Electrochemical study and dependence of 'transition state' in Co(II) and Ni(II) complexes with some antibiotics and cephalothin

Electrode kinetics and study of 'transition state' with applied potential in case of [M - antibiotics - cephalothin] system were reported at pH = 7.30 ± 0.01 at suitable supporting electrolyte at 25.0ºC. The M = Co or Ni and antibiotics were doxycycline, chlortetracycline, oxytetracycline, tetracycline, minocycline, amoxicillin and chloramphenicol used as primary ligands and cephalothin as secondary ligand. Kinetic parameters viz. transfer coefficient (a), degree of irreversibility (l), diffusion coefficient (D) and rate constant (k) were determined. The values of a and k varied from 0.41 to 0.59 and 2.60 X 10-3 cm s-1 to 9.67 X 10-3 cm s-1 in case of [Co - antibiotics - cephalothin] system. In case of [Ni - antibiotics - cephalothin], a and k varied from 0.41 to 0.58 and 2.34 X 10-3 cm s-1 to 9.19 X 10-3 cm s-1 respectively confirmed that transition state behaves between oxidant and reductant response to applied potential and it adjusts it self in such a way that the same is located midway between dropping mercury electrode and solution interface. The values of rate constant confirmed the quasireversible nature of electrode processes. The stability constants (logb) of complexes were also determined.

The physico-chemical properties of 4-chlorophenoxyacetates of Mn(II), Co(II), Ni(II) and Cu(II)

The complexes of 4-chlorophenoxyacetates of Mn(II), Co(II), Ni(II) and Cu(II) have been synthesized as polycrystalline solids, and characterized by elemental analysis, spectroscopy, magnetic studies and also by X-ray diffraction and thermogravimetric measurements. The analysed complexes have the following colours: pink for Co(II), green for Ni(II), blue for Cu(II) and a pale pink for Mn(II) compounds. The carboxylate group binds as monodentate and bidentate ligands. On heating to 1173K in air the complexes decompose in several steps. At first, they dehydrate in one step to anhydrous salts, that next decompose to the oxides of respective metals. Their magnetic moments were determined in the range of 76-303K. The results reveal them to be high-spin complexes of weak ligand fields.

Exploring potentialities of the HR-CS FAAS technique in the determination of Ni and Pb in mineral waters

National Health Surveillance Agency (ANVISA) established in the decree number 54 maximum allowed levels for Ni and Pb in mineral and natural waters at 20 µg L-1 and 10 µg L-1, respectively. For screening analysis purposes, the high-resolution continuum source flame atomic absorption spectrometry technique (HR-CS FAAS) was evaluated for the fast-sequential determination of nickel and lead in mineral waters.Two atomic lines for Ni (232.003 nm - main and 341.477 nm - secondary) and Pb (217.0005 nm - main and 283.306 nm - secondary) at different wavelength integrated absorbance (number of pixels) were evaluated. Sensitivity enhanced with the increase of the number of pixels and with the summation of the atomic lines absorbances. The main figures of merit associated to the HR-CS FAAS technique were compared with that obtained by line-source flame atomic absorption spectrometry (LS FAAS). Water samples were pre-concentrated about 5-fold by evaporation before analysis. Recoveries of Pb significantly varied with increased wavelength integrated absorbance. Better recoveries (92-93%) were observed for higher number of pixels at the main line or summating the atomic lines (90-92%). This influence was irrelevant for Ni, and recoveries in the 92-104% range were obtained in all situations.

Polarographic study and electrode kinetics of [Zn(II) - antibiotics - cephaloglycin] system vis a vis kinetics of electrode reactions

Electrode kinetics and complex formation of Zn(II) using doxycycline, chlortetracycline, oxytetracycline, tetracycline, minocycline, amoxicillin, chloramphenicol and cephaloglycin were reported at pH = 7.30 ± 0.01 in = 1.0 molL-1 NaClO4 used as supporting electrolyte at 25.0°C. Kinetic parameters viz. transfer coefficient (α), degree of irreversibility (λ) and rate constant (k) were determined. The study showed that 'Transition state' behaves between reactant (O) and product (R) response to applied potential. The stability constants varied from 2.14 to 10.31 showing that these drugs or their complexes could be used against Zn toxicity.

Otimização multivariada e aplicação do sorvente SiO2-Nb2O5 para determinação em linha de Ni(II) em matriz aquosa

Neste estudo foi desenvolvido uma metodologia para determinação de Ni(II) em amostras de água usando a extração em fase sólida (SPE) em um sistema por injeção em fluxo (FI) e detecção por espectrometria de absorção atômica em chama (F AAS). O adsorvente utilizado para a extração e pré-concentração do Ni(II) foi a sílica gel modificada com óxido de nióbio(V). Variáveis químicas e de fluxo do sistema em linha foram otimizadas usando planejamento fatorial completo (N = 2k + 3). As condições iniciais do sistema FI-F AAS foram volume de amostra de 10 mL e concentração de Ni(II) de 100 µg L-1. O tampão Sörensen foi selecionado neste estudo. A resposta analítica utilizada foi absorvância integrada. Após a otimização foram obtidos os parâmetros analíticos de mérito: faixa linear de trabalho estudada de 5-100 µg L-1; R = 0.9999; RSD = 1,5% (35 µg L-1, n = 7); limite de detecção de 0,8 µg L-1; limite de quantificação de 2,7 µg L-1 e fator de enriquecimento de 92,25. Foram analisadas amostras de água do rio Araranguá e a da rede de abastecimento da cidade de Florianópolis, ambas do estado de Santa Catarina. As duas amostras não apresentaram concentração de níquel acima do limite de detecção e após fortificação das mesmas os valores de recuperação foram na faixa de 100,2 a 103,8%.

Synthesis, characterization and thermal behaviour on solid pyruvates of some bivalent metal ions

Solid state M-L compounds, were M stands for bivalent Mn, Fe, Co, Ni, Cu, Zn and L is pyruvate, have been synthesized. Thermogravimetry and derivative thermogravimetry (TG/DTG), differential scanning calorimetry (DSC), X-Ray powder diffractometry, infrared spectroscopy, elemental analysis, and complexometry were used to characterize and to study the thermal behaviour of these compounds. The results led to information about the composition, dehydration, ligand denticity, and thermal decomposition of the isolated compounds.

Comparison of the dehydration kinetics of solid state compounds of 2-methoxybenzylidenepyruvate with some divalent metal ions

Divalent metal complexes of ligand 2-methoxybenzylidenepyruvate with Fe, Co, Ni, Cu and Zn as well as sodium salt were synthesized and investigated in the solid state. TG curves of these compounds were obtained with masses sample of 1 and 5mg under nitrogen atmosphere. Different heating rates were used to characterize and study these compounds from the kinetic point of view. The activation energy and pre-exponential factor were obtained applying the Wall-Flynn-Ozawa method to the TG curves. The obtained data were evaluated and the values of activation energy (Ea / kJ mol-1) was plotted in function of the conversion degree (α). The results show that due to mass sample, different activation energies were obtained. The results are discussed mainly taking into account the linear dependence between the activation energy and the pre exponential factor, where was verified the effect of kinetic compensation (KCE) and possible linear relations between the dehydrations steps of these compounds.

The physico-chemical properties of 2-methoxyphenoxyacetates of Mn(II), Co(II), Ni(II) and Cu(II)

The complexes of 2-methoxyhenoxyacetates of Mn(II), Co(II), Ni(II) and Cu(II)with the general formula: M(C9H9O4)3·4H2O, where M(II) = Mn, Co, Ni and Cu have been synthesized and characterized by elemental analysis, IR spectroscopy, magnetic and thermogravimetric studies and also X-ray diffraction measurements. The complexes have colours typical for M(II) ions (Mn(II) - a pale pink, Co(II) - pink, Ni(II) - green, and Cu(II) - blue). The carboxylate group binds as monodentate and bidentate ligands. On heating to 1273K in air the complexes decompose in the same way. At first, they dehydrate in one step to anhydrous salts, that next decompose to the oxides of respective metals with the intermediate formation of the oxycarbonates. Their solubility in water at 293K is of the order of 10-5 mol·dm-3. The magnetic moments of analysed complexes were determined in the range of 76-303K. The results reveal them to be high-spin complexes of weak ligand fields.

Synthesis, characterization and thermal behaviour of solid 2-methoxycinnamylidenepyruvate of some bivalent metal ions in CO2 and N2 atmospheres

Solid State M-2-MeO-CP compounds, where M stands for bivalent metals (Mn, Fe, Co, Ni, Cu and Zn) and 2-MeO-CP is 2-methoxycinnamylidenepyruvate, were synthesized. Simultaneous thermogravimetry and differential thermal analysis (TG-DTA), differential scanning calorimetry (DSC), elemental analysis and complexometry were used to establish the stoichiometry and to study the thermal behaviour of these compounds in CO2 and N2 atmospheres. The results were consistent with the general formula: M(L)2∙H2O. In both atmospheres (CO2, N2) the thermal decomposition occurs in consecutive steps which are characteristic of each compound. For CO2 atmosphere the final residues were: Mn3O4, Fe3O4, Co3O4, NiO, Cu2O and ZnO, while under N2 atmosphere the thermal decomposition is still observed at 1000 º C.

Thermal behaviour of succinic acid, sodium succinate and its compounds with some bivalent transitions metal ions in dynamic N2 and CO2 atmospheres

Thermal stability and thermal decomposition of succinic acid, sodium succinate and its compounds with Mn(II), Fe(II), Co(II), Ni(II), Cu(II) and Zn(II) were investigated employing simultaneous thermogravimetry and differential thermal analysis (TG-DTA) in nitrogen and carbon dioxide atmospheres and TG-FTIR in nitrogen atmosphere. On heating, in both atmospheres the succinic acid melt and evaporate, while for the sodium succinate the thermal decomposition occurs with the formation of sodium carbonate. For the transition metal succinates the final residue up to 1180 ºC in N2 atmosphere was a mixture of metal and metal oxide in no simple stoichiometric relation, except for Zn compound, where the residue was a small quantity of carbonaceous residue. For the CO2 atmosphere the final residue up to 980 ºC was: MnO, Fe3O4, CoO, ZnO and mixtures of Ni, NiO and Cu, Cu2O.

Teor de nutrientes em mudas de cedro (Cedrela fissilis Vell.) submetidas a doses crescentes de níquel, em solução nutritiva

O efeito da aplicação de níquel sobre o teor de nutrientes na raiz, no caule e nas folhas de mudas de cedro (Cedrela fissilis Vell.) foi estudado em um experimento realizado em casa de vegetação do Departamento de Ciência do Solo da Universidade Federal de Lavras. As mudas foram cultivadas em solução nutritiva de Clark e submetidas a doses crescentes de Ni: 0, 42, 84, 169 e 252 mimol. O experimento foi conduzido em delineamento estatístico de blocos ao acaso, e após 60 dias de exposição ao metal pesado foram feitas avaliações do teor de macro e de micronutrientes na matéria seca de raiz, caule e folha. Os resultados mostraram que a aplicação de níquel aumentou o teor de P, praticamente não afetou o teor de K e de S, no entanto reduziu o teor de Ca e de Mg. Os teores de Cu, Fe e Mn, de modo geral, sofreram redução, ao passo que o teor de Zn foi pouco afetado. O teor de Ni, na matéria seca de raiz, caule e folha, elevou-se com o aumento das doses deste metal pesado, que mostrou ser móvel nas plantas analisadas.

Índice de translocação de nutrientes em mudas de cedro (Cedrela fissilis Vell.) e de ipê-roxo (Tabebuia impetiginosa (Mart.) Standl.) submetidas a doses crescentes de cádmio, níquel e chumbo

Com o objetivo de avaliar os efeitos da toxidez de Cd, Ni e Pb, mudas de cedro e de ipê-roxo foram cultivadas em solução nutritiva de Clark, em condições de casa de vegetação do Departamento de Ciência do Solo da Universidade Federal de Lavras, com doses crescentes de Cd (0, 22, 44, 88 e 132 mimol/l), de Ni (0, 42, 84, 169 e 252 mimol/l) e de Pb (0, 48, 96, 192 e 288 mimol/l), adotando-se para tal um delineamento estatístico de blocos ao acaso, para os três ensaios. Ao final de 60 dias de exposição ao metal pesado, foram feitas avaliações do índice de translocação de macro e de micronutrientes da raiz para a parte aérea, tendo sido constatado que o aumento das doses de Cd, Ni e Pb exerceu efeitos sobre os índices de translocação de P, K, Ca, Mg, S, Cu, Fe, Mn e Zn, ora positivos, ora negativos, variando com a espécie, o metal pesado e o nutriente.

Concentração de Zn e Mn nos efluentes do beneficiamento de carvão mineral e em Typha domingensis Pers (TYPHACEAE)

O estudo objetivou investigar a concentração de zinco e manganês nos efluentes do beneficiamento de carvão e em Typha domingensis Pers. Amostras de sedimento, água, raízes, caules e folhas (n = 8 cada) foram coletadas no Lavador da Mina do Trevo, Siderópolis, SC, e em um banhado sem influência da mineração (área-controle). O conteúdo disponível dos metais no sedimento, dissolvido na água e total em T. domingensis, foi determinado por espectrofotometria de absorção atômica. Os dados de concentração de metais nos diferentes compartimentos e áreas foram submetidos ao teste "t", à análise de variância (ANOVA I) e à análise de correlação de Pearson (r). A significância estatística entre as diferenças verificadas na ANOVA foi avaliada por meio do teste SNK (Student-Newman-Keuls-Test), p < 0,05 e > 0,01. Zn e Mn apresentaram-se em concentrações mais elevadas no sedimento do que na água, nas duas áreas. Ambos os metais foram detectados na água em concentrações mais elevadas na área minerada do que na área-controle, enquanto no sedimento apenas o Zn seguiu essa tendência. T. domingensis concentrou Zn em valores mais elevados na raiz, enquanto o Mn, nas folhas, evidenciando, ainda, concentrações mais elevadas de Zn na área minerada do que na área-controle. A explotação do carvão, portanto, disponibilizou Zn e Mn em concentrações mais elevadas na área minerada do que aquelas verificadas na área não minerada, comprometendo, assim, a biota. T. domingensis comportouse como espécie concentradora de metais, o que comprova sua potencialidade para utilização na fitorremediação de áreas degradadas.

Pollution trends using bark of morus alba in the cities of buenos aires and mendoza (Argentina)

A comparative study of elements deposited on tree bark was carried out for urban and periurban areas of two of the most important cities in Argentina. The content of Fe, Mg, Al, Mn, Zn, Pb, Ba, Cr, Hg, Cu, Ni, Cd and Sb was determined by inductively coupled plasma atomic emission spectrometry (ICP-OES) in Morus alba tree bark collected in the cities of Buenos Aires and Mendoza. The main air pollutants detected in the Buenos Aires urban area were Ba, Cr, Cu and Ni and indicate significative difference from the Mendoza urban and periurban areas. Significantly, higher concentrations of Zn, Ba, Cr and Cu were recorded in the periurban area of the city of Buenos Aires than in Mendoza. Bark samples were strongly influenced by dust and show Al, Fe, Mg and other element accumulations that indicate that soil particles were carried out by wind. Elements like Ba and Zn, commonly linked to traffic emissions, showed the highest concentrations in the Buenos Aires metropolitan area, possibly due to more intensive vehicular traffic. Our results indicated that intensity of vehicular traffic and not city structure is responsible for air pollution.

Avaliação da utilização de composto orgânico produzido a partir dos resíduos de fábrica de celulose quanto aos níveis de organoclorados e metais

Lodos gerados em Estações de Tratamento de Efluentes de fábricas de celulose kraft branqueada podem conter metais pesados e compostos organoclorados mesmo para fábricas que possuam sequências de branqueamento ECF (livres de cloro elementar), devido à presença de dióxido de cloro. Neste trabalho, buscou-se avaliar o potencial de absorção de metais pesados e compostos organoclorados (PCDD e PCDF) por Brassica juncea, utilizando como substrato o composto orgânico constituído por lodo biológico de uma Estação de Tratamento de Efluentes por lodos ativados misturado com cascas de eucalipto de uma fábrica de celulose brasileira. As plantas de Brassica juncea foram cultivadas em vasos de 0,63 dm³ em casa de vegetação, durante 73 dias. Os seguintes parâmetros foram monitorados no substrato e nas plantas: Fe, Mn, Pb, Ni, Cu, Zn, Cr, Cl-, carbono orgânico total e AOX (compostos organo-halogenados adsorvíveis). Os níveis de metais pesados presentes no solo após a aplicação do composto ficaram dentro de faixas permissíveis da legislação brasileira para aplicação de composto orgânico para uso agrícola. Traços de PCDD e PCDF foram encontrados no substrato em concentrações menores do que 0,5 ng I-TEQ/kg (ppt). Tais valores ficaram abaixo de 17 ng I-TEQ/kg, considerado o limite mais exigente de qualidade de compostos adotados na Alemanha e no Canadá.