Chemical and spectroscopic studies of a new palladium(II) complex with N-acetyl-L-cysteine

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

Synthesis of a functionalized europium complex and deposition of luminescent Langmuir-Blodgett (LB) films

Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES)

Characterization and biological studies of a new platinum(II) complex with the amino acid L-alliin

Synthesis and characterization of a new Pt(II) complex with the amino acid L-alliin (S-allyl-L-cysteine sulfoxide, C(6)H(11)NO(3)S) are described. Elemental and mass spectrometric analyses of the solid complex are consistent with [PtCl(2)(alliin)], or [PtCl(2)(C(6)H(11)NO(3)S)]. (13)C nuclear magnetic resonance (NMR), [(1)H-(15)N] two dimensional (2D) NMR and infrared spectroscopy indicate coordination of the ligand to Pt(II) through the N and S atoms. The complex is very soluble in dimethyl sulfoxide. Biological analysis for evaluation of a potential cytotoxic effect of the complex was performed using HeLa cells derived from human cervical adenocarcinoma. The complex presented moderate cytotoxic activity, inducing about 40% cell death at a concentration of 400 mol L(-1).

Synthesis and solid-state structural characterization of bis (thiocyanatemercury)tetracarbonyliron

The bis (thiocyanatemercury)tetracarbonyliron, [Fe(CO)4(HgSCN)2], was prepared from [Fe(CO) 5] and Hg(SCN)2, and studied by IR spectroscopy and X-ray diffraction. The compound crystallizes in the tetragonal space group I4,1/a. The unit cell, with dimensions of a = 13.778(3), c = 13.234(3) Å, V = 2512.3(9) Å3, contains four molecules. The iron atom is octahedrally coordinated by four carbonyl groups and two mercury atoms in cis positions. The coordination of the mercury atoms is distorted square-planar, since, besides mercury-iron and mercury-sulphur bonds, there are also mercury-mercury and mercury-nitrogen interactions. The FeHg distance is 2.506(5)Å and the HgFeHg angle is 78.0(1)°. © 1987.

Kinetics, electrochemistry and resonance raman spectra of the (2-mercaptopyridine) (edta)ruthenium(III) complex

The chemistry of the pentadentate edta complexes of ruthenium(III) and (II) with 2-mercaptopyridine (HSpy) has been investigated based on spectroscopic, kinetic and electrochemical techniques. The reaction of [Ru(III)(edta)H2O]- with HSpy proceeds with a specific rate of 1.05 × 104 M-1 S -1 (25°C, I = 0.10 M, acetate buffer), forming a red complex (λmax = 550 nm) which undergoes a relaxation process as a function of pH, with an apparent pKa = 4.35 and kobs = 0.31 S -1. The second reaction depends on the concentration of HSpy and leads to a stable green product (λmax = 630 mn). A pronounced enhancement has been observed in the Raman spectra of the complexes, particularly in the region of the metal-ligand vibrations. The electronic and resonance Raman spectra are consistent with the coordination of HSpy via the sulfur atom in the red complex, and with a chelate binding in the green species. © 1987.

Preparation, characterization and spectroscopy of the europium diphenylphosphinate complex

The purpose of this work is to study the preparation and spectroscopic behavior of the europium diphenylphosphinate complex -Eu(DPP)3. Elemental and thermogravimetric analysis, powder X-ray diffractometry, and infrared spectroscopy were applied to characterize the formula of the final product and the sixfold coordination of the Eu3+ ion. Excitation and emission spectra have been recorded at liquid nitrogen and room temperatures. The 5D0→7F2 transition intensity decreases when T decreases in comparison to the 5D0→7F1 transition intensity. Molecular mechanic calculations were developed in order to obtain the spatial coordinates of the Eu3+ and ligand ions. The simple overlap model was used to calculate the total splitting of the 5D0→7F1 transition, 5D0→7F0/5D 0→7F2 ntensity ratio and the intensity parameters, Ωλ (λ=2 and 4). Good agreements between theoretical predictions and experimental results have been obtained with g=2/3 as the effective charge and α=0.8×10-24 cm3 as the isotropic polarizability of the oxygen. © 1998 Elsevier Science S.A.

White light emission of Eu3+-based hybrid xerogels

The luminescence spectra and extended x-ray-absorption fine-structure (EXAFS) measurements of a series of Eu3+-based organic/inorganic xerogels were reported and related to the local coordination of the lanthanide cations. The hybrid matrix of these organically modified silicates, classed as U(2000) ureasils, is a siliceous network to which short organic chains containing oxyethylene units are covalently grafted by means of urea bridges. The luminescent centers were incorporated as europium triflate, Eu(CF3SO3)3, and europium bromide, EuBr3, with concentrations 200≥n≥20 and n=80, 40, and 30, respectively - where n is the number of ether oxygens in the polymer chains per Eu3+ cation. EXAFS measurements were carried out in some of the U(2000)nEu(CF3SO3)3 xerogels (n=200, 80, 60, and 40). The obtained coordination numbers N ranging from 12.8, n=200, to 9.7, n=40, whereas the average Eu3+ first neighbors distance R is 2.48-2.49 Å. The emission spectra of these multiwavelength phosphors superpose a broad green-blue band to a series of yellow-red narrow 5D0→7F0-4 Eu3+ lines and to the eye the hybrids appeared to be white, even at room temperature. The ability to tune the emission of the xerogels to colors across the chromaticity diagram is achieved by changing the excitation wavelength and the amount of salt incorporated in the hybrid host. The local environment of Eu3+ is described as a continuous distribution of closely similar low-symmetry network sites. The cations are coordinated by the carbonyl groups of the urea moieties, water molecules, and, for U(2000)nEu(CF3SO3)3, by the SO3 end groups of the triflate anions. No spectral evidences have been found for the coordination by the ether oxygens of the polyether chains. A mean radius for the first coordination shell of Eu3+ is calculated on the basis of the emission energy assignments. The results obtained for U(2000)nEu(CF3SO3)3, 2.4 Å for 90 ≥n≥40 and 2.6 and 2.5 Å for n=30 and 20, respectively, are in good agreement with the values calculated from EXAFS measurements. The energy of the intraconfigurational charge-transfer transitions, the redshift of the 5D0→7F0 line, with respect to the value calculated for gaseous Eu3+, and the hypersensitive ratio between the 5D0→7F2 and 5D0→7F1 transitions, point out a rather low covalency nature of the Eu3+ first coordination shell in these xerogels, comparing to the case of analogous polymer electrolytes modified by europium bromide. ©1999 The American Physical Society.

Dominance hierarchy in different stages of development in colonies of the primitively eusocial wasp Mischocyttarus cerberus styx (Hymenoptera, Vespidae)

In primitively eusocial insect societies, reproductive division of labor is established by dominance-submission interactions which determine a linear dominance hierarchy. As previously observed for other species, in Mischocyttarus cerberus styx (Hymenoptera, Vespidae), the dominant female is the main egg layer. Most of her attacks were to the females directly beneath in the rank establishing a hierarchy. During the pre-emergence stage, the hierarchy was already defined and in the post-emergence stage, pre-male substage, the frequency of dominance interactions were strong but the hierarchy was still maintained by the first-ranked female. In the decline stage there were many neutral individuals which could be the reproductives of a new colony.

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.

Synthesis and spectroscopic characterization of new metal(II) complexes with methionine sulfoxide

Methionine sulfoxide complexes of iron(II) and copper(II) were synthesized and characterized by chemical and spectroscopic techniques. Elemental and atomic absorption analyses fit the compositions K2[Fe(metSO) 2]SO4 · H2O and [Cu(metSO)2] · H2O. Electronic absorption spectra of the complexes are typical of octahedral geometries. Infrared spectroscopy suggests coordination of the ligand to the metal through the carboxylate and sulfoxide groups. An EPR spectrum of the Cu(II) complex indicates tetragonal distortion of its octahedral symmetry. 57Fe Mössbauer parameters are also consistent with octahedral stereochemistry for the iron(II) complex. The complexes are very soluble in water.

Synthesis, characterization, and biological activity of a new palladium(II) complex with deoxyalliin

Synthesis, characterization, and biological activity of a new water-soluble Pd(II)-deoxyalliin (S-allyl-L-cysteine) complex are described in this article. Elemental and thermal analysis for the complex are consistent with the formula [Pd(C6H10NO2S)2]. 13C NMR, 1H NMR, and IR spectroscopy show coordination of the ligand to Pd(II) through S and N atoms in a square planar geometry. Final residue of the thermal treatment was identified as a mixture of PdO and metallic Pd. Antiproliferative assays using aqueous solutions of the complex against HeLa and TM5 tumor cells showed a pronounced activity of the complex even at low concentrations. After incubation for 24 h, the complex induced cytotoxic effect over HeLa cells when used at concentrations higher than 0.40 mmol/L. At lower concentrations, the complex was nontoxic, indicating its action is probably due to cell cycle arrest, rather than cell death. In agreement with these results, the flow cytometric analysis indicated that after incubation for 24 h at low concentrations of the complex cells are arrested in G0/G1. © 2005 NRC Canada.

No more!: the right of women to live a life free of violence in Latin America and the Caribbean

Includes bibliography

Modeling regional macroeconomic interactions: situation and perspectives for macroeconomic coordination in Latin America. Background paper prepared for the REDIMA workshop on Modeling Macroeconomic Coordination in the Andean Community, (Santiago, Chile 22 October 2003)""

Includes bibliography

The gender dimension of globalization: a survey of the literature with a focus on Latin America and the Caribbean

Includes bibliography

E-commerce environment and trade promotion for Latin America: policy implications from East Asian and advanced economies' experiences

Includes bibliography