Development of a new analytical approach based on cellulose membrane and chelator for differentiation of labile and inert metal species in aquatic systems

A new procedure was developed in this study, based on a system equipped with a cellulose membrane and a tetraethylenepentamine hexaacetate chelator (MD-TEPHA) for in situ characterization of the lability of metal species in aquatic systems. To this end, the DM-TEPHA system was prepared by adding TEPHA chelator to cellulose bags pre-purified with 1.0 mol L-1 of HCl and NaOH solutions. After the MD-TEPHA system was sealed, it was examined in the laboratory to evaluate the influence of complexation time (0-24 h), pH (3.0, 4.0, 5.0, 6.0 and 7.0), metal ions (Cu, Cd, Fe, Mn and Ni) and concentration of organic matter (15, 30 and 60 mg L-1) on the relative lability of metal species by TEPHA chelator. The results showed that Fe and Cu metals were complexed more slowly by TEPHA chelator in the MD-TEPHA system than were Cd, Ni and Mn in all pH used. It was also found that the pH strongly influences the process of metal complexation by the MD-TEPHA system. At all the pH levels, Cd, Mn and Ni showed greater complexation with TEPHA chelator (recovery of about 95-75%) than did Cu and Fe metals. Time also affects the lability of metal species complexed by aquatic humic substances (AHS); while Cd, Ni and Mn showed a faster kinetics, reaching equilibrium after about 100 min, and Cu and Fe approached equilibrium after 400 min. Increasing the AHS concentration decreases the lability of metal species by shifting the equilibrium to AHS-metal complexes. Our results indicate that the system under study offers an interesting alternative that can be applied to in situ experiments for differentiation of labile and inert metal species in aquatic systems. (c) 2006 Elsevier B.V. All rights reserved.

In situ differentiation of labile/inert metal species in Brazilian tropical rivers by means of a time-controlled batch-procedure based on TEPHA resin

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

Transition metal rates in latosol twice treated with sewage sludge

A reciclagem agrícola do lodo de esgoto tem provocado o acúmulo de metais pesados no solo e na água, podendo atingir níveis tóxicos e causar danos às plantas cultivadas, aos animais e ao homem, por meio da cadeia trófica. Neste intuito foi desenvolvido o presente experimento, em condições de campo, entre 2000 e 2002, onde foram avaliados os efeitos da aplicação de lodo de esgoto por dois anos, sobre a extração de metais de transição (essenciais e não) pelo extrator DTPA em um Latossolo Vermelho distrófico (LVd) de textura média. As concentrações dos elementos metálicos: Mn, Fe, Cd, Ni, Co, Pb e Cr não foram detectados pelo método da absorção atômica na solução obtida com o extrator DTPA. A aplicação de lodo de esgoto causou inicialmente pequena elevação no pH do solo, posteriormente a diminuição do mesmo, e manteve-se próximo ao original. Foi possível concluir que, com a aplicação consecutiva do lodo, os teores extraíveis de Fe e Mn nas amostras de solos aumentaram gradativamente nos dois anos agrícolas, com as doses do lodo de esgoto aplicado, época de amostragens, e foram superiores ao tratamento testemunha. O extrator apresentou capacidade restrita para avaliação da fitodisponibilidade dos metais pesados decorrentes das baixas concentrações nas amostras de solo.

Electrochemical modified electrodes based on metal-salen complexes

A general view of the electroanalytical applications of metal-salen complexes is discussed in this review. The family of Schiff bases derived from ethylenediamine and ortho-phenolic aldehydes (N,N'-ethylenebis(salicylideneiminato) - salen) and their complexes of various transition metals, such as Al, Ce, Co, Cu, Cr, Fe, Ga, Hg, Mn, Mo, Ni, and V have been used in many fields of chemical research for a wide range of applications such as catalysts for the oxygenation of organic molecules, epoxidation of alkenes, oxidation of hydrocarbons and many other catalyzed reactions; as electrocatalyst for novel sensors development; and mimicking the catalytic functions of enzymes. A brief history of the synthesis and reactivity of metal-salen complexes will be presented. The potentialities and possibilities of metal-Salen complexes modified electrodes in the development of electrochemical sensors as well as other types of sensors, their construction and methods of fabrication, and the potential application of these modified electrodes will be illustrated and discussed.

Electrical properties of polymer/metal interface in polymer light-emitting devices: electron injection barrier suppression

The electrical characterization of a high efficient multilayer polymer light emitting diode using poly[(2-methoxy-5-hexyloxy)-p-phenylenevinylene] as the emissive layer and an anionic fluorinated surfactant as the electron transport layer was performed. For the sake of comparison, a conventional single layer device was fabricated. The density current vs. voltage measurements revealed that the conventional device has a higher threshold voltage and lower current compared to the surfactant modified device. The effective barrier height for electron injection was suppressed. The influence of the interfaces and bulk contributions to the dc and high frequencies conductivities of the devices was also discussed. (c) 2006 Springer Science + Business Media, Inc.

Separating interface state response from parasitic effects in conductance measurements on organic metal-insulator-semiconductor capacitors

A simple model is developed for the admittance of a metal-insulator-semiconductor (MIS) capacitor which includes the effect of a guard ring surrounding the Ohmic contact to the semiconductor. The model predicts most of the features observed in a MIS capacitor fabricated using regioregular poly(3-hexylthiophene) as the active semiconductor and polysilsesquioxane as the gate insulator. In particular, it shows that when the capacitor is driven into accumulation, the parasitic transistor formed by the guard ring and Ohmic contact can give rise to an additional feature in the admittance-voltage plot that could be mistaken for interface states. When this artifact and underlying losses in the bulk semiconductor are accounted for, the remaining experimental feature, a peak in the loss-voltage plot when the capacitor is in depletion, is identified as an interface (or near interface) state of density of similar to 4 x 10(10) cm(-2) eV(-1). Application of the model shows that exposure of a vacuum-annealed device to laboratory air produces a rapid change in the doping density in the channel region of the parasitic transistor but only slow changes in the bulk semiconductor covered by the gold Ohmic contact. (C) 2008 American Institute of Physics.

Determining the interfacial density of states in metal-insulator-semiconductor devices based on poly(3-hexylthiophene)

Low frequency admittance measurements are used to determine the density of interface states in metal-insulator-semiconductor diodes based on the unintentionally doped, p-type semiconductor poly(3-hexylthiophene). After vacuum annealing at 90 degrees C, interface hole trapping states are shown to be distributed in energy with their density decreasing approximately linearly from similar to 20x10(10) to 5x10(10) cm(-2) eV(-1) over an energy range extending from 0.05 to 0.25 eV above the bulk Fermi level. (c) 2008 American Institute of Physics.

Ultrathin films of lignins as a potential transducer in sensing applications involving heavy metal ions

Lignins extracted from sugar cane bagasse using different alcohols in the organosolv-CO(2) supercritical pulping process have been applied in the fabrication of ultrathin films through the Langmuir-Blodgett technique. Langmuir films were characterized by surface pressure versus mean molecular area (Pi-A) isotherms to exploit the sensitivity of nanostructured lignin films to metallic ions (Cu(2+), Cd(2+) and Pb(2+)). The Pi-A isotherms were shifted to larger molecular areas when heavy metal ions are present into the subphase, which might be related to electrostatic repulsions between metallic ions entrapped within the lignin molecular structure. Taking the advantage of metal incorporation, Langmuir monolayers were transferred onto solid substrates forming Langmuir-Blodgett (LB) films to be used as a transducer in an "electronic tongue" system to detect Cu(2+) in aqueous solution below threshold standard established by the Brazilian regulation. Both techniques impedance spectroscopy and electrochemistry have been used in these experiments. Complementary, Fourier transform infrared (FTIR) spectroscopy recorded for LB films before and after soaking into Cu(2+) aqueous solution revealed an interaction between the lignin phenyl groups and the metallic ion. (C) 2007 Elsevier B.V.. All rights reserved.

Surface-enhanced raman scattering: metal nanostructures coated with langmuir-blodgett films

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

Factors affecting nucleolytic efficiency of some ternary metal complexes with DNA binding and recognition domains. Crystal and molecular structure of Zn(phen)(edda)

The binding selectivity of the M(phen)(edda) (M = Cu, Co, Ni, Zn; phen = 1,10-phenanthroline, edda = ethylenediaminediacetic acid) complexes towards ds(CG)(6), ds(AT)(6) and ds(CGCGAATTCGCG) B-form oligonucleotide duplexes were studied by CD spectroscopy and molecular modeling. The binding mode is intercalation and there is selectivity towards AT-sequence and stacking preference for A/A parallel or diagonal adjacent base steps in their intercalation. The nucleolytic properties of these complexes were investigated and the factors affecting the extent of cleavage were determined to be: concentration of complex, the nature of metal(11) ion, type of buffer, pH of buffer, incubation time, incubation temperature, and the presence of hydrogen peroxide or ascorbic acid as exogenous reagents. The fluorescence property of these complexes and its origin were also investigated. The crystal structure of the Zn(phen)(edda) complex is reported in which the zinc atom displays a distorted trans-N4O2 octahedral geometry; the crystal packing features double layers of complex molecules held together by extensive hydrogen bonding that inter-digitate with adjacent double layers via pi...pi interactions between 1,10-phenanthroline residues. The structure is compared with that of the recently described copper(II) analogue and, with the latter, included in molecular modeling. (C) 2008 Elsevier B.V. All rights reserved.

Impedance of carrier injection at the metal-organic interface mediated by surface states in electron-only tris(8-hydroxyquinoline) aluminium (Alq(3)) thin layers

Capacitance spectra of thin (< 200 nm) Alq(3) electron-only devices have been measured as a function of bias voltage. Capacitance spectra exhibit a flat response at high frequencies (> 10(3) Hz) and no feature related to the carrier transit time is observed. Toward low frequencies the spectra reach a maximum and develop a negative excess capacitance. Capacitance response along with current-voltage (J-V) characteristics are interpreted in terms of the injection of electrons mediated by surface states at the metal organic interface. A detailed model for the impedance of the injection process is provided that highlights the role of the filling/releasing kinetics of energetically distributed interface states. This approach connects the whole capacitance spectra to the occupancy of interface states, with no additional information about bulk trap levels. Simulations based on the model allow to derive the density of interface states effectively intervening in the carrier injection (similar to 1.5 x 10(12) cm (2)). (C) 2008 Elsevier B.V. All rights reserved.

Incommensurate spin-density-wave and metal-insulator transition in the one-dimensional periodic Anderson model

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

Electrocatalysis on noble metal and noble metal alloys dispersed on high surface area carbon

In this work, a simple route to prepare carbon supported Pt/C, Pt:Ru/C, Pt:Mo/C and Pt:Ru:Mo/C catalysts is reported. The electrochemical properties of the several carbon materials used as substrates in the absence and in the presence of supported platinum and platinum alloys catalysts were investigated using cyclic voltammetry and employing the thin porous coating electrode technique. The activity of the dispersed catalysts composed of Pt/C with respect to the oxygen reduction and of alloy/C with respect to methanol oxidation was investigated using steady state polarization measurements. The performance with respect to the oxygen reduction reaction of the Pt/C catalyst prepared on heat-treated Vulcan carbon substrate is equivalent to that reported in the literature for the state-of-the-art electrocatysts. Pt:Ru:Mo/C samples prepared in this work presented the higher catalytic effect for methanol electro-oxidation.

Synthesis, characterization and thermal studies on solid 3-methoxybenzoate of some bivalent transition metal ions

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

Synthesis, characterization and thermal studies of solid state 4-methylbenzylidenepyruvate of some trivalent metal ions

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