Searching for gallium bioactive compounds: Gallium(III) complexes of tridentate salicylaldehyde semicarbazone derivatives

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

Mono- and dinuclear palladium(II) compounds containing N,S donor ligands - Synthesis, characterization and thermal behavior

Synthesis, spectroscopic characterization and thermal analysis of the compounds [Pd-2(dmba)(2)(mu-NCO)(mu-2-qnS)] (1), [Pd-2(dmba)(2)(mu-NCO)(mu-8-qnS)] (2), [Pd(2-qnS)(2)] (3) and [Pd(8-qn(S))2] (4) (dmba=N,N-dimethylbenzylamine; 2-qnS=2-quinolinethiolate; 8-qnS=8-quinolinethiolate) are described. The thermal decomposition of these compounds occurs in four consecutive steps and the final decomposition products were identified as Pd(0) by X-ray powder diffraction. The thermal stability order of the complexes is 4 > 3 > 1 > 2.

Factors affecting nucleolytic efficiency of some ternary metal complexes with DNA binding and recognition domains. Crystal and molecular structure of Zn(phen)(edda)

The binding selectivity of the M(phen)(edda) (M = Cu, Co, Ni, Zn; phen = 1,10-phenanthroline, edda = ethylenediaminediacetic acid) complexes towards ds(CG)(6), ds(AT)(6) and ds(CGCGAATTCGCG) B-form oligonucleotide duplexes were studied by CD spectroscopy and molecular modeling. The binding mode is intercalation and there is selectivity towards AT-sequence and stacking preference for A/A parallel or diagonal adjacent base steps in their intercalation. The nucleolytic properties of these complexes were investigated and the factors affecting the extent of cleavage were determined to be: concentration of complex, the nature of metal(11) ion, type of buffer, pH of buffer, incubation time, incubation temperature, and the presence of hydrogen peroxide or ascorbic acid as exogenous reagents. The fluorescence property of these complexes and its origin were also investigated. The crystal structure of the Zn(phen)(edda) complex is reported in which the zinc atom displays a distorted trans-N4O2 octahedral geometry; the crystal packing features double layers of complex molecules held together by extensive hydrogen bonding that inter-digitate with adjacent double layers via pi...pi interactions between 1,10-phenanthroline residues. The structure is compared with that of the recently described copper(II) analogue and, with the latter, included in molecular modeling. (C) 2008 Elsevier B.V. All rights reserved.

Nanoparticles of octakis [3-(3-amino-1,2,4-triazole)propyl] octasilsesquioxane as ligands for Cu(II), Ni(II), Cd(II), Zn(II), and Fe(III) in aqueous solution

Nanoparticles of octakis[3-(3-amino-1,2,4-triazole)propyl]octasilsesquioxane (ATZ-SSQ) were tested as ligands, for transition-metal ions in aqueous solution with a special attention to sorption isotherms, ligand-metal interaction, and determination of metal ions in natural waters. The adsorption potential of the material ATZ-SSQ was compared with related [3(3-amino-1,2,4-triazole)propyl]silica gel (ATZ-SG). The adsorption was performed using a batchwise process and both organofunctionalized surfaces showed the ability to adsorb the metal ions from aqueous solution. The Langmuir model was used to simulate the sorption isotherms. The results suggest that the sorption of these metals on ATZ-SSQ and ATZ-SG occurs mainly by surface complexation. The equilibrium condition is reached at time lower than 3 min for ATZ-SSQ, while for ATZ-SG is only reached at time of 25 min. The maximum metal ion uptake values for ATZ-SSQ were higher than the corresponding values achieved with the ATZ-SG. In order to obtain more information on the ligand-metal interaction of the complexes on the surface of the ATZ-SSQ nanomaterial, ESR study with various degrees of copper loadings was carried out. The ATZ-SSQ was tested for the determination (in flow using a column technique) of the metal ions present in natural waters. (C) 2007 Elsevier B.V. All rights reserved.

Adsorção de Mn (II) e Zn (II) em soluções aquosas usando perlita expandida revestida com quitosana

In this work, chitosan was used as a coating of pure perlite in order to increase the accessibility of the groups OH- e NH2+the adsorptionof ions Mn2+ e Zn2+.The characterization results of the expanded perlite classified as microporous and whose surface area 3,176 m2 g-1after the change resulted in 4,664 m2g-1.From the thermogravimetry(TG) it was found that the percentage of coating was34,3%.The infrared analysis can prove the presence of groups Si-OH, Si-O e Al-O-Siresulting from the perlite and C=O, NH2and OH characterization of chitosan. The experiments on experiments on the adsorption of Mn and Zn were performed in the concentration range of10 a 50 mgL-1and the adsorption capacity inpH 5,8 e 5,2 was 19,49 and 23,09 mgg-1to 25 oC,respectively.The adsorption data were best fitted to Langmuir adsorption model to Langmuir adsorption model for both metalionsisindicative of monolayer adsorption. The kinetics of adsorption were calculated from the equation of Lagergren fitting the model pseudo-second-order for all initial concentrations, suggesting that adsorption of ions Mn2+ and Zn2+ follows the kinetics of pseudo-second-order and whose constant Speedk2(g/mg.min) are 0,105 e 3,98 and capacity and maximum removal qe 4,326 e 3,348,respectively.In this study we used a square wave voltammetry cathodic stripping voltammetry to quantify the adsorbed ions, and the working electrode glassy carbon, reference electrode silver / silver chloride and a platinum auxiliary electrode. The attainment of the peaks corresponding to ions Mn2+ and Zn2+ was evaluated in and electrochemical cell with a capacity of 30 mL using a buffer system (Na2HPO4/NaH2PO4)at pH 4 and was adjusted with solutionsH3PO4 0,1molL-1and NaOH 0,1 molL-1and addition of the analyte has been a cathodic peak in- 0,873 Vand detection limit of2,55x10-6molL-1para Zn.The dough used for obtaining the adsorption isotherm was 150 mg and reached in 120 min time of equilibrium for both metal ions.The maximum adsorption for 120 min with Mn concentration 20 mgL-1 and Zn 10 mgL-1,was91, 09 e 94, 34%, respectively

Avaliação cefalométrica do tratamento da Classe II, divisão 1, de Angle com os aparelhos extrabucal de Kloehn e fixo edgewise: influência do padrão facial

O presente estudo foi realizado com o propósito de avaliar respostas cefalométricas ao tratamento com aparelho extrabucal de Kloehn associado ao aparelho fixo edgewise convencional. Telerradiografias iniciais (T1) e finais (T2) de dois grupos de 30 pacientes tratados com estes aparelhos foram selecionadas e definidas pelo índice cefalométrico de Jarabak para determinação do padrão esquelético craniofacial. Os grupos foram denominados favorável (hipodivergente) e desfavorável (hiperdivergente). A idade média, no início do tratamento, foi de 11,03 anos e final de 14,72 com o tempo médio de tratamento de 3,6 anos para o grupo favorável. No grupo desfavorável a idade inicial foi de 11,51 anos e final de 15,17 anos com tempo médio de tratamento de 3,4 anos. Foi utilizado um sistema de análise de resposta de tratamento em coordenadas X e Y representativos dos movimentos dentários e das bases ósseas decompondo-os em seus vetores horizontais e verticais. Os resultados e respostas do tratamento foram analisados e comparados entre os grupos favorável e desfavorável utilizando o teste t-Student. Os resultados mostraram não haver diferenças estatisticamente significantes na resposta cefalométrica no tratamento com o aparelho extrabucal de Kloehn associados ao aparelho fixo edgewise quanto aos padrões faciais favorável e desfavorável. O tratamento promoveu uma restrição do deslocamento anterior maxilar e um menor deslocamento anterior mandibular. Quanto à movimentação dentária maxilar, houve uma restrição do movimento mesial e extrusivo dos molares superiores no grupo favorável, enquanto que o movimento dos dentes inferiores foi mínimo no sentido anterior e vertical.

Angiotensin II, progesterone, and prostaglandins are sequential steps in the pathway to bovine oocyte nuclear maturation

Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq)

Microeletrodos: II. Caracterização eletroquímica

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

Synthesis, spectral and thermal studies on dicarboxylate-bridged palladium(II) coordination polymers. Part I

This work describes the synthesis, IR and (13)C CPMAS NMR spectroscopic as well the thermal characterization of the new dicarboxylate complexes [Pd(2)(ox)(2)(4,4'-bipy)]n (1), [Pd(2)(ox)(2)(bpe)](n) (2) and [Pd(2)(ox)(2)(pz)](n) (3) {ox = oxalate, bipy = 4,4'-bipyridine, bpe = 1,2-bis(4-pyridyl)ethane, pz = pyrazine}. TG experiments reveal that compounds 1-3 undergo thermal decomposition in three steps. Metal palladium was the final product of the thermal decompositions, which was identified by X-ray powder diffraction.

Synthesis, spectral and thermal studies on dicarboxylate-bridged palladium(II) coordination polymers. Part II

The synthesis and thermal behavior of the new [Pd(fum)(bipy)] (n) center dot 2nH(2)O (1), [Pd(fum)(bpe)] (n) center dot nH(2)O (2) and [Pd(fum)(pz)] (n) center dot 3nH(2)O (3) {bipy = 4,4'-bipyridine, bpe = 1,2-bis(4-pyridyl)ethene and pz = pyrazine} fumarate complexes are described in this work as well their characterization by IR and (13)C CPMAS NMR spectroscopies. TG curves showed that the compounds released organic ligands and lattice water molecules in the temperature range of 46-491 A degrees C. In all the cases, metallic palladium was identified as the final residue.

A solid nickel(II) complex with methionine sulfoxide

Solid Ni(C(5)H(10)NO(3)S)(2) . 2H(2)O complex was prepared and characterized. Electronic absorption spectrum shows an octahedral geometry for the complex. Infrared spectroscopy analysis shows that the metal atom is coordinated to the ligand through (COO(-)) and (S = O) groups. Thermal analysis confirmed the composition of the complex and suggests that the water molecules are not coordinated to the metal ion. The complex shows extremely high solubility in water. (C) 2000 Elsevier B.V. S.A. All rights reserved.

The Ni-Cu-PGE sulfide ores of the komatiite-hosted Fortaleza de Minas deposit, Brazil: Evidence of hydrothermal remobilization

The Fortaleza de Minas Ni-Cu-PGE sulfide deposit is hosted by Archean komatiitic rocks of the Morro do Ferro greenstone belt, near the southwestern margin of the Sa (aFrancisco) over tildeo Francisco craton, Minas Gerais state, Brazil. The deposit contains 6 million tonnes of ore with an average grade of 2.2 wt% Ni, 0.4% Cu, 0.05% Co and 1.2 ppm PGE+Au, and comprises (i) a main orebody, which is metamorphosed, deformed and transposed along a regional shear zone, consisting mainly of disseminated, brecciated and stringer sulfide ores that are interpreted to be of early magmatic origin, and (ii) PGE-rich discordant veins that are hosted in N-S- and NE-SW-trending late faults that cross-cut the main orebody. The discordant PGE-rich ore (up to 4 ppm total PGE) is characterized by thin, discontinuous and irregular veins and lenses of massive sulfides hosted by serpentinite and talc schist, and is relatively undeformed if compared with the early types of ore. It is composed mainly of pyrrhotite, pentlandite, chalcopyrite, magnetite, carbonates, and amphiboles, with minor cobaltite-gersdorffite, sphalerite, ilmenite, and quartz, and rarely maucherite (Ni11Asg), tellurides and platinum-group minerals (PGM). Omeeite, irarsite, sperrylite, and Ni-bearing merenskyite are the main PGM, followed by minor amounts of testibiopalladite and an unknown phase containing Ru, Te, and As. The PGM occur either included in, or at the margins of, sulfides, sulfarsenides, silicates and oxides, or filling fractures in pyrrhotite, pentlandite, and chalcopyrite, suggesting that they started to precipitate with these minerals and continued to precipitate after the sulfides were formed. The mantle-normalized metal distribution of the two samples of discordant veins shows distinct patterns: one richer in Ni-Pd-Ir-Rh-Ru-Os and another with higher amounts of Cu-Pt-Bi. Both are strongly depleted in Cr if compared with the metamorphosed magmatic ore of this deposit, which follows the general Kambalda-type magmatic trend. on the basis of structural, mineralogical and geochemical evidence, we propose that the PGE-rich discordant ore may have formed by remobilization of metals from the deformed, metamorphosed magmatic orebody (which shows a depleted pattern in these elements) by reduced (pyrrhotite - pentlandite - pyrite are stable), neutral to alkaline and carbonic fluids (carbonate-stable). The PGE may have been transported as bisulfide complexes, and precipitated as tellurides (mainly Pd) and arsenides (Pt, Rh, Ru, Os, Ir) in the late N-S and NE-SW-trending faults owing to a decrease in the activity of S caused by the precipitation of sulfides in the veins.

Synthesis and thermal study of the barium complexes with 8-hydroxyquinolinate derivatives

In this present work, barium ion was reacted with different ligands which are 5,7-dibromo, 5,7-dichloro, 7-iodo and 5-chloro-7-iodo-8-hydroxyquinoline, in acetone/ammonium hydroxide medium under constant stirring and the obtained compounds were as follows: (I) Ba[(C9H4ONBr2)(2)].1.5H(2)O; (II) Ba[(C9H4ONCl2)(OH)]. 1H(2)O; (III) Ba[(C9H5ONI)(2)]. 1H(2)O and (IV) Ba[(C9H4ONICl)(2)]. 5H(2)O, respectively. The compounds were characterized by elemental analysis, infrared absorption spectrum (IR), inductively coupled plasma spectrometry (ICP), simultaneous thermogravimetry-differential thermal analysis (TG-DTA) and differential scanning calorimeter (DSC).The final residue of the thermal decomposition was characterized as orthorhombic BaBr2 from (I); the intermediate residue, as a mixture of orthorhombic BaCO3 and BaCl2 and cubic BaO and the final residue, as a mixture of cubic and tetragonal BaO and orthorhombic BaCl2 (II); the intermediate residue, as orthorhombic BaCO3 and as a final residue, a mixture of cubic and tetragonal BaO from (III); and the intermediate residue, as a mixture of orthorhombic BaCO3 and BaCl2 and as a final residue, a mixture of cubic and tetragonal BaO and orthorhombic BaCl2 from (IV).

Synthesis, spectral and thermal studies on pyrazolate-bridged palladium(II) coordination polymers

Synthesis, spectroscopic characterization and thermal behavior of pyrazolate-bridged palladium complexes [Pd(mu-Pz)(2)](n) (1), [Pd(mu-mPz)(2)](n) (2), [Pd(mu-dmPz)(2)](n) (3), [Pd(mu-IPz)(2)](n) (4) {pyrazolate (Pz(-)), 4-methylpyrazolate (mPz(-)), 3,5-dimethylpyrazolate (dmPz(-)), 4-iodopyrazolate (IPz(-))} have been described in this work. The exobidentate coordination mode of pyrazolato ligands in 1-4 was inferred on basis of IR spectroscopic evidences. TG investigations indicated that the introduction of substituents at the 4 position in the pyrazolyl moiety into coordination polymers do not affect significantly their thermal stability, whereas at the 3 and 5 position reduced the stability of the main chain. Metal palladium was the final product of the thermal decompositions, which was identified by X-ray powder diffraction.

Fluorescence study of the interaction between metal ions and methyl methacrylate methacrylic acid copolymers in aqueous solutions: thallium(I), calcium(II), and terbium(III)

The binding of the cations thallium(I), calcium(II) and terbium(III) to methyl methacrylate-methacrylic acid copolymers with different fractions of acid groups (x) has been studied in aqueous solution at, various pH values using the fluorescence of covalently bonded 9-vinyl anthracene as a probe. In all cases, the extent of binding increases as a function of the charge of the polymer with either increasing fraction of carboxylic acids or of pH. However, differences are observed in the behavior of the three cations, With Tl(I), quenching of the anthracene group fluorescence is observed. indicating that the thallium(I) approaches the probe and suggesting that the alkylanthracene is probably in a relatively polar region. Binding constants have been determined from anthracene quenching data and from studies with the fluorescent-probe sodium pyrenetetrasulfonate, Good agreement is obtained between the two methods, and values for the binding constants increase from 250 to 950 M-1 as x increases from 0.39 to 1. It is suggested that the cation is held in the polyelectrolyte domain, partly by Debye-Huckel effects and partly by more specific interactions. Stronger binding is found with calcium(II) and terbium(III), and in this case increases in fluorescence intensity are observed on complexation due to the anthracene group being in a more hydrophobic region, probably as a result of conformational changes in the polymer chain. In the former case the stoichiometry of the interaction was determined from the fluorescence data to involve two carboxylate groups bound per calcium. Association constants were found using murexide as an indicator of free calcium to vary from 8400 to 37 000 M-1 as x increases from 0.39 to 1. It is suggested that in this case specific calcium(II)-carboxylate interactions contribute to the binding. With terbium(III), a greater increase in the probe fluorescence intensity was observed than with calcium, and it is suggested that the interaction with the polymer is even stronger, leading to a more pronounced conformational change in the polymer. It is proposed that the terbium(III) interacts with sis carboxylic groups on the polymer chain, with three being coordinated and three attracted by electrostatic interactions.