Hydroxyquinoline derived vanadium(IV and V) and copper(II) complexes as potential anti-tuberculosis and anti-tumor agents

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

Complexes of platinum and palladium with beta-diketones and DMSO: Synthesis, characterization, molecular modeling, and biological studies

Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq)

Cytoxicity and Apoptotic Mechanism of Ruthenium(II) Amino Acid Complexes in Sarcoma-180 Tumor Cells

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

Synthesis, structural characterization, luminescent properties and theoretical study of three novel lanthanide metal-organic frameworks of Ho(III), Gd(III) and Eu(III) with 2,5-thiophenedicarboxylate anion

Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq)

Antitubercular activity of Ru (II) isoniazid complexes

Despite the resistance developed by the Mycobacterium tuberculosis (MTb) strains, isoniazid (INK) has been recognized as one of the best drug for treatment of Tuberculosis (Tb). The coordination of INH to ruthenium metal centers was investigated as a strategy to enhance the activity of this drug against the sensitive and resistant strains of MTb. The complexes trans-[Ru(NH3)(4)(L)(INH)](2+) (L = SO2 or NH3) were isolated and their chemical and antituberculosis properties studied. The minimal inhibitory concentration (MIC) data show that [Ru(NH3)(5)(INH)](2+) was active in both resistant and sensitive strains, whereas free INK (non-coordinated) showed to be active only against the sensitive strain. The coordination of INH to the metal center in both [Ru(NH3)(5)(INH)](2+) and trans-[Ru(NH3)(4)(SO2)(INH)](2+) complexes led to a shift in the INH oxidation potential to less positive values compared to free INH. Despite, the ease of oxidation of INH did not lead to an increase in the in vitro INH activity against MTb, it might have provided sensitivity toward resistant strains. Furthermore, ruthenium complexes with chemical structures analogous to those described above were synthesized using the oxidation products of INK as ligands (namely, isonicotinic acid and isonicotinamide). These last compounds were not active against any strains of MTb. Moreover, according to DFT calculations the formation of the acyl radical, a proposed intermediate in the INH oxidation, is favored in the [Ru(NH3)(5)(INH)](2+) complex by 50.7 kcal mol(-1) with respect to the free INH. This result suggests that the stabilization of the acyl radical promoted by the metal center would be a more important feature than the oxidation potential of the INH for the antituberculosis activity against resistant strains. (C) 2015 Elsevier B.V. All rights reserved.

Recent advances in nanoparticle carriers for coordination complexes

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

Correlation between i.r. spectra and thermal decomposition of cobalt(II), nickel(II), copper(II) and mercury(II) complexes with piperidinedithiocarbamate and pyrrolidinedithiocarbamate

The thermal decomposition of pyrrolidinedithiocarbamate and piperidinedithiocarbamate complexes of CoII, NiII, CuII and HgII have been studied by thermogravimetry and differential scanning calorimetry. The decomposition intermediates and final products were identified by their X-ray diffraction patterns. The i.r. spectra are discussed in terms of the thermal decomposition pathways.

Time differential perturbed angular correlation (TDPAC) study of some hafnium glycolate complexes

Time differential measurements of the 133-482 keV γ-γ angular correlation of 181Ta have been performed in solid hafnium complexes of the type [Hf(glycol)4] (glycol = p-chloromandelate, p-bromomandelate, b-naphthylglycolate and mandelate). The quadrupolar frequencies (ωQ) were found to increase within the series. This behaviour was explained by supposing a dissipation of electronic density at the metal level, caused by an increase in intermolecular hydrogen bonding in the complexes throughout the series studied. These results seem to agree with complementary data from IR spectroscopic studies. © 1988.

Structure of copper complexes adsorbed on a silica gel surface chemically modified with benzimidazole

Silica gel having a particle size between 0.2 and 0.05 mm and a specific surface area, S BET = 473 m 2 g -1, was chemically modified with benzimidazole. Adsorption isotherms of CuX 2 (X = Cl, Br or ClO 4) from ethanol and acetone solutions were studied at 298 K. The metal is bonded to the surface through the free nitrogen atom of the attached benzimidazole. The average number of ligands co-ordinated to the central metal ion was shown to depend on the solid surface loading by the solute. At low loading the electronic and ESR spectral parameters indicated that the copper ion is in a distorted-tetragonal symmetry field.

Metalosupramoléculas discretas e Metal Organic Frameworks (MOFs) baseados em íons lantanídeos: design, síntese, caracterização e propriedades

Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq)

Novel europium and gadolinium complexes with methaneseleninate as ligand: Synthesis, characterization and spectroscopic study

The methaneseleninate and 1,10-phenanthroline were used as ligands in the synthesis of new lanthanide complexes. The photostability, emission quantum yield (q) and quantum efficiency (eta) of the D-5(0) emitting level of the Eu3+ ion were determined. An energy level diagram was used to establish the most relevant channels involved in the ligand-to-metal intramolecular energy transfer process. The nephelauxetic effect was investigated to assess the covalency of the ligand-metal chemical bond. The values of the experimental 4f-4f intensity parameters, suggest that this ion is in a chemical environment less polarisable than in the case of complexes with beta-diketonates as ligands. (C) 2011 Elsevier B.V. All rights reserved.

Metal binding selectivity of oxa-aza macrocyclic ligand: a DFT study of first- and second-row transition metal for four coordination systems

A detailed theoretical study of the 1,7,1l,17-tetraoxa-2,6,12,16-tetraaza-cycloeicosane ligand ([20]AneN(4)O(4)) coordinated to Fe2+, Co2+, Ni2+, Ru2+, Rh2+, and Pd2+ transition metal ions was carried out with the B3LYP method. Two different cases were performed: when nitrogen is the donor atom (1a (q) ) and also with the oxygen as the donor atom (1b (q) ). For all the cases performed in this study 1a (q) structures were always more stable than the 1b (q) ones. Considering each row is possible to see that the energy increases with the increase of the atomic number. The M2+ cation binding energies for the 1a (q) complexes increase with the following order: Fe2+ < Ru2+ < Co2+ < Ni2+ < Rh2+ < Pd2+.

A broad study of two new promising antimycobacterial drugs: Ag(I) and Au(I) complexes with 2-(2-thienyl)benzothiazole

Synthesis, characterization, DFT simulation and biological assays of two new metal complexes of 2-(2-thienyl)benzothiazole - BTT are reported. The complexes [Ag(BTT)(2)NO3] - AgBTT2 and [Au(BTT)Cl]center dot 1/2H(2)O - AuBTT were obtained by mixing the ligand with silver (I) nitrate or gold(I) chloride in methanolic solution. Characterization of the complexes were based on elemental (C, H, N and S), thermal (TG-DTA) analysis, C-13 and H-1 NMR, FT-IR and UV-Vis spectroscopic measurements, as well as the X-ray structure determination for AgBTT2. Spectroscopic data predicted by DFT calculations were in agreement with the experimental data for both complexes. The ligand BTT was synthesized by the condensation of 2-thiophenecarboxaldehyde and 2-aminothiophenol in a microwave furnace. AgBTT2 has a monomeric structure. Both complexes show a good activity against Mycobacterium tuberculosis. Free BIT shows low antitubercular activity. (C) 2012 Elsevier Ltd. All rights reserved.

Observation of vinylidene emission in mixed phosphine/diimine complexes of Ru(II) at room temperature in solution

The mixed ruthenium(II) complexes trans-[RuCl(2)(PPh(3))(2)(bipy)] (1), trans-[RuCl(2)(PPh(3))(2)(Me(2)bipy)](2), cis-[RuCl(2)(dcype)(bipy)](3), cis-[RuCl(2)(dcype)(Me(2)bipy)](4) (PPh(3) = triphenylphosphine, dcype = 1,2-bis(dicyclohexylphosphino)ethane, bipy = 2,2'-bipyridine, Me(2)bipy = 4,4'-dimethyl-2,2'-bipyridine) were used as precursors to synthesize the associated vinylidene complexes. The complexes [RuCl(=C=CHPh)(PPh(3))(2)(bipy)]PF(6) (5), [RuCl(=C=CHPh)(PPh(3))(2)(Me(2)bipy)]PF(6) (6), [RuCl(=C=CHPh)(dcype)(bipy)]PF(6) (7), [RuCl(=C=CHPh)(dcype)(bipy)]PF(6) (8) were characterized and their spectral, electrochemical, photochemical and photophysical properties were examined. The emission assigned to the pi-pi* excited state from the vinylidene ligand is irradiation wavelength (340, 400, 430 nm) and solvent (CH(2)Cl(2), CH(3)CN, EtOH/MeOH) dependent. The cyclic voltammograms of (6) and (7) show a reversible metal oxidation peak and two successive ligand reductions in the +1.5-(-0.64) V range. The reduction of the vinylidene leads to the formation of the acetylide complex, but due the hydrogen abstraction the process is irreversible. The studies described here suggest that for practical applications such as functional materials, nonlinear optics, building blocks and supramolecular photochemistry. (C) 2011 Elsevier B.V. All rights reserved.

Preparation, characterization and structure of ruthenium phosphine complexes containing non-innocent ligands

Phosphine ruthenate complexes containing the non-innocent ligands 4-chloro-1,2-phenylenediamine (opda-CI) and 3,3',4,4'-tetraamminebiphenyl (diopda) were synthesized and characterized by means of X-ray diffraction, electrochemistry, P-31{H-1} NMR and electronic spectroscopies. Crystals of cis-[RuCl2 (dppb)(bqdi-CI)] complex were isolated as a mixture of two conformational isomers due to different positions of the chlorine atoms of the o-phenylene ligand in relation to the P1 atom of the phosphine moiety. (C) 2011 Elsevier Ltd. All rights reserved.