Spectrophotometric determination of manganese in steels by on-line electrochemical oxidation

The aim of this work is to propose a flow spectrophotometric procedure for manganese determination in steel based on electrochemical oxidation of Mn(II) to Mn(VII) at a Pt electrode surface by means of the catalytic effect of Ag(I). The on-line oxidation step was obtained by injecting sample and electrolyte solution directly into an electrolytic cell. After electrolysis, the injectate was homogenized by bubbling air. The permanganate ions produced were passed through the spectrophotometer where absorbance was monitored at 545 nm. Effects of direct current, silver concentration, timing, flow rates, concentration and composition of support electrolyte were investigated. Direct current and silver content manifested themselves as the most relevant parameters. For determination of manganese in the 5.00 - 150 mg L -1 range (r=0,9998) and 60 s electrolysis time, the sample throughput was 20 h -1. Accuracy was assessed by analyzing ten steel standard reference materials. Results are precise (R.S.D. <3%) and in agreement with certified values of reference materials and with standard methods at 95% confidence level.

An ellipsometric study of manganese oxide films: In situ characterization of the deposition and electroreduction of MnO2

The electrodeposition of manganese oxide films onto a platinum substrate was investigated by means of in situ ellipsometry. In the thickness range from 0 to 150 nm, the anodic oxide behaves as an Isotropic single layer with optical constants that are independent of thickness. Deviations at higher thickness are explained in terms of anisotropic properties of the film. The electroreduction of thin films (up to ca. 150 nm) in an alkaline electrolyte leads to a decrease in both the refractive index and the extinction coefficient and is accompanied by a thickness increase of ca. 10%. The Mn(IV) to Mn(III) conversion takes place from the oxide/electrolyte interface inwards. © 2004 The Electrochemical Society. All rights reserved.

Manganese determination by GFAAS in feces and fish feed slurries

This paper presents a simple, fast and sensitive method to determine manganese in samples of feces and fish feed by graphite furnace atomic absorption spectrometry (GFAAS) by the direct introduction of slurries into the graphite tube. The limits of detection (LOD) and quantification (LOQ) calculated for 20 readings of the blank of the standard slurries (0.50 % m/v of feces or feed devoid of manganese) were 28 and 92 μg kg-1 for the standard feces slurries and 34 and 110 μg kg-1 for the standard feed slurries. The proposed method was applied in bioavailability studies of manganese in different fish feeds and their results proved compatible with those obtained for samples mineralized by acid digestion using microwave oven. ©2007 Sociedade Brasileira de Química.

Electropolymerization mechanism in aqueous solution of the oxo-manganese complex biomimicking of the enzymatic center present on the photosystem II

The [Mn4 IVO5(terpy)4(H 2O)2]6+ complex, show great potential for electrode modification by electropolymerization using cyclic voltammetry. The electropolymerization mechanism was based on the electronic transfer between dx2-y2 orbitals of the center metallic and pπ orbital of the ligand, which show great complexity of the system due to orbitals overlap present in octahedral complex of the metal-μ-oxo. The voltammetric behavior both in and after electropolymerization process were also discussed, where the best condition of electropolymerization was observed for low scan rate and 50 potential cycles. A study in ITO/glass electrode for better characterization of polymer was also performed. ©The Electrochemical Society.

Cation distribution and magnetic characterization of the multiferroic cobalt manganese Co2MnO4 spinel doped with bismuth

The structural and magnetic properties of the cubic spinel oxide Co 2MnO4 (Fd3m space group) doped with different concentrations of bismuth, were investigated by X-ray diffraction and SQUID magnetometry. The Bi3+ ions entering into the CoIII octahedral sites do not alter the effective moment, μeff ∼8.2 μB, whereas both the magnetization M50 kOe at the highest field (50 kOe) and the field-cooled MFC magnetizations increased when increasing the Bi content. The ferrimagnetic character of the parent compound, Co2MnO4, is maintained for all materials although the antiferromagnetic interactions Co2+-Co2+ are affected, resulting in higher values of the Curie-Weiss temperature. Due to the large ionic radius of Bi, octahedra distortions occur as well as valence fluctuations of the Mn ions, giving rise to Jahn-Teller effects and enhancing the exchange interactions. The off-center Bi3+ ion is responsible of non-centrosymmetric charge ordering and should lead to multiferroïsme conditions for the BixCo2-xMnO4 material. © 2012 Elsevier B.V.

Biomimetic sensor based on 5,10,15,20-tetrakis(pentafluorophenyl)-21H,23H- porphyrin iron (III) chloride and MWCNT for selective detection of 2,4-D

Exploitation of the electronic properties of carbon nanotubes for the development of voltammetric and amperometric sensors to monitor analytes of environmental relevance has increased in recent years. This work reports the development of a biomimetic sensor based on a carbon paste modified with 5,10,15,20-tetrakis(pentafluorophenyl)-21H,23H-porphyrin iron (III) chloride (a biomimetic catalyst of the P450 enzyme) and multi-wall carbon nanotubes (MWCNT), for the sensitive and selective detection of the herbicide 2,4- dichlorophenoxyacetic acid (2,4-D). The sensor was evaluated using cyclic voltammetry and amperometry, for electrochemical characterization and quantification purposes, respectively. Amperometric analyses were carried out at -100 mV vs. Ag/AgCl(KClsat), using a 0.1 mol L-1 phosphate buffer solution at pH 6.0 as the support electrolyte. Under these optimized analytical conditions, the sensor showed a linear response between 9.9 × 10-6 and 1.4 × 10-4 mol L-1, a sensitivity of 1.8 × 104 (±429) μA L mol -1, and limits of detection and quantification of 2.1 × 10 -6 and 6.8 × 10-6 mol L-1, respectively. The incorporation of functionalized MWCNT in the carbon paste resulted in a 10-fold increase in the response, compared to that of the biomimetic sensor without MWCNT. In addition, the low applied potential (-100 mV) used to obtain high sensitivity also contributed to the excellent selectivity of the proposed sensor. The viability of the application of this sensor for analysis of soil samples was confirmed by satisfactory recovery values, with a mean of 96% and RSD of 2.1% (n = 3). © 2013 Elsevier B.V.

Development of an electrochemical sensor based on nanostructured hausmannite-type manganese oxide for detection of sodium ions

The preparation and electrochemical characterization of hausmannite-type manganese oxide to use as a sensing material for sodium ion is described. This paper reports a new via synthetic to obtain of the hausmannite-type manganese oxide and its application in the construction of modified electrode as a voltammetric sensor. The electrochemical activity of hausmannite-type manganese oxide is controlled by intercalation/deintercalation of the sodium ions within the oxide lattice. The detection is based on the measurement of anodic current generated by oxidation of MnIII-MnIV at electrode surface. The best electrochemical response was obtained for a sensor composition of 20% (w/w) hausmannite oxide in the paste, a TRIS buffer solution of pH 6.0-7.0 and a scan rate of 50 mV s-1. A sensitive linear voltammetric response for sodium ions was obtained in the concentration range of 2.01 × 10 -5-2.09 × 10-4 mol L-1 with a slope of 355 μA L mmol-1 and a detection limit of 7.50 × 10 -6 mol L-1 using cyclic voltammetry. The use of hausmannite has significantly improved the selectivity of the sensor compared to the birnessite-type manganese oxide modified electrode. Under the working conditions, the proposed method was successfully applied to determination of sodium ions in urine samples. © 2013 Elsevier B.V.

Electrochemical Properties of Oxo-Manganese Complex Biomimicking Enzyme Active Sites and Its Electrocatalytic Application for Dopamine Determination

This work describes the characterization of the [Mn2 IV,IVO2(terpy)2(H2O)2]4+ complex in aqueous solution by UV-vis spectrophotometry, cyclic voltammetry, and linear sweep voltammetry with a rotating disk electrode. The pH effect, potential scan rate, effect of perfluorosulfonate polymer, and anion of supporting electrode on the electrochemical behavior of the modified electrode for better performance were investigated. The potential peak of the modified electrode was linearly dependent upon the ratio [ionic charge]/[ionic radius]. The modified electrode exerted an electrocatalytic effect on dopamine oxidation in aqueous solution with a decrease in the overpotential compared with the unmodified glassy carbon electrode. This way, the modified electrode showed an enzymatic biomimicking behavior. Tafel plot analyses were used to elucidate the kinetics and mechanism of dopamine oxidation. © 2013 Springer Science+Business Media New York.

Determination of in situ speciation of manganese in treated acid mine drainage water by using multiple diffusive gradients in thin films devices

Acid mine drainage (AMD) is a serious environmental problem that creates acidic solution with high Mn concentrations. The speciation of residual Mn from AMD after an active treatment involving the addition of a neutralizing agent can reliably evaluate the treatment efficiency and provide knowledge of the Mn species being inputted into the environment. The aim of this study was to evaluate the in situ lability and speciation of Mn using the diffusive gradients in thin films (DGT) technique with treated drainage water from a uranium mine (TAMD). DGT devices with different binding phases (Chelex-100 and P81 and DE81membranes) were used to perform the in situ speciation of Mn. A comparison of the results from deploying DGT in the laboratory and in situ shows that the speciation of Mn in TAMD should be performed in situ. Linear deployment curves (from in situ experiments) indicate that the DGT device containing the Chelex-100 binding phase can be used to evaluate Mn lability in TAMD. The labile Mn fraction (from in situ measurements) obtained using the device containing the Chelex-100 resin ranged from 63 to 81% of the total Mn concentration and, when compared to the speciation obtained using the CHEAQS software, indicated that this device was capable of uptaking the free Mn2+ and a portion of the MnSO4(aq). The values obtained using the DGT technique were compared to those from on site solid phase extraction, and a good agreement was found between the results. The amount of negative Mn species sampled by DE81 device was insignificant (<1.5%) for all of the sites. Sites containing a relatively small amount of Ca (<40mgL-1) and measured using devices containing the P81 membrane agreed with the concentration predicted by the CHEAQS software for positive Mn species (Mn2+ and Mn(OH)+). Nevertheless, the speciation obtained using the CHEAQS software indicated that the concentrations of positive Mn species were underestimated for sites with relatively high Ca concentrations (>150mgL-1), which take place due to the saturation of binding sites in the P81 membrane. © 2013 Elsevier B.V.

Distribution and availability of copper, iron, manganese and zinc in the archaeological black earth profile from the Amazon region

Os solos de terra preta arqueológica são ricos em matéria orgânica, contêm fragmentos cerâmicos e artefatos líticos e apresentam nutrientes em concentrações mais elevadas do que outros tipos de solos. Com o intuito de contribuir com informações sobre concentrações de micronutrientes disponíveis em solos de terra preta, foram avaliadas através de extrações químicas sequenciais, a distribuição e disponibilidade de Cu, Fe, Mn e Zn em um perfil de terra preta arqueológica no município de Juruti, estado do Pará. As maiores concentrações de Cu, Fe, Mn e Zn no perfil são encontradas na fração residual. Este estudo mostrou que ferro, manganês e zinco são preferencialmente disponíveis a partir das frações, associados aos óxidos de Fe-Mn, variando de 1265,39 a 1818,12 mg kg^-1, 0,83 a 48,51 mg kg^-1 e 1,92 a 12,05 mg kg^-1, respectivamente, e o cobre a partir da matéria orgânica, variando de 0,13 a 0,45 mg kg^-1.

Interaction of Curcumin with Manganese May Compromise Metal and Neurotransmitter Homeostasis in the Hippocampus of Young Mice

Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq)

Manganese(II) complexes with thiosemicarbazones as potential anti-Mycobacterium tuberculosis agents

Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)

Geological and geophysical data integration for delimitation of mineralized areas in a supergene manganese deposits

Geophysical methods are widely used in mineral exploration. This paper discusses the results of geological and geophysical studies in supergene manganese deposits of southern Brazil. Mineralized zones as described in geological surveys were characterized as of low resistivity (20 Omega.m) and high chargeability (30ms), pattern found also in oxides and sulfite mineral deposits. Pseudo-3D modeling of geophysical data allowed mapping at several depths. A relationship between high chargeability and low resistivity may define a pattern for high grade gonditic manganese ore. Large areas of high chargeability and high resistivity may result in accumulation of manganese and iron hydroxides, due to weathering of the gonditic ore, dissolution, percolation and precipitation.

Electrochemical Properties of the Oxo-Manganese-Phenanthroline Complex Immobilized on Ion-Exchange Polymeric Film and Its Application as Biomimetic Sensor for Sulfite Ions

Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)

Effect of manganese supplementation on the membrane integrity and the mitochondrial potential of the sperm of grazing Nelore bulls

Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)