Solid phase extraction of zinc with octadecyl silica membrane disks modified by N,N'-disalicylidene-1,2-phenylendiamine and determination by flame atomic absorption spectrometry

A procedure for separation and preconcentration of trace amounts of Zn(II) from aqueous media is proposed. The procedure is based on the adsorption of Zn2+ on octadecyl bonded silica membrane disk modified with N,N'-disalicylidene-1,2-phenylendiamine at pH 7. The retained zinc ions were then stripped from the disk with a minimal amount of 1.5 mol L-1 hydrochloric acid solution as eluent, and determined by flame atomic absorption spectrometry. Maximum capacity of the membrane disk modified with 5 mg of the ligand was found to be 226 µg Zn2+. The relative standard deviation of zinc for ten replicate extraction of 10 µg zinc from 1000 mL samples was 1.2%. The limit of detection of the proposed method was 14 ng of Zn2+ per 1000 mL. The method was successfully applied to the determination of zinc in natural water samples and accuracy was examined by recovery experiments and independent analysis by graphite furnace atomic absorption spectrometry (GFAAS).

Biheterocyclic ligands: synthesis, characterization and coordinating properties of bis(4-amino-5-mercapto-1,2,4-triazol-3-yl) alkanes with transition metal ions and their thermokinetic and biological studies

The Co(II), Ni(II) and Cu(II) metal ions complexes of Bis(4-amino-5-mercapto-1,2,4-triazol-3-yl) alkanes (BATs) have been prepared and characterized by elemental analysis, conductivity measurements infrared, magnetic susceptibility, the electronic spectral data and thermal studies. Based on spectral and magnetic results, the ligands are tetradentate coordinating through the N and S-atoms of BATs; six-coordinated octahedral or distorted octahedral and some times four-coordinated square planar were proposed for these complexes. Activation energies computed for the thermal decomposition steps were compared. The ligands and their metal complexes were tested in vitro for their biological effects. Their activities against two gram-positive, two gram-negative bacteria and two fungal species were found to vary from moderate to very strong.

Spectrophotometric flow injection system for determination of Zn2+ in ophthalmic formulations using Alizarin red S

A spectrophotometric flow injection method for the determination of Zn(II) in ophthalmic formulations was developed. In this work, Zn(II) ion was complexed with Alizarin red S in borate buffer solution (pH 9.0) and the chromophore produced was monitored at 520 nm. The analytical curve was linear in the Zn(II) concentration range from 6.05 x 10-6 to 1.50 x 10-4 mol L-1 with a detection limit of 3.60 x 10-6 mol L-1. Recoveries ranged from 96.3 to 105 % and a relative standard deviation of 1.2 % (n = 10) for 5.5x10-5 mol L-1 Zn(II) reference solution were obtained. The sampling rate was 60 h-1 and the results obtained of Zn(II) in ophthalmic products using this procedure are in close agreement with those obtained using a comparative spectrophotometric procedure at 95 % confidence level.

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.

Antileishmanial action of organometallic complexes of Pt(II) and Rh(I)

The three organometallic complexes [(Cis-PtII (DDH) (2,5-Dihidroxibenzensulfonic)2, RhI (CO)2 Cl(2-Aminobenzothiazole) and RhI (CO)2 Cl(5-Cl-2-Methilbenzothiazole)] used in this study had been previously found to have a high in vitro activity against promastigote and amastigote like forms of Leishmania donovani. Here, the cytotoxic effect of these new organometallic complexes on the J-774 macrophages were studied. Only the RhI(CO)2 Cl (2-Aminobenzothiazole) complex induced substantial toxicity in the cells. Also, we assayed the effect of this complex on the parasite's biosynthesis of macromolecules. The RhI(CO)2Cl (5-Cl-2-Methylbenzothiazole) complex inhibited DNA, RNA, and protein synthesis. On the other hand, the two other compounds tested did not inhibit the incorporation of radioactive precursors. Finally important ultrastructural alterations in the parasites treated with the two non-cytotoxic complexes were observed.

Antiplasmodial activity of iron(II) and ruthenium(II) organometallic complexes against Plasmodium falciparum blood parasites

This work reports the in vitro activity against Plasmodium falciparumblood forms (W2 clone, chloroquine-resistant) of tamoxifen-based compounds and their ferrocenyl (ferrocifens) and ruthenocenyl (ruthenocifens) derivatives, as well as their cytotoxicity against HepG2 human hepatoma cells. Surprisingly with these series, results indicate that the biological activity of ruthenocifens is better than that of ferrocifens and other tamoxifen-like compounds. The synthesis of a new metal-based compound is also described. It was shown, for the first time, that ruthenocifens are good antiplasmodial prototypes. Further studies will be conducted aiming at a better understanding of their mechanism of action and at obtaining new compounds with better therapeutic profile.

Decomposição térmica de complexos de Zn e Cd com isomaleonitriladitiolato (imnt)

Thermal decomposition of [Bu4N]2[Zn(imnt)2] and [M(NH3)2(imnt)] complexes with M = Zn and Cd, and imnt = (bis 1,1-dicyanoethylene-2,2 dithiolate) in inert atmosphere was investigated by thermogravimetric analysis (TG) and differential scanning calorimetry (DSC). Pyrolysis studies at different temperatures, 300, 400, 500, and 600 ºC, in N2 atmosphere were performed and the products were characterized by X-ray diffraction (XRD), infrared and Raman spectroscopy, and scanning electron microscopy (SEM). The products were identified as sulfide sub-micron particles, along with amorphous carbon. Particle sizes estimated by SEM were ca. 50 nm for the cationic complexes and 500 nm for the neutral complexes.

Utilização de um eletrodo de grafite-epóxi recoberto com [Zn(FEN)3][tetratris(4-clorofenil) borato]2 sensível a zinco(II) em meio 1,10-fenantrolina como eletrodo indicador em titulações potenciométricas de precipitação

The construction and analytical evaluation of a coated graphite-epoxy electrode sensitive to the zinc-1,10-phenantroline complex based on the [Zn(fen)3][tetrakis(4-chlorophenyl)borate]2 incorporated into a poly(vinylchloride) (PVC) matrix are described. A thin membrane film of this ion-pair, dibutylphthalate (DBPh) and PVC were deposited directly onto an electrically conductive graphite-epoxy support located inside a Perspex® tube. The best PVC polymeric membrane contains 65% (m/m) DBPh, 30% (m/m) PVC and 5% (m/m) of the ion-pair. This electrode shows a response of 19.5 mV dec-1 over the zinc(II) concentration range of 1.0 x 10-5 to 1.0 x 10-3 mol L-1 in 1,10-phenantroline medium, at pH 6.0. The response time was less than 20 seconds and the lifetime of this electrode was more than four months (over 1200 determinations by each polymeric membrane). It was successfully used as an indicator electrode in the potentiometric precipitation titration of zinc(II) ions.

Syntheses, characterization and antifungal activity of tris(1,10-phenanthroline)iron(ii) bis(n-r-sulfonyldithiocarbimate)zincate(ii)

Four new compounds with the general formula [Fe(phen)3][Zn(RSO2N=CS2)2], where phen = 1,10-phenanthroline, R = 4-FC6H4 (1), 4-ClC6H4 (2), 4-BrC6H4 (3) and 4-IC6H4 (4), respectively, were obtained by the reaction of the appropriate potassium N-R-sulfonyldithiocarbimate (RSO2N=CS2K2) and tris(1,10-phenanthroline)iron(II) sulfate, with zinc(II) acetate dihydrate in dimethylformamide. The elemental analyses and the IR data were consistent with the formation of the expected complexes salts. The ¹H and 13C NMR spectra showed the signals for the cationic iron(II) complex and dithiocarbimate moieties. The molar conductance data were consistent with the 1:1 cation:anion complexes in 1-4. The antifungal activities of the compounds were tested in vitro against Candida albicans, Candida tropicalis and Colletotrichum gloeosporioides.

Complexes of 3,4-dimethoxybenzoic acid anion with Cu(II), Co(II), La(III), and Nd(III)

Physico-chemical properties of 3,4-dimethoxybenzoates of Co(II), Cu(II), La(III) and Nd(III) were studied. The complexes were obtained as hydrated or anhydrous polycrystalline solids with a metal ion-ligand mole ratio of 1 : 2 for divalent ions and of 1 : 3 in the case of trivalent cations. Their colours depend on the kind of central ion: pink for Co(II) complex, blue for Cu(II), white for La(III) and violet for Nd(III) complexes. The carboxylate groups in these compounds are monodentate, bidentate bridging or chelating and tridentate ligands. Their thermal decomposition was studied in the range of 293-1173 K. Hydrated complexes lose crystallization water molecules in one step and form anhydrous compounds, that next decompose to the oxides of respective metals. 3,4 - Dimethoxybenzoates of Co(II) is directly decomposed to the appropriate oxide and that of Nd(III) is also ultimately decomposed to its oxide but with the intemediate formation of Nd2O2CO3.. The magnetic moment values of 3,4-dimethoxybenzoates determined in the range of 76-303 K change from 4.22 µB to 4.61 µB for Co(II) complex , from 0.49 µB to 1.17 µB for Cu(II) complex , and from 2.69 µB to 3.15 µB for Nd(III) complex.

Estudos sobre a alimentação mineral do algodoeiro. II. Deficiências de micronutrientes na variedade I. A. C. 11

No sentido de se obter o quadro sintomatológico da carência dos micronutrientes, assim como dados analíticos, cultivou-se em solução nutritiva purificada plantas de algodão da variedade I. A. C. 11. Foi obtido o quadro sintomatológico das carências de B, Cu, Fe, Mn, Mo e Zn. A análise química das folhas novas afetadas pelas carências apresentou os seguintes valores (ppm): B=33; Cu=4,8; Fe=238; Mn=8,7; Mo = 0,12: Zn=25,2.

Acumulação diferencial de nutrientes por cinco cultivares de milho (zea mays L): II - acumulação de micronutrientes

No presente trabalho, os autores apresentam os resultados de um ensaio de campo empregando os cultivares Agroceres 256, Agroceres 504, Centralmex, H-7974 e Piranao no sentido de aquilatar diferenças na acumulação e exportação de micronutrientes. O ensaio foi conduzido num regossol de fertilidade mediana, exceto em relação ao K que é baixo, situado no município de Piracicaba, SP. O delineamento experimental utilizado foi de blocos ao acaso com 4 repetições. Foram seguidas as práticas culturais comuns e a adubação constituiu de 83 g da fórmula 30--120-70 por metro linear por ocasião do plantio e 33 g por metro linear da fórmula 50-0-4, em cobertura 22 dias após a germinação. Plantas foram coletadas a partir dos 20 dias após a germinação, em intervalos de 20 dias até os 120 dias. As plantas foram divididas em "colmo + folhas", pendão e espiga e analisadas para B, Cu, Fe, Mn e Zn. Concluíram os autores que diferenças na acumulação de micronutrientes manifestam-se antes da fase de crescimento intenso. Os cultivares atingem o máximo da quantidade dos nutrientes nas seguintes épocas, em dias:Cu (61-85); Fe (71-76); Mn (82-94); Zn (87-108). Verificaram, ainda, que as quantidades máximas extraídas em mg/planta são:Cu (2,06--3,49); Fe (26,66-36,28); Mn (9,92-14,39); Zn (5,88-6,69). Finalmente a exportação de nutrientes nas espigas por hectare (50.000 plantas) colhidas é: Cu (26-35 g); Fe (200-220 g); Mn (90-140 g) e Zn (160-250 g).

Nutrição mineral do cajueiro (Anacardium occidentale L.): II - deficiências dos micronutrientes - nota prévia

Na presente nota prévia, os autores relatam as observações iniciais acerca da sintomatologia de carência dos micro nutrientes, obtida em casa-de-vegetação. Observaram que as carências de B e Fe são de fácil identificação ; sendo que as carências em Cu e Zn são complexas e de difícil obtenção. Não conseguiram obter o quadro sintomatológico para o Mo e Mn. Os autores apresentam, em primeira aproximação, os níveis adequados e de carência pela análise foliar.

Nutrição mineral de Andropogon gayanus Kunth var. bisquamulatus (Hochst) Hack: II. recrutamento de micronutrientes

Sendo o capim gambá (Andropogon gayanus var. bisquamulatus) uma espécie promissora para a América Tropical, o trabalho foi conduzido no sentido de se determinar a concentração e acúmulo de micronutrientes a partir dos 20 dias após a germinação até o florescimento aos 140 dias. Foi plantada uma área de meio hectare situada em uma terra roxa estruturada e convenientemente adubada. Em intervalos de 20 dias após a germinação até aos 140 dias, plantas foram coletadas e sub-divididas em folhas e caule. 0 material seco a 80°C foi analisado para B, Cu, Fe, Mn e Zn. Aos 80 dias de idade, a gramínea extrai por planta (colmo): 0,15 mg B; 0,05 mg Cu; 3,74 mg Fe; 1,15 mg Mn e 0,23 mg Zn. A concentração de Mn diminui nas folhas com a idade da planta, sendo que a concentração de B nas folhas não é afetada. No caule há diminuição na concentração de B, Cu e Fe com o aumento da idade, sendo que a concentração de Mn e Zn não é afetada.

Nutrição mineral do gergelim (Sesamum indicum L): II - Concentração e acúmulo de micronutrientes em condições de campo

Tendo-se como objetivo conhecer o comportamento nutricional da cultura de Gergelim (Sesamum indicum L.), instalou-se um ensaio no campo experimental do Departamento de Agricultura e Horticultura, da Escola Superior de Agricultura "Luiz de Queiroz" da Universidade de São Paulo, visando determinar as concentrações e acúmulo de micronutrientes pelo cultivar Venezuela em diferentes estádios de desenvolvimento, e avaliar a exportação pela colheita. O experimento foi conduzido no decorrer do ano agrícola 1981/1982, num solo Terra Roxa Estruturada, Série Luiz de Queiroz. O delineamento estatístico foi inteiramente casualizado, com um cultivar, oito épocas de amostragem e quatro repetições. As primeiras amostras foram coletadas 28 dias após a emergência das plantulas (desbaste) e as demais em intervalos regulares de 12 dias, de tal maneira que sempre houvessem outras quatro competitivas na fileira. No material coletado (folha, caule e fruto), determinou-se os teores e acúmulo de micronutrientes, com exceção do molibdênio e cloro. Concluiu-se que: - a concentração dos micronutrientes foi sempre maior nas folhas do que nos caules; - a acumulação dos micronutrientes foi sempre maior nas folhas do que nos caules, com exceção do zinco; - a concentração dos micronutrientes nos órgãos amostrados, ocorreu na seguinte ordem: Folha: Fe(772,46ppm) > Mn(311,83ppm) > Zn(117,20ppm) > B(95,33ppm) > Cu(22,99 ppm). Caule: Fe(528,08ppm) > Mn(148,41ppm) > B (72,28ppm) > Zn(65,09ppm) > Cu(15,89 ppm). Fruto: Fe(282,24ppm) > B(4104ppm) > Mn (30,87ppm) > Zn(22,04ppm) > Cu(l6,33 ppm). - A acumulação total dos micronutrientes pela planta inteira foi crescente com a idade até os 112 dias, com exceção do B nas folhas e B e Fe nos caules; - a acumulação pela planta (mg/planta) foi em ordem decrescente: Fe(13M2) > Mn(21,64) > Zn(10,54) > B(8,01) > Cu(3,81); - a exportação através da colheita (mg/planta) foi em ordem decrescente: Fe(67J7) > B(3,92) > Mn(3,75) > Zn (2,67) > Cu(1,54).