The influence of preparation method of OC1OC6-PPV films on the photo-oxidation process

Poly(p-phenylene vinylene) (PPV) derivatives are well known for their applications in polymer light emitting diodes (PLEDs). PPV derivatives are highly susceptible to photo-oxidation though, which is mainly caused by the scission of the vinyl double bond on the polymer backbone. In this work, we show that Langmuir-Blodgett (LB) films are less degraded than cast films of a PPV derivative (OC1OC6-PPV). Both films had similar thickness (similar to 50 nm) to allow for a more realistic comparison. Degradation was monitored with UV-vis and FTIR spectroscopies. The results indicated that cast films were completely degraded in ca. 400 min, while LB took longer time, i.e. about four times the values for the cast films. The differences can be attributed to the more compact morphology in the LB than in the cast films. With a compact morphology the diffusion of oxygen in the LB film is hampered and this causes a delay in the degradation process. (c) 2006 Elsevier Ltd. All rights reserved.

Photodegradation of the pharmaceuticals amoxicillin, bezafibrate and paracetamol by the photo-Fenton process - Application to sewage treatment plant effluent

Photodegradation of the pharmaceuticals amoxicillin (AMX), bezafibrate (BZF) and paracetamol (PCT) in aqueous solutions via the photo-Fenton process was investigated under black-light and solar irradiation. The influences of iron source, initial H2O2 concentration and matrix (distilled water and sewage treatment plant effluent) on degradation efficiency were discussed in detail. The results showed that (i) the degradation of the drugs was favored in the presence of potassium ferrioxalate (FeOx) in comparison to Fe(NO3)(3): (ii) the increase of the H2O2 concentration improved the efficiency of AMX and BZF oxidation; however, the same was not observed for PCT: (iii) the influence of the matrix was observed for the degradation of BZF and PCT: (iv) under solar irradiation, the oxidation of the BZF and PCT is faster than under black-light irradiation. All these pharmaceuticals can be efficiently degraded employing the process evaluated. (C) 2008 Elsevier B.V. All rights reserved.

Monitoring pharmaceuticals photo-Fenton degradation process by using Solid Phase Extraction and liquid chromatography

The recovery of the pharmaceuticals bezafibrate and tetracycline from water was evaluated, using Solid Phase Extraction (SPE) with the aim of applying this technique to interrupt the pharmaceuticals' photodegradation by photo-Fenton process for further analysis. Sep-Pack C-18, Strata X, and Oasis HLB cartridges were evaluated. Oasis HLB showed the most satisfactory recovery and repeatability results: 98% (CV - 1%) for bezafibrate (20.0 mg L-1) and 76% (CV = 1%) for tetracycline (25.0 mg L-1). There was not a significant decrease in recovery at lower concentrations of the pharmaceuticals, and neither when present in Sewage Treatment Plant (STP) effluent matrix.

Diclofenac Abatement using Modified Solar Photo-Fenton Process with Ammonium Iron(III) Citrate

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

Degradation of tetracycline by photo-Fenton process - Solar irradiation and matrix effects

The degradation of the antibiotic tetracycline (TC) by the photo-Fenton process was evaluated under black-light and solar irradiation. The influences of iron source (Fe(NO3)(3) or ferrioxalate), hydrogen peroxide and matrix (pure water, surface water and a sewage treatment plant effluent-STP) were evaluated. Under black-light irradiation, TC degradation was favored in the presence of Fe(NO3)(3), achieving total degradation after 1 min irradiation, while under solar light the use of ferrioxalate favors the degradation. Nevertheless, no significant difference in total organic carbon removal was observed between these two iron sources, achieving a residual concentration of around 5 mg L-1 under black-light and 2 mg L-1 under solar light irradiation. No decrease of the degradation efficiency relative to pure water was observed when TC was irradiated in a sample of surface water, under either black-light or solar irradiation. However, lower efficiency was obtained under black-light when TC was present in a sample of STP effluent, indicating the interference of the constituents of this sample on the overall efficiency of the process. on the other hand, under solar irradiation in the presence of ferrioxalate, no influence of the matrix was observed, even in the sample of STP effluent, achieving total degradation of TC in 1.5 min. (c) 2006 Elsevier B.V. All rights reserved.

Synthesis, characterization and biological analysis of the complex [VO(Hdhp)(2)] (H(2)dhp=2,3-dihydroxypyridine)

A new vanadium (IV) complex with the monoanion of 2,3-dihydroxypyridine (H(2)dhp), or 3-hydroxy-2(1H)-pyridone, was synthesized, characterized by physicochemical techniques and tested biologically. The EPR data for the [VO(Hdhp)(2)] complex in DMF are: g(x) = 1.9768, g(y) = 1.9768 and g(z) = 1.9390; A values (10(-4) cm(-1)): A(x), 59.4; A(y//), 59.4; A(z), 171.0. The vV=O band in the IR spectrum of the complex is at 986 cm(-1). The complex is paramagnetic, with mu(eff) = 1.65 BM (d(1), spin-only) at 25 degrees C. The irreversible oxidation process [V(V)/V(IV)] of the [VO(Hdhp)(2)] complex, as revealed in a cyclic voltammogram, occurs at 876 mV. The calculated molecular structure of [VO(Hdhp)(2)] shows the vanadium(IV) center in a distorted square pyramidal environment, with the oxo ligand in the apical position and the oxygen donor atoms of the Hdhp ligands in the basal positions. The ability of [VO(Hdhp)(2)] to mimic insulin, and its toxicity to hepato-biliary functions, were investigated in streptozotocin-induced diabetic rats and it was concluded that the length of treatment and the amount of [VO(Hdhp)(2)] administered were effective in reducing experimental diabetes.

Electrochemical Redox Behavior of Omeprazole Using a Glassy Carbon Electrode

Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES)

Evaluation of the photoelectrocatalytic method for oxidizing chloride and simultaneous removal of microcystin toxins in surface waters

The production of chlorine was investigated in the photoelectrocatalytic oxidation of a chloride-containing solution using a TiO(2) thin-film electrode biased at current density from 5 to 50 mA cm(-2) and illuminated by UV light. Such parameters as chloride concentrations from 0.001 to 0.10 mol L(-1), pH 2-12, and interfering salts were varied in this study in order to determine their effect on this oxidation process. At an optimum condition this photoelectrocatalytic method can produce active chlorine at levels compatible to water disinfections processes using a chloride concentration higher than 0.010 mol L(-1) at a pH of 4 and a current density of 30 mA cm(-2). The method was successfully applied to treat surface water collected from a Brazilian river. After 150 min of photoelectrocatalytic oxidation, we obtained a 90% reduction in total organic carbon removal, a 100% removal of turbidity, a 93% decrease in colour and a chemical oxygen demand (COD) removal of around 96% (N=3). The proposed technology based on photoelectrocatalytic oxidation was also tested in treating 250 mL of a solution containing 0.05 mol L(-1) NaCl and 50 mu g L(-1) of Microcystin aeruginosa. The bacteria is completely removed after 5 min of photoelectrocatalysis following an initial rate constant removal of -0.260 min(-1), suggesting that the present method could be considered as a promising alternative to chlorine-based disinfections. (C) 2008 Elsevier Ltd. All rights reserved.

Cinética e mecanismo da reação de auto-oxidação deS(IV) catalisada por íons metálicos de transição

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

Dissociation and electrooxidation of primaquine diphosphate as an approach to the study of anti-chagas prodrugs mechanism of action

This paper describes the voltammetric behavior of primaquine as a previous support to the further understanding of the delivery and action mechanisms of its respective synthesized prodrugs. There are few papers describing the drug behavior and most of the time no correlation between oxidation process and pH is done. Our results showed that primaquine oxidation is a one-step reaction involving two electrons with the charge transfer process being strongly pH-dependent in acid medium and pH-independent in a weak basic medium, with the neutral form being easily oxidized.This leads to the conclusion that quinoline nitrogen ring neutralization is a determinant step to the formation of the oxidized primaquine form. The existence of a relationship between the primaquine dissociation equilibrium and its electrooxidation process is shown.This work points the importance of voltammetric methodology as a tool for further studies on quantitative relationship studies between chemical structure and biological activity (QSAR) for electroactive drugs. (C) 2000 Elsevier B.V. S.A. All rights reserved.

Multivariate analysis of photo-Fenton degradation of the herbicides tebuthiuron, diuron and 2,4-D

The degradation of herbicides in aqueous solution by photo-Fenton process using ferrioxalate complex (FeOx) as source of Fe2+ was evaluated under blacklight irradiation. The commercial products of the herbicides tebuthiuron, diuron and 2,4-D were used. The multivariate analysis, more precisely, the response surface methodology was applied to evaluate the role of FeOx and hydrogen peroxide concentrations as variables in the degradation process, and in particular, to define the concentration ranges that result in the most efficient degradation of the herbicides. The degradation process was evaluated by the determination of the remaining total organic carbon content (TOC), by monitoring the decrease of the concentrations of the original compounds using HPLC and by the chloride ion release in the case of diuron and 2,4-D. Under optimized conditions, 20min were sufficient to mineralize 93% of TOC from 2,4-D and 90% of diuron, including oxalate. Complete dechlorination of these compounds was achieved after 10 min reaction. It was found that the most recalcitrant herbicide is tebuthiuron, while diuron shows the highest degradability. However, under optimized conditions the initial concentration of tebuthiuron was reduced to less than 15%, while diuron and 2,4-D were reduced to around 2% after only 1 min reaction. Furthermore, it was observed that the ferrioxalate complex plays a more important role than H2O2 in the photodegradation of these herbicides in the ranges of concentrations investigated. (C) 2004 Elsevier Ltd. All rights reserved.

CATHODIC BEHAVIOUR of ANODIZED TITANIUM IN SIMULATED PHYSIOLOGICAL CONDITIONS

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

Preparation of CeO2 by a simple microwave-hydrothermal method

Cerium carbonate hydroxide (orthorhombic Ce(OH)CO3) hexagonal-shaped microplates were synthesized by a simple and fast microwave-hydrothermal method at 150 degrees C for 30 min. Cerium nitrate, urea and cetyltrimethylammonium bromide were used as precursors. Ceria (cubic CeO2) rhombus-shape was obtained by a thermal decomposition oxidation process at 500 degrees C for 1 h using as- synthesized Ce(OH)CO3. The products were characterized by X-ray powder diffraction, field-emission scanning electron microscopy, thermogravimetric analysis and Fourier transformed infrared spectroscopy. The use of microwave-hydrothermal method allowed to obtain cerium compounds at low temperature and shorter time compared to other synthesis methods. (C) 2008 Elsevier B.V. All rights reserved.

Avaliação dos produtos de degradação oxidativa da Hb S em eritrócitos de doentes falcêmicos

Analysis of the products of oxidative degradation of Hb S was made by methahemoglobin measurement and a count of red blood cells with Heinz bodies. Free radicals originating from oxidation cause extensive injury to erythrocytes, decreasing their useful survival period especially in Hb S carriers. The Superoxide ion (O 2) is the most responsible for the oxidation process of Hb forming membrane-bound haemachromes which afterwards evolve to Heinz bodies, damaging the membrane and provoking erythrocytes hemolysis. The results from this work showed that the SS genotype is more susceptible to the action of the free radicals than the S/Tal genotype. The β genotype has a lower oxidative susceptibility than the SS because it has only one β s mutation. The results allowed us to conclude that: a) the simple presence of Hb S, independent of its genotype and its concentration, is sufficient to produce methaemoglobin from this Hb; b) there is not a direct relationship between methaetnoglobin concentration and the Heinz bodies count; c) the intensity of Heinz bodies in the sickled erythrocytes seems to be independent of the Hb Fetal concentration; d) The genotype SS is more susceptible to Hb oxidation with the release of products of oxidative degradation; e) methaemoglobin formation in blood of people with Hb AA and Hb AS, assessed over 24, 48, 72 and 163 hourly-periods, showed greater oxidative intensity in the Hb AS compared with Hb AA.

Anaerobic effluent disinfected with ozone/hydrogen peroxide efluente anaeróbio desinfetado com ozônio/peróxido de hidrogênio

This research aimed at studying the oxidation process, to verify the effectiveness of coliform inactivation and to evaluate the formation of ozonation disinfection byproducts (DBP) in anoxic sanitary wastewater treated with ozone/hydrogen peroxide applied at doses of 2.6 mg O3 L-1 and 2.0 mg H2O2 L-1 with contact time of 10 min and 8.1 mg O3 L-1 and 8.0 mg H2O2 L-1 with contact time of 20 min. The mean chemical oxygen demand (COD) reductions were 7.50 and 9.40% for applied dosages of 2.5-2.8 and 6.4-9.4 mg O3 L-1 + 2.0 and 8.0 mg H2O2.L-1, respectively. The Escherichia coli (E. coli) inactivation range was 2.98-4.04 log10 and the total coliform inactivation range was 2.77-4.01 log10. The aldehydes investigated were formaldehyde, acetaldehyde, glyoxal and methylglyoxal. It was observed only the formation of acetaldehyde that ranged 5.53 to 29.68 μg L-1.