Organic and conventional fertilisation procedures on the nitrate, antioxidants and pesticide content in parts of vegetables

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

Photoluminescence of bulks and thin films of Eu3+-doped organic/inorganic hybrids

Organic-inorganic hybrids formed by polyether-based chains grafted to both ends to a siliceous backbone through urea cross-linkages (-NHC=O)NH-), named di-ureasil, have been used as host for incorporation of Eu3+ in the form of EuCl3. The bulks and the thin films, both optically transparent, were characterized by excitation, absorption and emission spectroscopy. Photoluminescence results point out that the Eu3+ ions occupy, at least, two distinct local environments. Besides, the processing method (thin films or bulks) has influence on the energy levels of the hybrid host probably due to the lower degree of organization of the thin films structure. (c) 2007 Elsevier B.V. All rights reserved.

Electrochemistry of organometallic compounds. Part II. Oxidations of alkyl and aryl derivatives of bis(salicylaldehyde)ethylenediimine cobalt(III) in dimethylformamide

The influence of the axial organic ligand R on the electrochemical oxidation of the compounds [RCoIII(salen)DMF)], where salen is bis(salicylaldehyde)ethylenediimine, and R CH3, C2H5, n-C3H7, n-C4H9, s-C4H9, i-C4H9, CH2Cl, CF3CH2, c-C6H11CH2, c-C6H11, C6H5, C6H5CH2, p-CH3C6H4CH2, and p-NO2C6H4CH2, was studied by means of cyclic voltametry in dimethylformamide (DMF), 0.2 M in tetraethylammonium perchlorate (TEAP), at 25 and -20°C, with a platinum disc working electrode. The above-mentioned compounds can be classified according to their electrochemical behavior. (a) The complexes with R CH3, C2H5, n-C3H7, n-C4H9, c-C6H11CH2, and C6H5 undergo a reversible one-electron oxidation in the 10-50 V s-1 potential scan range. At slower scan rates, the oxidized product decomposes chemically. At -20°C, this chemical step is slow, and a reversible one-electron electrochemical oxidation is observed. (b) The compounds with R CH2Cl, C6H5CH2, p-CH3C6H4CH2 and p-NO2C6H4CH2 undergo a quasi-reversible one-electron oxidation at room temperaure. At -20°C, the electrochemical process becomes more complex. A following chemical reactions is coupled to the quasi-reversible one-electron transfer. Two reduction peaks are observed. (c) The compounds with R i-C4H9, s-C4H9, and c-C6H11 undergo a reversible one-electron oxidation at -20°C. At room temperature, the irreversible chemical reaction following the electron transfer step is too fast to allow the isolation of the electrochemical step. (d) At -20°C, the derivatives with R C2H5, c-C6H11 CH2 and c-C6H11 are adsorbed at the electrode surface. Evidence indicates that the reagent in these reactions is the pentacoordinated species [RCoIII(salen)]. A linear free-energy relationship between E1/2 (for reversible processes) and the Taft polar parameters o* was obtained with a slope of ρ* = 0.25 ± 0.03. As expected, the benzyl derivatives which present mesomeric effects do not fit this polar correlation. The rated of the electrochemical oxidation is also affected by the nature of the ligand R. For the ligands which are strong electron-withdrawing groups and for the benzyl derivatives, the rate of the electrochemical oxidation of the metal ion decreases at room temperature. At lower temperatures, it is suggested that the oxidation to the CoIV-R species is followed by a chemical reaction in which this complex is partly transformed into a CoIII(R*) species, which is reduced at a much more cathodic potential than the Co(IV) species. © 1979.

Kinetics of the reaction of alkylamines with 7,7,8,8-tetracyanoquinodimethane (TCNQ) in organic solvents

The following sequence of substitution reactions was studied spectrophotometrically in organic solvents: RNH2 + TCNQ →-HCN 7-substituted TCNQ →-HCN +RNH2 7.7-disubstituted TCNQ where R = butyl, octyl, dodecyl, and hexadecyl. The production of 7-(alkylamino)-7,7,8-tricyanoquinodimethanes proceeds via the formation of the anion radical of TCNQ (TCNQ-·) whose rate of appearance was found to be a function of the chain length of R, reaching a maximum for octylamine. The formation of TCNQ-· was sensitive to the solvent polarity and electron-donor power and was associated with a small enthalpy and a highly negative entropy of activation. Above a certain [C8H17NH2] the rate of disappearance of TCNQ-· was independent of the amine concentration, and the reaction had a much higher enthalpy and entropy of activation. The occurrence of tautomerism precluded an investigation of the conversion of 7-(octylamino)-7,8,8-tricyanoquinodimethane into 7,7-bis(octylamino)-8,8-dicyanoquinodimethane. A study of the reaction of octylamine with 7-morpholino-7,8,8-tricyanoquinodimethane (which does not exist in tautomeric forms) showed that the second substitution step proceeds with the same mechanism as the first one. The only difference between the two compounds (TCNQ and its monosubstituted morpholino derivative) is one of reactivity. © 1985 American Chemical Society.

Effect of organic synthetic food colours on mitochondrial respiration

Eleven organic synthetic dyes, currently or formerly used as food colours in Brazil, were tested to determine their effect on mitochondrial respiration in mitochondria isolated from rat liver and kidney. The compounds tested were: Erythrosine, Ponceau 4R, Allura Red, Sunset yellow, Tartrazine, Amaranth, Brilliant Blue, Indigotine Blue, Fast Red E, Orange GGN and Scarlet GN. All food colours tested inhibited mitochondrial respiration (State III respiration, uncoupled) supported either by α-ketoglutarate or succinate. this inhibition varied largely, e.g. from 100% to 16% for Erythrosine and Tartrazine respectively, at a concentration of 0.1 mg food colour per mitochondrial protein. Both rat liver and kidney mitochondria showed similar patterns of inhibition among the food colours tested. This effect was dose related and the concentration to give 50% inhibition was determined for some of the dyes. The xanthene dye Erythrosine, which showed the strongest effect, was selected for further investigation on mitochondria in vivo.

Small-scale method for the determination of selected organochlorine pesticides in soil

A small-scale method was developed for the simultaneous determination of γ-HCH, heptachlor, aldrin, dicofol, mirex, endosulfan I, endosulfan II and endosulfan sulphate in soil. The extraction and clean-up steps were combined into one step by transferring soil samples to chromatographic columns prepacked with neutral alumina. The pesticides elution was processed with n-hexane : dichloromethane (7:3) and the concentrated eluate was analysed using gas-liquid chromatography with electron capture detection. Analyses of the in vitro fortified samples with the selected pesticides were performed at three different levels. Mean recoveries for aldrin, γ-HCH and heptachlor, at levels of 2, 10 and 20 ng/g, ranged from 71 to 87%; for dicofol, at levels of 8, 40 and 80 ng/g, ranged from 97 to 103%; for endosulfan I and II, at levels of 5, 25 and 50 ng/g, ranged from 88 to 96%; for mirex, at levels of 6, 30 and 60 ng/g, ranged from 86 to 110%; and for endosulfan sulphate, at levels of 15, 75 and 150 ng/g, ranged from 93 to 104%. The method can be used for rapid determination of these pesticides in soil. © Springer-Verlag 1996.

Phase analysis of seeded and doped PbMg1/3Nb2/3O3 prepared by organic solution of citrates

PbMg1/3Nb2/3O3 (PMN) prepared by organic solution of citrates was analyzed by the Rietveld method to determine the influence of seeds and dopants on the perovskite and pyrochlore phase formation. It was observed that pyrochlore phase formation increases with an increase in calcination time when no additives are included during the preparation. It was also observed that a greater amount of perovskite phase appeared in doped or seeded samples. The fraction of perovskite phase increased from 88 mol % in pure sample to ∼95 mol % in doped and seeded samples calcined at 800°C for 1 h. It is clear that the addition of dopants or seeds during PMN preparation can enhance the formation of perovskite phase.

Reduction of dissolved oxygen in water: Hydrazine and its organic substitutes

In industrial processes using aqueous solutions, corrosion of metal surfaces may occur at various locations. Much of the damage to steam generators and boilers is caused by corrosion. Dissolved oxygen in water is one of the most potent corrosion-causing factors, and therefore oxygen should be eliminated from steam-generating systems' feedwater. Chemical reduction, by reagents such as hydrazine or organic compounds, generally is used for the deoxygenation of water. This article reviews the major oxygen scavengers currently available.

Preparation of 9.5/65/35 PLZT powders by organic precursor method

In this study the preparation of 9.5/65/35 PLZT ceramic powders were investigated. The powders with the formula Pb0.905La0.095(Zr0.65 Ti0.35)0.976O3 + 3.5 w% PbO were prepared using Pechini process and partial oxalate method. The powder phase formation, powder morphology, and green density of PLZT were shown.

Room temperature visible/infrared emission and energy transfer in Nd3+-based organic/inorganic hybrids

The photoluminescence features and the energy transfer processes of Nd3+-based siloxanepoly(oxyethylene) hybrids are reported. The host matrix of these materials, classed as di-ureasils, is formed by a siloxane backbone covalently bonded to polyether chains of two molecular weights by means of urea cross-links. The room-temperature photoluminescence spectra of these xerogels show a wide broad purple-blue-green band (350-570 nm), associated with the emitting centres of the di-ureasil host, and the typical near infrared emission of Nd3+ (700-1400 nm), assigned to the 4F3/2 → 4I9/2,11/2,13/2 transitions. Self-absorptions in the visible range, resonant with intra-4f3 transitions, indicate the existence of an energy conversion mechanism of visible di-ureasil emission into near infrared Nd3+ luminescence. The existence of energy transfer between the di-ureasil's emitting centres and the Nd3+ ions is demonstrated calculating the lifetimes of these emitting centres. The efficiency of that energy transfer changes both with the polymer molecular weight and the Nd3+ concentration.

Thermal Behavior and Spectroscopic Study of Neutral and Cationic Mononuclear Cyclopalladated Compounds

The reactions of the precursor [Pd(N,C-dmba)(MeCN)2](NO 3) (1) (dmba = N,N-dimethylbenzylamine), with the proligands 3,5-dimethylpyrazole (Hdmpz), 2-quinolinethiol (qnSH) and 1,1′- bis(diphenylphosphine)ferrocene (dppf) afforded the compounds [Pd(N,C-dmba)(Hdmpz)(ONO2)]0.5CH2Cl2 (2), [Pd(N,C-dmba)(qnSH)(ONO2)] 0.5CH2Cl2 (3) and [Pd(N,C-dmba)(dppf)](NO3) (4), respectively. The mononuclear species 2,3 and 4 were characterized by elemental analysis, infrared spectroscopy, NMR and thermogravimetric analysis. The IR spectra show bands which are consistent with terminal monodentate nitrate group for 2-3 and ionic nitrate for 4. The 1H and 13C NMR data confirm that coordination of the organic ligands has occurred and the 31P{1H} NMR data for 4 clearly evidences the occurrence in solution of three cyclopalladated species with the dppf acting as a bridging ligand in two cases and as a chelate in one. The thermal behavior of compounds 1-4 suggests that complex 2 is the most stable. The X-ray diffractometry results show the formation of PdO from 1 and 2, Pd2OSO4 from 3, and of a mixture of PdO and Fe 2(PO4)3 from 4, as final decomposition products.

Pollution by hexachlorobenzene and pentachlorophenol in the coastal plain of São Paulo state, Brazil

Organochlorine compounds were dumped by chemical industries during the 1970s in many areas of the coastal plain of São Paulo state in Brazil. These dumps, located on hillsides and in valleys, in both rural and urban environments, are responsible for soil and water pollution. The objective of this work was to determine how the pollutants have spread in an area occupied by a spodosol-type soil mantle. The study combines soil morphological observations with soil and water analysis of hexachlorobenzene (HCB) and pentachlorophenol (PCP) in soil toposequences. The results indicate that the highest pollutant concentrations are observed near the dump site and that the compounds contamination is increasing. A map integrating topography and chemical concentrations was created to visualize the spatial distribution of HCB levels in the landscape. Physical and chemical analyses were performed to measure HCB and PCP levels in the soil. Soil water appears to act as a vector of HCB, probably through complexation with and dispersal of dissolved organic matter. The persistence of HCB at the studied site is most likely due to the low pH values in combination with a high content of organic matter. HCB was consistently found in higher concentrations than PCP. It is plausible that the cause of this difference is that PCP is degraded more easily under sunlight than HCB and that degradation of PCP under acid conditions leads to the formation of HCB. © 2003 Published by Elsevier B.V.

Chlorine evolution during the fusion of chlorofluoroindate glasses

Samples with a composition of 40InF 3-20ZnF 2-5MCl- xBaF 2-ySrF 2, where M=Na, Li and x+y=35 mol%, were prepared. The thermal properties related to the Ba/Sr ratio and to the remaining chlorine content in the glasses were studied. Thermal stability is improved with the addition of chlorine. However, chlorine concentration is regulated by the sublimation of indium fluorides which takes place at about 600°C. Indium fluorides arc formed during glass fusion. The mechanisms of chlorine sublimation were studied. © 2005 Akadémiai Kiadó, Budapest.

Waveguide features in self-patternable amine functionalized organic-inorganic hybrids

We report the use of organic-inorganic sol-gel derived poly(oxyehylene)/ siloxane hybrid doped with methacrylic acid modified zirconium (IV) n-propoxide for the fabrication of low cost waveguides trough direct UV laser writing. The organic-inorganic hybrids were processed as monoliths with size and shape control. The effective guiding region was identified and the number of modes was estimated via mode field analyses. A grating was successfully superimposed on the channel and the respective reflection spectrum was measured, enabling the determination of the guiding region dimension, the calculation of the effective refractive index of the guided mode. © 2007 IEEE.

Heterogeneous photocatalytic treatment of organic dyes in air and aqueous media

This review focuses on the heterogeneous photocatalytic treatment of organic dyes in air and water. Representative studies spanning approximately three decades are included in this review. These studies have mostly used titanium dioxide (TiO2) as the inorganic semiconductor photocatalyst of choice for decolorizing and decomposing the organic dye to mineralized products. Other semiconductors such as ZnO, CdS, WO3, and Fe2O3 have also been used, albeit to a much smaller extent. The topics covered include historical aspects, dark adsorption of the dye on the semiconductor surface and its role in the subsequent photoreaction, semiconductor preparation details, photoreactor configurations, photooxidation kinetics/mechanisms and comparison with other Advanced Oxidation Processes (e.g., UV/H2O2, ozonation, UV/O3, Fenton and photo-Fenton reactions), visible light-induced dye decomposition by sensitization mechanism, reaction intermediates and toxicity issues, and real-world process scenarios. © 2008 Elsevier B.V. All rights reserved.