated. Nontreated (N) rhIFNα2b was immunogenic in the wild-type mice but not in the transgenic mice, showing that the latter were immune tolerant for rhIFNα2b. The anti-rhIFNα2b antibody levels in the wild-type mice depended on the degradation product: M-rhIFNα2b > H-rhIFNα2b ∼ N-rhIFNα2b ≫ B-rhIFNα2b; G-rhIFNα2b did not induce anti-rhIFNα2b antibodies. In the transgenic mice, only M-rhIFNα2b could break the immune tolerance. Conclusions: RhIFNα2b immunogenicity is related to its structural integrity. Moreover, the immunogenicity of aggregated rhIFNα2b depends on the structure and orientation of the constituent protein molecules and/or on the aggregate size.

Characterization of airborne particles generated from metal active gas welding process

This study is focused on the characterization of particles emitted in the metal active gas welding of carbon steel using mixture of Ar + CO2, and intends to analyze which are the main process parameters that influence the emission itself. It was found that the amount of emitted particles (measured by particle number and alveolar deposited surface area) are clearly dependent on the distance to the welding front and also on the main welding parameters, namely the current intensity and heat input in the welding process. The emission of airborne fine particles seems to increase with the current intensity as fume-formation rate does. When comparing the tested gas mixtures, higher emissions are observed for more oxidant mixtures, that is, mixtures with higher CO2 content, which result in higher arc stability. These mixtures originate higher concentrations of fine particles (as measured by number of particles by cm 3 of air) and higher values of alveolar deposited surface area of particles, thus resulting in a more severe worker's exposure.

The effect of metal transfer modes and shielding gas composition on the emission of ultraafine particles in MAG steel welding

The present study aims to characterize ultrafine particles emitted during gas metal arc welding of mild steel and stainless steel, using different shielding gas mixtures, and to evaluate the effect of metal transfer modes, controlled by both processing parameters and shielding gas composition, on the quantity and morphology of the ultrafine particles. It was found that the amount of emitted ultrafine particles (measured by particle number and alveolar deposited surface area) are clearly dependent from the main welding parameters, namely the current intensity and the heat input of the Welding process. The emission of airborne ultrafine particles increases with the current intensity as fume formation rate does. When comparing the shielding gas mixtures, higher emissions were observed for more oxidizing mixtures, that is, with higher CO2 content, which means that these mixtures originate higher concentrations of ultrafine particles (as measured by number of particles. by cubic centimeter of air) and higher values of alveolar deposited surface area of particles, thus resulting in a more hazardous condition regarding welders exposure.

Mono(Eta(5)-cyclopentadienyl)metal(II) complexes with thienyl acetylide chromophores: synthesis, electrochemical studies, and first hyperpolarizabilities

A series of mono(eta(5)-cyclopentadienyl)metal-(II) complexes with nitro-substituted thienyl acetylide ligands of general formula [M(eta(5)-C5H5)(L)(C C{C4H2S}(n)NO2)] (M = Fe, L = kappa(2)-DPPE, n = 1,2; M = Ru, L = kappa(2)-DPPE, 2 PPh3, n = 1, 2; M = Ni, L = PPh3, n = 1, 2) has been synthesized and fully characterized by NMR, FT-IR, and UV-Vis spectroscopy. The electrochemical behavior of the complexes was explored by cyclic voltammetry. Quadratic hyperpolarizabilities (beta) of the complexes have been determined by hyper-Rayleigh scattering (HRS) measurements at 1500 nm. The effect of donor abilities of different organometallic fragments on the quadratic hyperpolarizabilities was studied and correlated with spectroscopic and electrochemical data. Density functional theory (DFT) and time-dependent DFT (TDDFT) calculations were employed to get a better understanding of the second-order nonlinear optical properties in these complexes. In this series, the complexity of the push pull systems is revealed; even so, several trends in the second-order hyperpolarizability can still be recognized. In particular, the overall data seem to indicate that the existence of other electronic transitions in addition to the main MLCT clearly controls the effectiveness of the organometallic donor ability on the second-order NLO properties of these push pull systems.

The effect of metal transfer stability (spattering) on fume generation, morphology and composition in short-circuit MAG welding

The main objective of this work was to evaluate the hypothesis that the greater transfer stability leads also to less volume of fumes. Using an Ar + 25%CO2 blend as shielding gas and maintaining constant the average current, wire feed speed and welding speed, bead-on-plate welds were carried out with plain carbon steel solid wire. The welding voltage was scanned to progressively vary the transfer stability. Using two conditions of low stability and one with high stability, fume generation was evaluated by means of the AWS F1.2:2006 standard. The influence of these conditions on fume morphology and composition was also verified. A condition with greater transfer stability does not generate less fume quantity, despite the fact that this condition produces fewer spatters. Other factors such as short-circuit current, arcing time, droplet diameters and arc length are the likely governing factors, but in an interrelated way. Metal transfer stability does not influence either the composition or the size/morphology of fume particulates. (c) 2014 Elsevier B.V. All rights reserved.

Trits(Pyrazol-1-YL)methane metal complexes for catalytic mild oxidative functionalizations of alkanes, alkanes and ketones

This work concerns recent advances (since 2005) in the oxidative functionalization of alkanes, alkenes and ketones, under mild conditions, catalyzed by homoscorpionate tris(pyrazol-1-yl)methane metal complexes. The main types of such homogeneous or supported catalysts are classified, and the critical analysis of the most efficient catalytic systems in the different reactions is presented. These reactions include the mild oxidation of alkanes (typically cyclohexane as a model substrate) with hydrogen peroxide (into alkyl hydroperoxides, alcohols, and ketones), the hydrocarboxylation of gaseous alkanes (with carbon monoxide and potassium peroxodisulfate) into the corresponding Cn+1 carboxylic acids, as well as the epoxidation of alkenes and the Baeyer-Villiger oxidation of linear and cyclic ketones with hydrogen peroxide into the corresponding esters and lactones. Effects of various reaction parameters are highlighted and the preferable requirements for a prospective homogeneous or supported C-scorpionate-M-based catalyst in oxidative transformations of those substrates are identified. (C) 2014 Elsevier B.V. All rights reserved.

Greener Selective Cycloalkane Oxidations with Hydrogen Peroxide Catalyzed by Copper-5-(4-pyridyl)tetrazolate Metal-Organic Frameworks

Microwave assisted synthesis of the Cu(I) compound [Cu(µ4-4-ptz)]n [1, 4-ptz = 5-(4-pyridyl)tetrazolate] has been performed by employing a relatively easy method and within a shorter period of time compared to its sister compounds. The syntheses of the Cu(II) compounds [Cu3(µ3-4-ptz)4(µ2-N3)2(DMF)2]n∙(DMF)2n (2) and [Cu(µ2-4-ptz)2(H2O)2]n (3) using a similar method were reported previously by us. MOFs 1-3 revealed high catalytic activity toward oxidation of cyclic alkanes (cyclopentane, -hexane and -octane) with aqueous hydrogen peroxide, under very mild conditions (at room temperature), without any added solvent or additive. The most efficient system (2/H2O2) showed, for the oxidation of cyclohexane, a turnover number (TON) of 396 (TOF of 40 h−1), with an overall product yield (cyclohexanol and cyclohexanone) of 40% relative to the substrate. Moreover, the heterogeneous catalytic systems 1–3 allowed an easy catalyst recovery and reuse, at least for four consecutive cycles, maintaining ca. 90% of the initial high activity and concomitant high selectivity.

Hydrogenating activity of Pt/zeolite catalysts focusing acid support and metal dispersion influence

Toluene hydrogenation was studied over catalysts based on Pt supported on large pore zeolites (HUSY and HBEA) with different metal/acid ratios. Acidity of zeolites was assessed by pyridine adsorption followed by FTIR showing only small changes before and after Pt introduction. Metal dispersion was determined by H2–O2 titration and verified by a linear correlation with the intensity of Pt0–CO band obtained by in situ FTIR. It was also observed that the electronic properties of Pt0 clusters were similar for the different catalysts. Catalytic tests showed rapid catalyst deactivation with an activity loss of 80–95% after 60 min of reaction. The turnover frequency of fresh catalysts depended both on metal dispersion and the support. For the same support, it changed by a 1.7-fold (HBEA) and 4.0-fold (HUSY) showing that toluene hydrogenation is structure-sensitive, i.e. hydrogenating activity is not a unique function of accessible metal. This was proposed to be due to the contribution to the overall activity of the hydrogenation of adsorbed toluene on acid sites via hydrogen spillover. Taking into account the role of zeolite acidity, the catalysts series were compared by the activity per total adsorbing sites which was observed to increase steadily with nPt/(nPt + nA). An increase of the accessible Pt atoms leads to an increase on the amount of spilled over hydrogen available in acid sites therefore increasing the overall activity. Pt/HBEA catalysts were found to be more active per total adsorbing site than Pt/HUSY which is proposed to be due to an augmentation in the efficiency of spilled over hydrogen diffusion related to the proximity between Pt clusters and acid sites. The intervention of Lewis acid sites in a greater extent than that measured by pyridine adsorption may also contribute to this higher activity of Pt/HBEA catalysts. These results reinforce the importance of model reactions as a closer perspective to the relevant catalyst properties in reaction conditions.