New palladium(II) complexes with pyrazole ligands Part II. Synthesis, spectral and thermal studies, and antitumor evaluation

This study describes the synthesis, IR, (1)H, and (13)C{(1)H} NMR spectroscopic as well the thermal characterization of the new palladium(II) pyrazolyl complexes [PdCl(2)(HmPz)(2)] 1, [PdBr(2)(HmPz)(2)] 2, [PdI(2)(HmPz)(2)] 3, [Pd(SCN)(2)(HmPz)(2)] 4 {HmPz = 4-methylpyrazole}. The residues of the thermal decomposition were identified as Pd(0) by X-ray powder diffraction. From the initial decomposition temperatures, the thermal stability of the complexes can be ordered in the sequence: 1 > 2 > 4 a parts per thousand 3. The cytotoxic activities of the complexes and the ligand were investigated against two murine cancer cell lines: mammary adenocarcinoma (LM3) and lung adenocarcinoma (LP07) and compared to cisplatin under the same experimental conditions.

Immunomodulatory Effects of Palladium(II) Complexes of 1,2,4-Triazole on Murine Peritoneal Macrophages

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

3,5-Dimethyl-1-thiocarbamoylpyrazole and its Pd(II) complexes: Synthesis, spectral studies and antitumor activity

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

New palladium(II) complexes with pyrazole ligands Part I. Synthesis, spectral and thermal studies, and antitumor evaluation

The pyrazole ligand 3,5-dimethyl-4-iodopyrazole (HdmIPz) has been used to obtain a series of palladium(II) complexes (1-4) of the type [PdX(2)(HdmIPz)(2)] {X = Cl(-) (1); Br(-) (2); I(-) (3); SCN(-) (4)}. All compounds have been isolated, purified, and characterized by means of elemental analysis, IR spectroscopy, (1)H and (13)C{(1)H}-NMR experiments, differential thermal analysis (DTA), and thermogravimetry (TG). The TG/DTA curves showed that the compounds released ligands in the temperature range 137-605 A degrees C, yielding metallic palladium as final residue. The complexes and the ligand together with cisplatin have been tested in vitro by MTT assay for their cytotoxicity against two murine cancer cell lines: mammary adenocarcinoma (LM3) and lung adenocarcinoma (LP07).

Antimycobacterial and antitumor activities of Palladium(II) complexes containing isonicotinamide (isn): X-ray structure of trans-[Pd(N-3)(2)(isn)(2)]

Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES)

Synthesis of 4-aminoquinoline analogues and their platinum(II) complexes as new antileishmanial and antitubercular agents

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

Adsorption of Cu(II) and Co(II) complexes on a silica gel surface chemically modified with 2-mercaptoimidazole

The isotherms of adsorption of MeX2 (Me = Cu2+, Co2+; X = Cl-, Br-, ClO4-) by silica gel chemically modified with 2-mercaptoimidazole (SiMI) were studied in acetone and ethanol solutions, at 25 degrees C. Covalently attached 2-mercaptoimidazole molecule to silica gel surface adsorbs MeX2 from solvent by forming a surface complex. The metal is bonded to the surface through the nitrogen atom of attached 2-mercaptoimidazole. At low loading, the electronic and ESR spectral parameters indicated that the Cu2+ complexes are in a distorted-tetragonal symmetry field. The d-d electronic transition spectra showed that for Cu(ClO4)(2) complex, the peak of absorption did not change for any degree of metal loading and for Cl- and Br- complexes, the peak maxima shifted to higher energy with lower metal loading. The CoX2(X = Cl-, Br-, ClO4-) analogues possess a distorted-tetrahedral field.

Adsorption of copper(II) and cobalt(II) complexes on a silica gel surface chemically modified with 3-amino-1,2,4-triazole

The isotherms of adsorption of MX2 (M = Cu2+, Co2+; X = Cl-, Br-, ClO4) by silica gel chemically modified with 3-amino-1,2,4-triazole (SiATR) were studied in acetone and ethanol solutions, at 25 degrees C. The 3-amino-1,2,4-triazole molecule, covalently bound to the silica gel surface, adsorbs MX2 from solvent by forming a surface complex. At low loading, the electronic and electron spin resonance spectral parameters indicated that the Cu2+ complexes have distorted tetragonal symmetry. The CoX2 (X = Cl-, Br-) analogues exhibit a distorted-tetrahedral geometry, whilstthe (SiATR)mCo)ClO4)(2) complex has a tetragonally distorted octahedral geometry, with four equatorial nitrogen atoms around the cobalt. (C) 1998 Elsevier B.V. B.V. All rights reserved.

Preparação de membranas de acetato de celulose organomodificadas para adsorção dos íons Cu(II), Cd(II), Mn(II) e Ni(II)

Cellulose acetate polymeric membranes had been prepared by a procedure of two steps, combining the method of phase inversion and the technique of hydrolysis-deposition. The first step was the preparation of the membrane, and together was organomodified with tetraethylortosilicate and 3-aminopropyltrietoxysilane. Parameters that exert influence in the complexation of the metallic ion, as pH, time of complexation, metal concentration, had been studied in laboratory using tests of metal removal. The membranes had presented resistance mechanics and reactivity to cations, being able to be an alternative for the removal, daily pay-concentration or in the study of the lability of metals complexed.

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

Structure of copper(II) complexes adsorbed on functionalized polyhedral oligomeric silsesquioxane

The 3-amino-1,2,4-triazole-modified silsesquioxane nanoplatforms have been prepared and characterized. The silsesquioxane nanocages readily react with CuX(2) in aqueous solution to form copper complex-substituted silsesquioxanes. Adsorption isotherms of CuX(2) from aqueous solution were studied at 25 degrees C. The electronic and ESR spectral parameters indicated that the copper ion is in a distorted-tetragonal symmetry field. (C) 2007 Elsevier B.V. All rights reserved.

Synthesis, characterization, thermal studies, and DFT calculations on Pd(II) complexes containing N-methylbenzylamine

This work describes the synthesis, characterization, and the thermal behavior investigation of four palladium(II) complexes with general formulae [PdX(2)(mba)(2)], in which mba = N-methylbenzylamine and X = OAc(-) (1), Cl(-) (2), Br(-) (3) or I(-) (4). The complexes were characterized by elemental analysis, infrared vibrational spectroscopy, and (1)H nuclear magnetic resonance. The stoichiometry of the complexes was established by means of elemental analysis and thermogravimetry (TG). TG/DTA curves showed that the thermodecomposition of the four complexes occurred in 3-4 steps, leading to metallic palladium as final residue. The palladium content found in all curves was in agreement with the mass percentages calculated for the complexes. The following thermal stability sequence was found: 3 > 2 > 4 > 1. The geometry optimization of 1, 2, 3, and 4, calculated using the DFT/B3LYP method, yielded a slightly distorted square planar environment around the Pd(II) ion made by two anionic groups and two nitrogen atoms from the mba ligand (N1 and N2), in a trans-relationship.

Self-assembly of organometallic Pd(II) complexes via CH3 center dot center dot center dot pi interactions: the first example of a cyclopalladated compound with herringbone stacking pattern

Two binuclear cyclometallated compounds [Pd(C-2,N-dmba)(mu-N-3)](2) (1) and [Pd-2(C-2,N-dmba)(2)(mu-N-3)(mu-Cl)] (2) (dmba = N,N-dimethylbenzylarnine) have been synthesized and characterized by elemental 3 analysis, IR and NMR spectroscopies and single crystal X-ray diffraction crystallography. The ability of CH3 groups to form C(sp(3))-H...pi hydrogen bonds with phenyl rings is responsible for the molecular self-assembly within the crystals of 1 and 2. Compound 1 crystallizes as one-dimensional supramolecular chains whereas the crystal packing of 2 consists of a herringbone of sandwiches composed by two inversely related [Pd-2(C-2,N-dmba)(2)(mu-N-3)(mu-Cl)] molecules. (c) 2007 Elsevier B.V. All rights reserved.

3D hydrogen-bonded network built from copper(II) complexes of 1,3-propanediamine

The reaction of Cu(NO3)(2).3H(2)O with 1,3-propanediamine (pn), in the presence of NaN3, afforded a 1:1 co-crystal formed by [Cu(NO3)(2)(pn)(2)] and [Cu(N-3)(NO3)(pn)(2)] (1 and 2), which were characterized by elemental analysis, IR spectroscopy and single crystal X-ray diffraction. In both compounds, the copper(II) centers are in a distorted octahedral environment, formed by four N atoms of two bidentate pn ligands in the basal plane, whereas the axial bonds are formed by two O atoms from the nitrate ligands in 1 and one O atom from the nitrate ligand and one N atom from the azide ion in 2. The asymmetric unit of the crystal consists of two crystallographically independent 1 and 2 complexes, which are held together in a 3D network by a series of N - H center dot center dot center dot O and N - H center dot center dot center dot N hydrogen bonds, as well C - H center dot center dot center dot O interactions. New supramolecular synthons are identified by the occurrence of two geometrically distinct molecular recognition patterns involving the NO3- ion and amino groups from pn ligands.

Thermal behavior of the Ti(IV), Zr(IV) and Pb(II) complexes with 5-nitro-8-hydroxyquinoline

Ti(IV), Zr(IV) and Pb(II) complexes with 5-nitro-8-hydroxyquinoline (5-NQ) were obtained by precipitation in acetone/ammonium solution medium. The compounds TiO(C9H5N2O3)(2).0.5H(2)O, ZrO(C9H5N2O3)(2)2H(2)O and Pb(C9H5N2O3)(2) were characterized by Elemental Analysis, X-ray Diffratometry and Infrared Absorption Spectrometry and their thermal behavior followed by TG/DTA. This present study intends to show the variations in the thermal behavior of the compounds and in the composition and/or structure of final oxide residues, in different atmospheres and heating rates.