Spectroscopic and electrochemical properties of iron(II) complexes of polydentate Schiff bases containing pyrazine, pyridine and imidazole groups

We report the synthesis and spectroscopic/electrochemical properties of iron(II) complexes of polydentate Schiff bases generated from 2-acetylpyridine and 1,3-diaminopropane, acetylpyrazine and 1,3-diaminopropane, and from 2-acetylpyridine and L-histidine. The complexes exhibit bis(diimine)iron(II) chromophores in association with pyrazine, pyridine or imidazole groups displaying contrasting pi-acceptor properties. In spite of their open geometry, their properties are much closer to those of macrocyclic tetraimineiron(II) complexes. An electrochemical/spectroscopic correlation between E degrees(Fe(III/II)) and the energies of the lowest MLCT band has been observed, reflecting the stabilization of the HOMO levels as a consequence of the increasing backbonding effects in the series of compounds. Mossbauer data have also confirmed the similarities in their electronic structure, as deduced from the spectroscopic and theoretical data. (C) 2008 Elsevier B.V. All rights reserved.

Organic additive-copper(II) complexes as plating precursors

Cu(II) ions previously coordinated with typical electroplating organic additives were investigated as an alternative source of metal for plating bath. The coordination complexes were isolated from reaction between CuSO(4) and organic additives as ligands (oxalate ion, ethylenediamine or imidazole). Deposits over 1010 steel were successfully obtained from electroplated baths using the complexes without any addition of free additives, at pH = 4.5 (H(2)SO(4)/Na(2)SO(4)). These deposits showed better morphologies than deposits obtained from CuSO(4) solution either in the absence or presence of oxalate ion as additive (40 mmol L(-1)), at pH = 4.5 (H(2)SO(4)/Na(2)SO(4))It is suggestive that the starting metal plating coordinated with additives influences the electrode position processes, providing deposits with corrosion potentials shifted over + 200 mV in 0.5 mol L(-1) NaCl (1 mV s(-1)). The resistance against corrosion is sensitive to the type of additive-complex used as precursor. The complex with ethylenediamine presented the best deposit results with the lowest pitting potential (-0.27 V vs 3.0 mol L(-1) CE). It was concluded that the addition of free additives to the electrodeposition baths is not necessary when working with previously coordinated additives. Thus, the complexes generated in ex-situ are good alternatives as plating precursors for electrodeposition bath. (C) 2009 Elsevier B.V. All rights reserved.

Cationic and neutral phenylmercury(II) complexes with heterocyclic thione ligands. X-ray structures of [HgPh(dmpymtH)][BF(4)] center dot H(2)O and [{HgPh}(2)(mu-dtu)]

The neutral complex [HgPh(dmpymt)] 1 (dmpymtH = 4,6-dimethylpyrimidine-2(1H)-thione) reacts with HBF(4) to give the cationic complex [HgPh(dmpymtH)][BF(4)] 2. The X-ray molecular structure of the later revealed a [2+1] coordination sphere about the mercury(II) atom (C-Hg-S and Hg center dot center dot center dot N). In the dinuclear complex [(HgPh)(2)(mu-dtu)] 3 [dtuH(2) = 2,4(1H,3H)-pyrimidinedithione or dithiouracil] the coordination spheres are also [2+1] although dissimilar regarding the Hg center dot center dot center dot N secondary bonds. NMR spectroscopy ((1)H, (13)C and (199)Hg) studies were undertaken in solution and the results discussed in the light of the X-ray structures. (C) 2008 Elsevier B. V. All rights reserved.

Removal of Zn(2+) from Electroplating Wastewater Using Modified Wood Sawdust and Sugarcane Bagasse

This paper describes the preparation of new adsorbents derived from sugarcane bagasse and wood sawdust (Manilkara sp.) to remove zinc (II) ions from electroplating wastewater. The first part deals with the chemical modification of sugarcane bagasse and wood sawdust, using succinic anhydride to introduce carboxylic acid functions into the material. The obtained materials (modified sugarcane bagasse MB2 and modified wood sawdust MS2) were then characterized by infrared spectroscopy (IR) and used in adsorption experiments. The adsorption experiments evaluates Zn(2+) removal from aqueous single metal solution and real electroplating wastewater on both batch and continuous experiments using fixed-bed columns prepared in laboratorial scale with the obtained adsorbents. Adsorption isotherms were then developed using Langmuir model and the Thomas kinetic model. The calculated Zn(2+) adsorption capacities were found to be 145 mg/g for MS2 and 125 mg/g for MB2 in single metal aqueous solution, whereas for the industrial wastewater these values were 61 mg/g for MS2 and 55 mg/g for MB2.

Novel catalyst systems based on Ni(II), Ti(IV), and Cr(III) complexes for oligo-and polymerization of ethylene

The complex of Brookhart Ni(α-diimine)Cl2 (1) (α-diimine = 1,4-bis(2,6- diisopropylphenyl)-acenaphthenediimine) has been characterized after impregnation on silica (S1) and MAO-modified silicas (4.0, 8.0 and 23.0 wts.% Al/SiO2 called S2, S3 and S4, respectively). The treatment of these heterogeneous systems with MAO produces some active catalysts for the polymerization of the ethylene. A high catalytic activity has been gotten while using the system supported 1/S3 (196 kg of PE/mol[Ni].h.atm; toluene, Al/Ni = 1000, 30ºC, 60 min and atmospheric pressure of ethylene). The effects of polymerization conditions have been tested with the catalyst supported in S2 and the best catalytic activity has been gotten with solvent hexane, MAO as cocatalyst, molar ratio Al/Ni of 1000 and to the temperature of 30°C (285 kg of PE/mol[Ni].h.atm). When the reaction has been driven according to the in situ methodology, the activity practically doubled and polymers showed some similar properties. Polymers products by the supported catalysts showed the absence of melting fusion, results similar to those gotten with the homogeneous systems by DSC analysis. But then, polymers gotten with the transplanted system present according to the GPC’s curves the polydispersity (MwD) varies between 1.7 and 7.0. A polyethylene blend (BPE/LPE) was prepared using the complex Ni(α-diimine)Cl2 (1) (α-diimine = 1,4-bis(2,6-diisopropylphenyl)-acenaphthenediimine) and {TpMs*}TiCl3 (2) (TpMs* = hydridobis(3-mesitylpyrazol-1-yl)(5-mesitylpyrazol-1-yl)) supported in situ on MAO-modified silica (4.0 wts. -% Al/SiO2, S2). Reactions of polymerization of ethylene have been executed in the toluene in two different temperatures (0 and 30°C), varying the molars fraction of nickel (xNi), and using MAO as external cocatalyst. To all temperatures, the activities show a linear variation tendency with xNi and indicate the absence of the effect synergic between the species of nickel and the titanium. The maximum of activity have been found at 0°C. The melting temperature for the blends of polyethylene produced at 0 °C decrease whereas xNi increases indicating a good compatibility between phases of the polyethylene gotten with the two catalysts. The melting temperature for the blends of polyethylene showed be depend on the order according to which catalysts have been supported on the MAO-modified silica. The initial immobilization of 1 on the support (2/1/S2) product of polymers with a melting temperature (Tm) lower to the one of the polymer gotten when the titanium has been supported inicially (1/2/S2). The observation of polyethylenes gotten with the two systems (2/1/S2 and 1/2/S2) by scanning electron microscopy (SEM) showed the spherical polymer formation showing that the spherical morphology of the support to been reproduced. Are described the synthesis, the characterization and the catalytic properties for the oligomerization of the ethylene of four organometallics compounds of CrIII with ligands ([bis[2-(3,5-dimethyl-1-pyrazolyl)ethyl]amine] chromium (III) chloride (3a), [bis[2-(3,5- dimethyl-l-pyrazolyl)ethyl]benzylamine] chromium (III) chloride (3b), [bis[2-(3,5-dimethyl-lpyrazolyl) ethyl]ether] chromiun(III)chloride (3c), [bis[2-(3-phenyl-lpyrazolyl) ethyl]ether]chromiun(III)chloride (3d)). In relation of the oligomerization, at exception made of the compounds 3a, all complex of the chromium showed be active after activation with MAO and the TOF gotten have one effect differentiated to those formed with CrCl3(thf)3. The coordination of a tridentate ligand on the metallic center doesn't provoke any considerable changes on the formation of the C4 and C6, but the amount of C8 are decrease and the C10 and C12+ have increased. The Polymers produced by the catalyst 3a to 3 and 20 bar of ethylene have, according to analyses by DSC, the temperatures of fusion of 133,8 and 136ºC respectively. It indicates that in the two cases the production of high density polyethylene. The molar mass, gotten by GPC, is 46647 g/mols with MwD = 2,4 (3 bar). The system 3c/MAO showed values of TOF, activity and selectivity to different α-olefins according to the pressure of ethylene uses. Himself that shown a big sensibility to the concentration of ethylene solubilized.

Reduction capability of soil humic substances from the Rio Negro basin, Brazil, towards Hg(II) studied by a multimethod approach and principal component analysis (PCA)

This paper characterizes humic substances (HS) extracted from soil samples collected in the Rio Negro basin in the state of Amazonas, Brazil, particularly investigating their reduction capabilities towards Hg(II) in order to elucidate potential mercury cycling/volatilization in this environment. For this reason, a multimethod approach was used, consisting of both instrumental methods (elemental analysis, EPR, solid-state NMR, FIA combined with cold-vapor AAS of Hg(0)) and statistical methods such as principal component analysis (PCA) and a central composite factorial planning method. The HS under study were divided into groups, complexing and reducing ones, owing to different distribution of their functionalities. The main functionalities (cor)related with reduction of Hg(II) were phenolic, carboxylic and amide groups, while the groups related with complexation of Hg(II) were ethers, hydroxyls, aldehydes and ketones. The HS extracted from floodable regions of the Rio Negro basin presented a greater capacity to retain (to complex, to adsorb physically and/or chemically) Hg(II), while nonfloodable regions showed a greater capacity to reduce Hg(II), indicating that HS extracted from different types of regions contribute in different ways to the biogeochemical mercury cycle in the basin of the mid-Rio Negro, AM, Brazil. (c) 2007 Published by Elsevier B.V.

Dynamics and Heterogeneity of Pb(II) Binding by SiO2 Nanoparticles in an Aqueous Dispersion

Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq)

Changes in phytoplankton composition in response to tides, wind-induced mixing conditions, and freshwater outflows in an urbanised estuarine complex

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

Faixa de suficiência para a cultura do algodão no centro-oeste do Brasil: II. micronutrientes

For to establish the micronutrients sufficiency range for the cotton, was used the method of mathematical chance for nutritional monitory data of three cotton growth locations in the Midwest of the Brazil, evaluating 152 areas. The method of mathematical chance was adequate for to establish cotton micronutrients references values, can be to help parameters were the conventional research cannot to prove in the short time. The micronutrients sufficiency range for productivity of 4000kg ha(-1) were, in the mg kg(-1), 41-89; 4-14; 90-230; 23-100; 25-50, and for 4500kg ha(-1) was 53-83; 4-12; 110-440; 40-60 e 25-50 for B, Cu, Fe, Mn and Zn, respectively. The sufficiency ranges indicated was similar to the existing official recommendations, however, is indicated the approach for to supply the specifics of the systems. The limitations of the method can be minimized with the expansion of the nutritional monitoring system in the cotton crops.

Immunohistochemical characterization of mononuclear cells and MHC II expression in the brain of horses with experimental chronic Trypanosoma evansi infection

Este estudo objetivou caracterizar a resposta imune celular no sistema nervoso central (SNC) de eqüinos com infecção crônica experimental por Trypanosoma evansi. Para este propósito, foram utilizados os métodos histoquímicos (HE) e imunoistoquímicos do complexo avidina-biotina peroxidase (ABC). O fenótipo do infiltrado celular foi caracterizado com o auxílio de anticorpos anti - CD3, para linfócitos T e antiBLA36 para linfócitos B. Os macrófagos foram marcados com anticorpo antiantígenos da linhagem mielóide/histiócitos (Clone Mac387). A lesão no sistema nervoso central (SNC) dos eqüinos infectados com T. evansi foi caracterizada como meningoencefalite e meningomielite não supurativa. A gravidade das lesões variou em diferentes segmentos do SNC, refletindo distribuição irregular das alterações vasculares. A distribuição de células T e B e antígenos do complexo maior de histocompatibilidade classe II foram avaliados dentro do SNC de eqüinos cronicamente infectados com T. evansi. O infiltrado perivascular e meníngeo eram constituídos predominantemente por células T e B. Macrófagos foram raramente visualizados. T.evansi não foi identificado no parênquima do SNC dos eqüinos.

Candida parapsilosis complex water isolates from a haemodialysis unit: biofilm production and in vitro evaluation of the use of clinical antifungals

Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES)

Produção de mudas de caramboleiras 'B-10' e 'Golden Star': II - marcha de absorção e acúmulo de nutrientes

A participação do Brasil no mercado externo de frutas tem aumentado consideravelmente e com potencial para crescer ainda mais. A constante ascensão dos dados de exportação brasileira é resultado da combinação de avanços tecnológicos do setor produtivo e de acesso a novos mercados consumidores. A caramboleira apresenta-se como uma excelente opção de cultivo de frutas exóticas, com grande potencial para atender ao mercado interno e às exportações. Assim, objetivou-se avaliar a marcha de absorção e de acúmulo de nutrientes em mudas de caramboleiras cultivadas em solução nutritiva. O experimento foi realizado em parcelas subdivididas, sendo utilizadas como parcela as duas cultivares de caramboleira ('B-10' e 'Golden Star') e, como subparcelas, cinco épocas de coleta de plantas, realizadas aos 208; 233; 258; 283 e 308 dias após o transplantio para a solução nutritiva. O delineamento foi inteiramente casualizado, com três repetições. As mudas foram cultivadas em vasos (8L) com solução nutritiva (pH=5,5 ± 0,5), com aeração. O experimento iniciou-se em 24-08-2005. Nos diferentes órgãos das mudas (folhas, caule e raízes), determinaram-se a marcha de absorção, o acúmulo de nutrientes e os índices nutricionais. Não houve diferenças no acúmulo de nutrientes entre as mudas de caramboleira de ambas as cultivares, sendo a ordem decrescente dos nutrientes em cada muda de 'B-10', no final do período experimental: N > K > Ca > Mg > S > P > Fe > Mn > B > Cu > Zn. Para a 'Golden Star', a ordem foi: N > K > Ca > Mg > P > S > Fe > Mn > B > Cu > Zn. Para as duas cultivares, o acúmulo médio foi maior nas folhas > caule > raízes. O período de maior exigência para 'B-10' foi entre 208 - 233 e, para 'Golden Star', entre 233 - 283 dias após o transplantio. As diferentes taxas de acumulação líquida dos nutrientes, nos diferentes órgãos da caramboleira, nem sempre acompanharam a taxa de acumulação de nutrientes do respectivo órgão.

Extração e exportação de nutrientes em cultivares de batata: II - micronutrientes

Cultivares de batata mais produtivas possivelmente exigem maior quantidade de micronutrientes, porém no Brasil há carência de informações sobre extração e exportação de micronutrientes pelas principais cultivares de batata utilizadas. O objetivo deste trabalho foi avaliar a produtividade de tubérculos, a extração e a exportação de micronutrientes nas cultivares de batata Ágata, Asterix, Atlantic, Markies e Mondial. O experimento foi conduzido durante a safra de inverno, em um Latossolo Vermelho, no município de Itaí (SP). As parcelas foram constituídas pelas cinco cultivares, e as subparcelas, por épocas de coletas, realizadas no momento do plantio e a cada sete dias após a emergência. As cultivares Mondial e Asterix, mais produtivas, apresentaram maior extração de micronutrientes, com quantidades médias por hectare de 71 g de B, 122 g de Cu, 2.228 g de Fe, 618 g de Mn e 405 g de Zn. As menores quantidades extraídas foram observadas na cultivar Atlantic, com valores de 50, 81, 1.960, 544 e 270 g ha-1 de B, Cu, Fe, Mn e Zn, respectivamente. A fase de maior demanda por B ocorre logo após o início da formação de tubérculos, aos 34 DAP, enquanto a maior demanda por Fe e Mn inicia-se a partir dos 42 DAP e vai até 63 DAP. O Cu e o Zn são absorvidos em maiores proporções a partir dos 64 DAP até o final do ciclo. A quantidade de B, Cu, Mn e Zn exportada foi dependente da cultivar, com valores por hectare variando de 48 a 22 g de B, 79 a 16 g de Cu, 65 a 37 g de Mn e 167 a 83 g de Zn. A quantidade de Fe exportada não variou entre as cultivares, sendo, em média, de 243 g ha-1. A quantidade de micronutrientes extraída e exportada pela batateira variou com as cultivares utilizadas, indicando necessidade de manejo diferencial da adubação.

Extração e exportação de nutrientes pelo híbrido de mamona Savana: II – micronutrientes

Information about micronutrients extraction and exportation by castor bean hybrids of short stature, and the periods of highest demand for each micronutrient, are most importance for correct management to fertilization. This study aimed to evaluate the micronutrients extraction and exportation by Savana hybrid castor bean, on season and out-of-season growing. The experiments were conducted during season of 2005/2006 and out-of-season of 2006 in an Oxisol. The experimental design was a randomized block with four replications. The plots were consisted by harvest times of plants, which were carried out at 17, 31, 45, 59, 73, 97 and 120 days after emergence (DAE) during the season and at 17, 31, 45, 59, 80; 100 and 120 DAE in the out-of-season. In both seasons the order of micronutrients extraction by hybrid Savanna is: Fe> Mn> Zn> B> Cu> Mo, but with larger amounts of season cultivation. The time of greatest Zn and Mo absorption during the season and the Fe in out-of-season occurs at 80 DAE, although the other micronutrients are absorbed at higher rates between 50 and 65 DAE. In season the yield, nutrients extraction and exportation from soil are higher than out-of-season, but the nutrients extraction and exportation per ton show less variation between growing seasons. Fifty percent of zinc and 60% of Cu uptaken, on average, in out-of-season is exported with grains, but for the other micronutrients the proportion exported with grains is less than 40%.

Metais pesados do solo após aplicação de biossólido: II - Disponibilidade

Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES)