SYNTHESIS, CHARACTERIZATION AND THERMAL ANALYSIS OF 1:1 AND 2:3 LANTHANIDE(III) CITRATES

The synthesis and characterization of lanthanide(III) citrates with stoichiometries 1:1 and 2:3; [LnL center dot xH(2)O] and [Ln(2)(LH)(3)center dot 2H(2)O], Ln=La, Ce, Pr, Nd, Sm and Eu are reported. L stands for (C6O7H5)(3-) and LH for (C6O7H6)(2-). Infrared absorption spectra of both series evidence coordination of carboxylate groups through symmetric bridges or chelation. X-ray powder patterns show the amorphous character of [LnL center dot xH(2)O]. The compounds [Ln(2)LH(3)center dot 2H(2)O] are crystalline and isomorphous. Emission spectra of Eu compounds suggest C-2v symmetry for the coordination polyhedron of [LnL center dot xH(2)O] and C-4v for [Ln(2)(LH)(3)center dot 2H(2)O]. Thermal analyses (TG-DTG-DTA) were carried out for both series. The thermal analysis patterns of the two series are quite different and both fit in a 4-step model of thermal decomposition, with lanthanide oxides as final products.

Luminescent nanoparticles of MgAl(2)O(4):Eu, Dy prepared by citrate sol-gel method

MgAl(2)O(4):Eu, Dy nanoparticles were prepared by citrate sol-gel method and thermally treated at 600, 700, 800 and 900 degrees C. The trivalent europium ion is partially reduced to the divalent state at 700 and 800 degrees C. Infrared spectra of the phosphors showed bands around 700 and 520 cm(-1) corresponding to the AlO(6) groups. X-ray diffraction patterns present sharp reflections of samples heated from 700 to 900 degrees C indicating the MgAl(2)O(4) spinel phase. Grain size in the range 20-30 nm were observed by measurement of transmission electron microscopy (TEM). The emission spectra of the phosphors show a broadened band at 480 nm assigned to the 4f(G)5d -> 4f(7) ((8)S(7/2)) transition of Eu(2+) ion overlapped to the (4)F(9/2) -> (6)H(15/2) transition of the Dy(3+) ion. Besides, the (4)F(9/2) -> (6)H(13/2) transition (579 nm) of Dy(3+) ion is overlapped with the (5)D(0) -> (7)F(0) (578 nm) and (5)D(0) -> (7)F(1) (595 nm) transitions from the Eu(3+) ion. Excitation spectra of the sample heated at 900 degrees C monitoring the excitation at 615 nm of (5)D(0) -> (7)F(2) transition of Eu(3+) ion exhibit a broad band assigned to the O -> Eu(3+) ligand-to-metal charge-transfer states (LMCT) around 280 nm. The samples present green persistent luminescence after exposure to UV radiation. The chromaticity coordinates were obtained from the luminescence emission spectrum. (C) 2008 Elsevier B.V. All rights reserved.

Double-strand DNA cleavage induced by oxindole-Schiff base copper(II) complexes with potential antitumor activity

Some oxindole-Schiff base copper(II) complexes have already shown potential antitumor activity towards different cells, inducing apoptosis in a process modulated by the ligand, and having nuclei and mitochondria as main targets. Here, three novel copper(II) complexes with analogous ligands were isolated and characterized by spectroscopic techniques, having their reactivity compared to the so far most active complex in this class. Cytotoxicity experiments carried out toward human neuroblastoma SH-SY5Y cells confirmed its proapoptosis property. DNA cleavage studies were then performed in the presence of these complexes, in order to verify the influence of ligand structural features in its nuclease activity. All of them were able to cause double-strand DNA scissions, giving rise to nicked circular Form II and linear Form III species, in the presence of hydrogen peroxide. Additionally, DNA Form II was also detected in the absence of peroxide when the most active complex, [Cu(isaepy)(2)](2+) 1, was used. In an effort to better elucidate their interactions with DNA, solutions of the different complexes titrated with DNA had their absorption spectra monitored. An absorbance hyperchromism observed at 260 nm pointed to the intercalation of these complexes into the DNA structure. Further, investigations of 2-deoxy-D-ribose (DR) oxidation catalyzed by each of those complexes, using 2-thiobarbituric acid reactive species (TBARS) method, and detection of reactive oxygen species (ROS) formation by spin-trapping EPR, suggested that their mechanism of action in performing efficiently DNA cleavage occurs preferentially, but not only by oxidative pathways. (C) 2007 Elsevier Inc. All rights reserved.

Luminescence enhancement of the Tb(III) ion with the thenoyltrifluoroacetonate ligand acting as an efficient sensitizer

The synthesis, structural investigation, and photophysical properties of the complex [Tb(TTA)(2)(NO(3)) (TPPO)(2)] are reported. Unlike the analog tris-diketonate complex [Tb(TTA)(3)(TPPO)(2)], the new complex presents abnormally high luminescence intensity centered on the terbium ion. Our results clearly suggest a higher energy transfer efficiency from the TEA antenna ligand to the Tb(III) ion in the bis-diketonate complex compared with that in the tris-diketonate complex. A mechanism involving the increasing of triplet state energy when one TTA ligand is replaced by the NO(3)(-) group in the first coordination sphere is suggested and experimentally investigated to explain the anomalous luminescence properties of the new complex [Tb(TTA)(2)(NO(3))(TPPO)(2)]. (C) 2010 Elsevier B.V. All rights reserved.

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.

Functionalization of PAMAM dendrimers with [Ru-III(edta)(H2O)](-)

The anchoring of K[Ru-III(edta)(Cl)] on poly(amidoamine) dendrimers (PAMAM of three generations G(x)/Ru (x = 0, 2 and 3)) through a peptide type bond yielded the aquo species, [Ru-III(edta)(H2O)] on dendrimer surface, and upon NO exposure, yielded their nitrosyl analogues, Gx/RuNO. Characterization of these compounds by elemental analysis, and a UV-vis, IR and C-13 NMR spectroscopies indicated the immobilization of 4,12 and 29 molecules of [Ru-III(edta)(H2O)](-) or of the nitrosyl complex [Ru(II)edta)NO] on the dendrimer surface for G(X) = 0, 2 and 3, respectively. For each complex the electrochemical spectrum presented only one redox process with redox potential values of -0.20 and -0.32 V(vs SCE) attributed to the Ru/Run and NO+/NO0 couples in G(x)/Ru and G./RuNO, respectively. The one-electron reduction of Gx/RuNO` generates Gx/RuNOo, which undergoes aquation with a k(-NO) of 2.1 +/- 0.7 x 10(-3) s(-1) (pH 1.0, mu = 0.2 mol/L, CF3COOH/NaCF3COO, 25 degrees C). The Gx/RuNO species induced a relaxing effect in aortic rings denuded of endothelium and exhibited in vitro assay trypanocidal activity. (c) 2008 Elsevier Inc. All rights reserved.

An insight into the beginning stage of the aqueous ring opening metathesis polymerization of exo,exo-7-oxabicyclo[2.2.1]hept-5-ene-2,3-dicarboxylic acid with Ru(III) compounds: the consumption of Ru(III) species in the presence of carboxylic acids monitored by ESR spectroscopy

The presence of paramagnetic species in the aqueous ring opening metathesis polymerizations of the exo,exo-7-oxabicyclo[2.2.1]hept-5-ene-2,3-dicarboxylic acid monomer with RuCl(3) and K(2)[RuCl(5)H(2)O] compounds was studied using ESR techniques. It was observed that the intensities of the Ru(III) signals in the ESR spectra decrease on the time scale of the induction period so that the ROMP can take place. The intensity of the Ru(III) signal almost disappeared 50 min after reacting with K(2)[RuCl(5)H(2)O] and after 100 mm in the case of RuCl(3). Reactions of the cis-[Ru(NH(3))(4)(H(2)O)(2)](tfms)(3) and [Ru(NH(3))(5)H(2)O](tfms)(3) complexes with the monomer and different organic compounds representing the organic functions in the monomer (furan, norbornene, but-2-ene-1,4-diol and formic, acetic, oxalic and maleic acids) were also monitored by ESR and UV/vis spectra. It was deduced that the organic acids provide the disappearance of the Ru(III) signal. The proton NMR relaxation times of the residual water in D(2)O for reactions with oxalic acid suggested that the presence of paramagnetic ions in the solution decreases along with

Mixed-Ligand Complexes of Technetium and Rhenium with Tridentate Benzamidines and Bidentate Benzoylthioureas

Mixed-ligand complexes of technetium(V) or rhenium(V) containing tridentate N-[(dialkylamino)(thiocarbonyl)]benzamidine (H(2)L(1)) and bidentate N,N-dialkyl-N`-benzoylthiourea (HL(2)) ligands were formed in high yields when (NBu(4))[MOCl(4)] (M = Tc or Re) or [ReOCl(3)(PPh(3))(2)] was treated with mixtures of the proligands. Other approaches for the synthesis of the products are reactions of [MOCl(L(1))] complexes with HL(2) or compounds of the-composition [ReOCl(2)(PPh(3))(L(2))] with H(2)L(1). The resulting air-stable [MO(L(1))(L(2))] complexes possess potential for the development of metal-based radiopharmaceuticals. [TcO(L(1))(L(2))] complexes are readily reduced by PPh3 with formation of [Tc(L(1))(L(2))(PPh(3))]. The resulting Tc(III) complexes undergo two almost-reversible oxidation steps corresponding to one-electron transfer processes. ((C) Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2009)

Synthesis and structural characterization of Eu(III)-doped Zn7Sb2O12

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

6-Mercaptopurine complexes with silver and gold ions: Anti-tuberculosis and anti-cancer activities

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

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.

Síntese, caracterização e estudo fotofísico de complexos de 4,4- diaminoestilbeno-2,2-dissulfonato com íons lantanídeos

This is a work involving fundamental studies of chemistry where the synthesis and structural characterization, as well as a possible future application of these new compounds as luminescent sensors or sunscreen agents, complexes with 4,4 diaminostilbene-2,2-disulfonic (DSD) and trivalent lanthanide ions La3+, Nd3+, Eu3+, Gd3+ and Yb3+, were synthesized in the ratio of 3 mmol: 1 mmol (DSD: lanthanides). The complexes obtained with these ions were present in powder form and were characterized by complexometric titration with EDTA CHN Elemental analysis, molecular absorption spectroscopy in the ultraviolet region, the absorption spectroscopy in the infrared, thermal analysis (TG / DTG), Nuclear Magnetic Resonance - NMR 1H and Luminescence Spectroscopy. The complexometric titration and CHN analysis, confirmed the TG / DTG which suggest that these complexes have the following general chemical formulas: [La2(C14H12S2O6N2)2(H2O)2Cl2].7H2O,[Nd2(C14H12S2O6N2)2(H2O)2Cl2].6H2O,[Eu2(C14 H12S2O6N2)2(H2O)2Cl2].7H2O,[Gd2(C14H12S2O6N2)2(H2O)2Cl2].4H2O e [Yb2(C14H12S2O6N2)2(H2O)2].6H2O. The disappearance of the bands in the infrared spectrum at 2921 cm-1 and 2623 cm-1 and the displacement of the bands in the spectra of the amine complex indicate that the lanthanide ion is coordinated to the oxygen atoms and the sulfonate groups of the nitrogens amines, suggesting the formation of the dimer. The disappearance of the signal and the displacement signal SO3H amines in the 1H NMR spectrum of this complex are also indicative coordination and dimer formation. The Thermogravimetry indicates that the DSD is thermally stable in the range of 40º to 385°C and their complexes with lanthanide ions exhibit weight loss between 4 and 5 stages. The Uv-visible spectra indicated that the DSD and complexes exhibit cis isomers. The analysis of luminescence indicates that the complexes do not exhibit emission in the region of the lanthanides but an intense emission part of the binder. This is related to the triplet states of the ligand, which are in the lowest energy state emitting lanthanide ions, and also the formation of the dimer that suppress the luminescence of ion Eu3+. The formation of dimer was also confirmed by calculating the europium complex structure using the model Hamiltonian PM6 and Sparkle

APTES-Modified RE2O3:Eu3+ Luminescent Beads: Structure and Properties

Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES)

New phosphinate ligand synthesis and its effect on optical properties of the europium beta-diketonate complex

The synthesis and characterization of a new organic ligand monooctyldiphenylphosphinate (L) is described, as well as a new Eu(3+) diketonate complex [Eu(tta)(3)(L)(2)] (tta = thenoyltrifluoracetone). The ligand (L) was formed by substitution reaction (80% yield) and characterized by uni- and bidimensional (1)H, (13)C and (31)P NMR experiments, to confirm its molecular structure. The coordination of (L) to Eu(3+) in the complex [Eu(tta)(3)(L)(2)] was confirmed by FT-IR spectra. The emission spectra present the same profile when excited in Eu(3+) or in the ligands, suggesting an energy transfer from ligands to Eu(3+) ions. The emission spectra of the precursor [Eu(tta)(3)(H(2)O)(2)], and [Eu(tta)(3)(L(2))] present bands arising from f-f intra-configurational transitions. The only (5)D(0)-(7)F(0) transition shows the presence of at least one site without symmetry center. The FWHM of such transition is 7 cm(-1) and 57 cm(-1) for [Eu(tta)(3)(H(2)O)(2)] and [Eu(tta)(3)(L)(2)] complexes, respectively. This widening is provided by the presence of large groups around Eu(3+) ion. The calculated intensity parameters Omega(2) and Omega(4) show that the interaction features between center-ion and ligand are different; the small value of Omega(4) is related to long range effects of alkyl chain. The Langmuir isotherms of this ligand and complex have been investigated although their hydrolysis in water subphase does not allow stable monolayers. (C) 2009 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim

Visible and near-infrared luminescent Eu3+ or Er3+ doped laponite-derived xerogels and thick films: Structural and spectroscopic properties

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