An XRD/XPS approach to structural change in conducting PPy

Electrochemically synthesised polypyrrole (PPy) with 1,5 naphthalene disulfonate (1,5-NDS) counterions treated with simple acid and base was characterised using X-ray diffraction (XRD) and X-ray photoelectron spectroscopy (XPS). The as synthesised film was found to be amorphous with short-range ordering in the polymer backbone. Ordering was lost after thermal ageing with evidence of counterion degradation. Base treatment lead to loss of ordering as well as dedoping of the polymer whereas acid treatment at high temperature increases short range ordering. Conductivity was also increased dramatically with evidence of ion exchange. Ordering induced by the treatment was maintained even after thermal ageing.

Platinum electrodeposition for polymer electrolyte membrane fuel cells

A novel electrodeposition technique for preparing the catalyst layer in polymer electrolyte membrane fuel cells has been designed, which may enable an increase in the level of platinum utilisation currently achieved in these systems. This method consists of a two-step procedure involving the impregnation of platinum ions into a preformed catalyst layer (via an ion-exchange into the Nafion polymer electrolyte), followed by a potentiostatic reduction. The concentration of Nafion within the catalyst layer was found to have a significant bearing on the size of the platinum deposits. The preparation of catalyst layers containing a desired platinum loading should also be possible using this method. Surface areas of the platinum deposits were determined using cyclic voltammetry. The prepared catalyst was compared with a conventional electrode made from E-TEK Pt/C. Scanning electron microscopy was used to investigate the dispersion of the platinum particles. Platinum loadings were determined quantitatively by atomic absorption spectroscopy.

Recent progress on biosorption of heavy metals from liquids using low cost biosorbents : characterization, biosorption parameters and mechanism studies

A significant number of biosorption studies on the removal of heavy metal from aqueous solutions have been conducted worldwide. Nearly all of them have been directed towards optimizing biosorption parameters to obtain the highest removal efficiency while the rest of them are concerned with the biosorption mechanism. Combinations of FTIR, SEM-EDX, TEM as well as classical methods such as titrations are extremely useful in determining the main processes on the surfaces of biosorbents. Diverse functional groups represented by carboxyl, hydroxyl, sulfate and amino groups play significant roles in the biosorption process. Solution pH normally has a large impact on biosorption performance. In brief, ion exchange and complexation can be pointed out as the most prevalent mechanisms for the biosorption of most heavy metals.

Raw materials and process chemical recovery in industrial wastewater pollution control

This article illustrates the different methods employed to recover raw materials and process chemicals in various industries. Although only a few industries such as car painting, metal cutting, electroplating, textile, abattoir and pesticide formulation have been illustrated in case studies, almost all the industries can recover raw materials and process chemicals from their waste streams. The case studies show that the investments on new processes or systems used to recover raw materials and process chemicals have a short payback period and hence bring huge savings to those industries. Thus, each industry should try to recover raw material and process chemicals from waste streams.

Immobilization of large, aliovalent cations in the small-pore zeolite K-natrolite by means of pressure

High-pressure ion exchange of small-pore zeolite K-natrolite allows immobilization of nominally non-exchangeable aliovalent cations such as trivalent europium. A sample exchanged at 3.0(1) GPa and 250 °C contains about 4.7 Eu^III ions per unit cell, which is equivalent to over 90 % of the K⁺ cations being exchanged.

Electrochemical behavior of CrN coating for polymer electrolyte membrane fuel cell

CrN films on a bipolar plate in polymer electrolyte membrane fuel cells have several advantages owing to their excellent corrosion resistance and mechanical properties. Three CrN samples deposited at various radio frequency (RF) powers by RF magnetron sputtering were evaluated under potentiodynamic, potentiostatic and electrochemical impedance spectroscopy conditions. The electrochemical impedance spectroscopy data were monitored for 168 h in a corrosive environment at 70 °C to determine the coating performance at +600 mV_SCE under simulated cathodic conditions in a polymer electrolyte membrane fuel cell. The electrochemical behavior of the coatings increased with decreasing RF power. CrN films on the AISI 316 stainless steel substrate showed high protective efficiency and charge transfer resistance, i.e. increasing corrosion resistance with decreasing RF power. X-ray diffraction confirmed the formation of a CrN(200) preferred orientation at low RF power.

Novel dithiolene complexes incorporating conjugated electroactive ligands

A series of new metal (M) dithiolene complexes bearing terthiophene (3, 12, M = Ni; 4, M = Pd; 5, 6, M = Au) and 2,5-bis(para-methoxyphenyl)thiophene units (14, M = Ni; 15, 16, M = Au; 17, M = Pd) have been synthesised in 38–99% yield. The electrochemical properties of the materials have been characterised by cyclic voltammetry and UV-vis spectroelectrochemistry. The nickel complexes possess low oxidation potentials (−0.12 to −0.25 V vs Ag/AgCl) due to the electron-rich dithiolene centres and all complexes display ligand-based redox activity. The terthiophene derivatives have been polymerised by electrochemical oxidation to give stable films with, in the case of poly(3), broad absorption characteristics. Charge transfer materials have been isolated from 14 and 16 with conductivities in the range 9 × 10⁻⁶ to 7 × 10⁻⁸ S cm⁻¹.

Geochemical changes during recharge with tertiary-treated wastewater at a coastal sandfill

Results of experiments investigating geochemical changes during artificial recharge of treated wastewater at a coastal sandfill, reclaimed with sand dredged from the seabed, are reported in this paper. Laboratory batch experiments were conducted using secondary effluent (SE) and SE treated with an additional ultrafiltration process (UF), and wastewater treated by reverse osmosis (RO) process, mixed with surface sand obtained from the sandfill. Experiments with RO showed a net increase of 0.41 meq/L, 0.12 meq/L and 0.31 meq/L for Ca(2 + ), Mg(2 + ) and HCO(3) (-), respectively. UF and SE also exhibited net increase in Ca(2 + ), Mg(2 + ) and HCO(3) (-) indicating carbonate mineral dissolution. All three waters were found to be over-saturated with respect to calcite. Carbonate dissolution reactions were observed in the field experiments. However, the presence of imported clays from the borrow source gave rise to ion exchange reactions where Na(+) attached to the clay particles were exchanged for Ca(2 + ) and Mg(2 + ) inducing mineral dissolution, driven by sub-saturation conditions. This resulted in an increase in pH with maximum values in excess of 9.0. It was also found that the sodium adsorption ratio remained high (>10) even after the groundwater had been diluted sufficiently to freshwater levels (ionic strength, I <0.015) indicating a potential for the dispersion of clay particles. This could have a deleterious consequence on porosity and hydraulic conductivity.

Monoethanolamine reclamation using electrodialysis

Monoethanolamine (MEA) is the benchmark solvent for the capture of carbon dioxide from both natural gas and flue gas streams. Despite its effectiveness in absorbing CO2, this solvent can react with impurities in the gas stream to form heat stable salts and other degradation products. These impurities can cause problems such as an increase in solvent viscosity and corrosion of the operating units. Thus, a number of approaches have been considered to mitigate the occurrence of these problems. In this paper, the use of electrodialysis as an online MEA reclamation process in a postcombustion CO2 capture facility is investigated. The study shows that high heat stable salts removal can be achieved with a high MEA recovery. However, it is necessary to limit the current density, particularly at lower salt concentrations, to reduce water splitting. The stability of the commercial ion-exchange membranes in the highly alkaline solvent is also investigated. The results show that the membranes are stable upon exposure to 30 wt % MEA for at least 4.5 months.

Nanofiltration for the concentration of heat stable salts prior to MEA reclamation

While monethanolamine has shown great potential as a solvent for the capture of carbon dioxide, impurities can build within the solution over time, leading to increased viscosity and corrosivity. Classically, these impurities are removed by a combination of neutralization and either thermal reclamation, ion exchange or electrodialysis. In this work, we evaluate the use of nanofiltration to concentrate the heat stable salts within the solution prior to such reclamation. This allows the recirculating solvent to operate with low concentrations of these impurities, while providing a low volume, concentrated solution for reclamation. Results show that nanofiltration can reject greater than 80% of the heat stable anions, while allowing the monoethanolamine to permeate through the membrane, for return to the process. Rejection of the MEA itself is less than 7%. The nanofiltration operation is only effective on lean solvent with CO2 loadings of less than 0.2 and neutralization would be required upstream to deprotonate the amine. The two membranes tested (Koch MPF-34 and MPF-36) appeared stable to exposure to the solvent for over four months.

Modificação estrutural de bentonitas nacionais : caracterização e estudos de adsorção

São apresentados os aspectos teóricos, práticos e bibliográficos envolvidos no desenvolvimento da tese de doutorado intitulada Modificação estrutural de bentonitas nacionais: caracterização e estudos de adsorção. O trabalho consistiu no desenvolvimento de um material adsorvente a partir de bentonitas, do tipo montmorilonitas, modificadas estruturalmente com o objetivo de aumentar sua capacidade de adsorção de poluentes, orgânicos e inorgânicos. O estudo visa incrementar o valor agregado deste recurso mineral e insere-se na área de tratamento de efluentes líquidos usando adsorventes não tradicionais, eficientes e de baixo custo em substituição ao carvão ativado ou às resinas de troca iônica. Foram estudadas as propriedades físicas e químicas; distribuição de tamanho de partículas, área superficial, potenciais eletrocinéticos, capacidade de troca catiônica, composição mineralógica, morfologia superficial e espaçamento basal, bem como as propriedades adsorptivas dos argilominerais não tratados e modificados, não modificadas e pilarizadas respectivamente. Também são discutidos os mecanismos de adsorção envolvidos e o desenvolvimento de um reator contínuo (adsorção em flocos) e de separação sólido/líquido. As modificações estruturais dos argilominerais foram realizadas via homoionização com cloreto de cálcio e posterior intercalação com compostos orgânicos com ação quelante de metais. A FENAN, bentonita obtida pela intercalação com Orto Fenantrolina (OF), foi a que apresentou melhor viabilidade técnica em termos de adsorção, adsorção/dessorção, floculação e de acumulação de poluentes na forma floculada e não floculada. Adicionalmente os estudos de reversibilidade da intercalação revelaram a alta estabilidade da OF na FENAN, em soluções fortemente ácidas, onde aproximadamente 90% da OF permanece ligada à superfície da argila. A quantidade de OF adsorvida na forma de unidades micelares foi de 112 mg por grama de bentonita a pH 8,5 ± 0,5. A caracterização das bentonitas, via difração de Raios X, análise térmica, microscopia eletrônica de varredura e por microscopia de força atômica, revelou que as FENAN possuem um comportamento estrutural muito estável ao longo da seqüência de adsorção/dessorção e que após a adsorção de poluentes inorgânicos, o quelato metálico formado apresenta alta estabilidade dentro da estrutura da organobentonita. A capacidade de acumulação alcançada nas FENAN foi de 110 mg de Cu/g de bentonita, valor superior à de diversos materiais adsorventes alternativos propostos em outros trabalhos similares. Os estudos de acumulação das FENAN floculadas – FENANFLOC, indicaram que a presença de floculante, na quantidade utilizada, não afeta significativamente a capacidade de remoção das bentonitas modificadas. Este comportamento apresentado, permitiu o desenvolvimento do Reator Expandido de Flocos Adsorventes (REFA), cujas características e parâmetros operacionais são discutidos em detalhe. Finalmente, os resultados são discutidos em termos dos fenômenos interfaciais envolvidos e dos potenciais práticos deste novo adsorvente e da nova técnica de adsorção em flocos no REFA.

Homogalactanas sulfatadas da alga Codium isthmocladum com atividade anticoagulante

Since the first description of sulfated polysaccharides from seaweeds, the biological activities of these compounds have been evaluated under different aspects and experimental procedures. Among the broad biological activities presented by seaweed polysaccharides, anticoagulant action appears as a promising function. In this present study we have obtained sulfated polysaccharides from the green seaweed Codium isthmocladium by proteolytic digestion, followed by separation into five fractions (0.3, 0.5, 0.7, 0.9 and 1.2) by sequential acetone precipitation. The chemical analyses have demonstrated that all fractions are composed mainly by sulfated polysaccharides. The anticoagulant activity of these fractions was determined by activated partial thromboplastin time (aPTT) and prothrombin time test (PT) using citrate normal human plasma. None fraction has shown anticoagulant activity by PT test. Furthermore, all of them have shown anticoagulant activity by aPTT test. These results indicated that the molecular targets of these sulfated polysaccharides are mainly in the intrinsic via of the coagulation cascade. Agarose gel electrophoresis in 1,3-diaminopropane acetate buffer, pH 9.0, stained with 0.1% toluidine blue showed the presence of two or three bands in several fractions while the fraction 0.9 showed a single spot. By anion exchange chromatography, the acid polysaccharides from the 0.9 acetone fraction were separated into two new fractions eluted respectively with 2.0 and 3.0 M NaCl. These compounds showed a molecular weight of 6.4 and 7.4 kDa respectively. Chemical analyses and infrared spectroscopy showed that Gal 1 and Gal 2 are sulfated homogalactans and differ one from the other in degree and localization of sulfate groups. aPPT test demonstrated that fractions 2,0 and 3,0M (Gal1 and Gal 2, respectively) have anticoagulant activity. This is the first time that anticoagulant sulfated homogalatans have been isolated from green algae. To prolong the coagulation time to double the baseline value in the aPTT, the required amount of sulfated galactan 1 (6,3mg) was similar to low molecular heparin Clexane®, whereas only 0,7mg of sulfated galactan 2 was needed to obtain the same effect. Sulfated galactan 2 in high doses (250mg) induces platelet aggregation. These results suggest that these galactans from C. isthmocladum have a potential application as an anticoagulant drug

Novas propriedades do SKTI (Inibidor de tripsina de soja): inibição para elastase neutrofílica humana e efeitos no processo de injúria pulmonar aguda

Seeds from legumes including the Glycine max are known to be a rich source of protease inhibitors. The soybean Kunitz trypsin inhibitor (SKTI) has been well characterised and has been found to exhibit many biological activities. However its effects on inflammatory diseases have not been studied to date. In this study, SKTI was purified from a commercial soy fraction, enriched with this inhibitor, using anion exchange chromatography Resource Q column. The purified protein was able to inhibit human neutrophil elastase (HNE) and bovine trypsin. . Purified SKTI inhibited HNE with an IC50 value of 8 µg (0.3 nM). At this concentration SKTI showed neither cytotoxic nor haemolytic effects on human blood cell populations. SKTI showed no deleterious effects on organs, blood cells or the hepatic enzymes alanine amine transferase (ALT) and aspartate amino transferase (AST) in mice model of acute systemic toxicity. Human neutrophils incubated with SKTI released less HNE than control neutrophils when stimulated with PAF or fMLP (83.1% and 70% respectively). These results showed that SKTI affected both pathways of elastase release by PAF and fMLP stimuli, suggesting that SKTI is an antagonist of PAF/fMLP receptors. In an in vivo mouse model of acute lung injury, induced by LPS from E. coli, SKTI significantly suppressed the inflammatory effects caused by elastase in a dose dependent manner. Histological sections stained by hematoxylin/eosin confirmed this reduction in inflammation process. These results showed that SKTI could be used as a potential pharmacological agent for the therapy of many inflammatory diseases

Métodos de determinação de cálcio e magnésio trocáveis e estimativa do calcário residual em um Latossolo submetido à aplicação de calcário e gesso em superfície

A determinação da fração do calcário remanescente no solo (calcário residual), em área onde foi realizada aplicação de calcário em superfície, sem incorporação, na implantação do sistema plantio direto, pode ser uma ferramenta importante para auxiliar na definição do momento em que se faz necessária a reaplicação de calcário. Nesse sentido, os objetivos deste trabalho foram avaliar: quais os teores de Ca e Mg trocáveis, extraídos por percolação com solução de KCl e resina trocadora de íons; a quantidade do calcário aplicado que ainda não havia reagido no solo, mediante a determinação dos teores de Ca e Mg não-trocáveis; e qual a influência do gesso nos teores de Ca e Mg trocáveis e na dissolução do calcário, 18 meses após a aplicação em superfície. O experimento foi realizado em um Latossolo Vermelho distroférrico, em Botucatu (SP). O delineamento experimental foi de blocos casualizados com parcelas subdivididas e quatro repetições. Nas parcelas, foram aplicadas quatro doses de calcário dolomítico (0, 1.100, 2.700 e 4.300 kg ha-1), com PRNT = 71,2 %, e nas subparcelas, duas doses de gesso agrícola (0 e 2.100 kg ha-1). O calcário e o gesso foram aplicados em superfície, sem incorporação. Houve alta correlação na determinação de Ca e Mg trocável entre os métodos de percolação com solução de KCl e resina trocadora de íons. A extração pelo método da resina trocadora de íons superestimou os teores de Ca e Mg trocáveis em solo com recente aplicação de calcário em superfície. A aplicação de gesso em superfície reduziu a dissolução do calcário na camada superficial (0-0,10 m). Os teores de Ca e Mg não-trocáveis podem ser utilizados para estimar a quantidade de calcário residual no solo.