Interference effects of oxyanions commonly found in natural waters on the catalytic reduction of nitrate in water.

In this work, the influence of oxyanions on the catalytic reduction of nitrates using formic acid as the reducing agent was studied as well as the influence of bicarbonate, sulfate, and phosphate co-anions on the catalytic nitrate reduction with Pd:In/Al2O3 (1:0.25 wt.%). A negative effect on nitrate conversion was observed in the following order: phosphate > sulfate > bicarbonate, showing a strong influence of electrostatic adsorption on the catalytic reduction of nitrate. However, no direct trend was observed relating the levels of interferents to the impact on the selectivity of the bimetallic catalyst using formic acid as a reducing agent. For both bicarbonate and phosphate, at lower levels, higher selectivity to nitrogen was obtained than for the reaction in the absence of interferents. On the other hand, increasing sulfate concentration led to a decrease in nitrate conversion. The mixtures of co-anions also showed a decrease in the catalytic activity. At 120 min, a N2 selectivity higher than 95% was obtained, except for the C50-S20 (bicarbonate 50 ppm-sulfate 20 ppm) mixture which showed the lowest selectivity to N2 value (87.3%). The loss of catalyst activity was found to be reversible and not permanent.

Use of a two-step process to denitrification of synthetic brines: electroreduction in a dual-chamber cell and catalytic reduction.

Membrane separation processes are being currently applied to produce drinking water from water contaminated with nitrate. The overall process generates a brine with high nitrate/nitrite concentration that is usually send back to a conventional wastewater treatment plant. Catalytic processes to nitrate reduction are being studied, but the main goal of achieving a high selectivity to nitrogen production is still a matter of research. In this work, a two-step process was evaluated, aiming to verify the best combination of operational parameters to efficiently reduce nitrate to nitrogen. In the first step, the nitrate was reduced to nitrite by electroreduction, applying a copper electrode and different cell potentials. A second step of the process was carried out by reducing the generated nitrite with a catalytic process by hydrogenation. The results showed that the highest nitrate reduction (89%) occurred when a cell potential of 11 V was applied. In this condition, the nitrite ion was generated with all experimental conditions evaluated. Then, to reduce the nitrite ion formed by catalytic reduction, activated carbon fibers (ACF) and powder γ-alumina (γ-Al2O3) were tested as supports for palladium (Pd). With both catalysts, the total nitrite conversion was obtained, being the selectivity to gaseous compounds 94% and 97% for Pd/Al2O3 and Pd/ACF, respectively. Considering the results obtained, a two-stage treatment setup to brine denitrification may be proposed. With electrochemistry, an operating condition was achieved in which ammonium production can be controlled to very low values, but the reduction is predominant to nitrite. With the second step, all nitrite is converted to nitrogen gas and just 3% of ammonium is produced with the most selective catalyst. The main novelty of this work is associated to the use of a two-stage process enabling 89% of nitrate reduction and 100% of nitrite reduction.

Quantum Reality in the Selective Reduction of a Benzofuran System.

Two 2,3-disubstituted benzofurans (1 and 2), analogs of gamma-aminobutyric acid (GABA), were synthesized to obtain their 2,3-dihydro derivatives from the Pd/C-driven catalytic reduction of the double bond in the furanoid ring. The synthesis produced surprising by-products. Therefore, theoretical calculations of global and local reactivity were performed based on Pearson's hard and soft acids and bases (HSAB) principle to understand the regioselectivity that occurred in the reduction of the olefinic carbons of the compounds. Local electrophilicity (ωk) was the most useful parameter for explaining the selectivity of the polar reactions. This local parameter was defined with the condensed Fukui function and redefined with the electrophilic (Pk+) Parr function. The similar patterns of both resulting sets of values helped to demonstrate the electrophilic behavior (soft acid) of the olefinic carbons in these compounds. The theoretical calculations, nuclear magnetic resonance, and resonance hybrids showed the moieties in each compound that are most susceptible to reduction.

Polycyclic Aromatic Hydrocarbons (PAHs) and nitrated analogs associated to particulate matter emission from a Euro V-SCR engine fuelled with diesel/biodiesel blends.

Among the new technologies developed for the heavy-duty fleet, the use of Selective Catalytic Reduction (SCR) aftertreatment system in standard Diesel engines associated with biodiesel/diesel mixtures is an alternative in use to control the legislated pollutants emission. Nevertheless, there is an absence of knowledge about the synergic behaviour of these devices and biodiesel blends regarding the emissions of unregulated substances as the Polycyclic Aromatic Hydrocarbons (PAHs) and Nitro-PAHs, both recognized for their carcinogenic and mutagenic effects on humans. Therefore, the goal of this study is the quantification of PAHs and Nitro-PAHs present to total particulate matter (PM) emitted from the Euro V engine fuelled with ultra-low sulphur diesel and soybean biodiesel in different percentages, B5 and B20. PM sampling was performed using a Euro V - SCR engine operating in European Stationary Cycle (ESC). The PAHs and Nitro-PAHs were extracted from PM using an Accelerated Solvent Extractor and quantified by GC-MS. The results indicated that the use of SCR and the largest fraction of biodiesel studied may suppress the emission of total PAHs. The Toxic Equivalent (TEQ) was lower when using 20% biodiesel, in comparison with 5% biodiesel on the SCR system, reaffirming the low toxicity emission using higher percentage biodiesel. The data also reveal that use of SCR, on its own, suppress the Nitro-PAHs compounds. In general, the use of larger fractions of biodiesel (B20) coupled with the SCR aftertreatment showed the lowest PAHs and Nitro-PAHs emissions, meaning lower toxicity and, consequently, a potential lower risk to human health. From the emission point of view, the results of this work also demonstrated the viability of the Biodiesel programs, in combination with the SCR systems, which does not require any engine adaptation and is an economical alternative for the countries (Brazil, China, Russia, India) that have not adopted Euro VI emission standards.

Redução voltamétrica de artemisinina e sua interação com grupo heme (hemina) / Voltammetric reduction of artemisinin and its interaction with heme (hemin)

A malária é a endemia tropical mais devastadora do mundo e esse quadro é agravado pela ausência de tratamento eficaz. Entretanto, a resistência dos plasmódios à artemisinina não apresenta relevância clínica e seu mecanismo de ação está associado ao grupo heme, com formação de radicais livres e rompimento da ponte endoperóxido. O comportamento voltamétrico da artemisinina foi estudado por voltametria cíclica e voltametria de onda quadrada. O fármaco é irreversivelmente reduzido em eletrodos de carbono vítreo e os valores de potencial de pico não sofrem influência da acidez do meio, porém observou-se o maior valor de corrente em pH 6,0. O comportamento voltamétrico da artemisinina foi significativamente alterado na presença do grupo heme, provocando uma antecipação de seu pico de redução em cerca de 600 mV. Por voltametria de onda quadrada observou-se que este novo pico foi sensível à adição crescente de concentração de hemina, atingindo valor de corrente cerca de 10 vezes maior em relação ao pico original da artemisinina, numa relação de concentração de 20 mmol/L para o primeiro e 50 mmol/L do segundo. Além disso, resultados indicaram que esse processo eletrocatalítico ocorreu pela formação de Fe(II)-hemina na superfície do eletrodo, com provável processo de eletro-polimerização da hemina sobre o eletrodo de carbono vítreo. Esse efeito adsortivo foi avaliado a partir da estimativa da concentração superficial (G) de hemina sobre o eletrodo de trabalho em pH 6,0. A modificação do eletrodo de carbono vítreo por hemina mostrou que a interação entre artemisinina e o grupo heme ocorre predominantemente sobre a superfície do eletrodo e não em solução. Portanto, esclarecer o mecanismo de ação da artemisinina é importante para o planejamento e desenvolvimento de novos agentes antimaláricos.

Malaria is the tropical disease most devastating of the world and this situation is worsened by the absence of effective treatment. However, the plasmodium resistance to artemisinin does not show clinical relevance. The drug mechanism of action is associated to the heme group, with free radical formation and endoperoxide moiety breakage. The voltammetric behavior of artemisinin was studied by cyclic and square-wave voltametries. This drug was irreversibly reduced on glassy carbon electrode and the peak potential values are pH independent, however the biggest value of current peak was observed at pH 6.0. The voltammetric behavior of artemisinin was significantly changed in the heme group presence, provoking an anticipation of about 600 mV on cathodic peak. By square-wave voltammetry it was observed that this new peak was sensitive to the hemin concentration, reaching a value around 10 times larger regarding the original cathodic peak of artemisinin, being the concentration of 20 mmol/L for the former and 50 mmol/L for the latter. In addition, results indicated that this electro-catalytic process depends on the Fe(II)-hemin formation on the electrode surface, indicating the possible electro-polymerization of hemin on the glassy carbon electrode. This adsorptive effect was evaluated from the superficial concentration (G) estimation of the hemin on the working electrode at pH 6.0. The modification of the glassy carbon electrode using hemin showed that the interaction between artemisinin and the heme group predominantly occurs on the electrode surface and not in solution. Therefore, clarifying artemisinin mechanism of action is important in order to contribute for the design and development of new antimalarial agents.