Unprecedented Pt(II) complex of an asymmetric 2,6-diacetylpyridine bis(4N-substituted thiosemicarbazone) ligand

NOTICE: this is the author’s version of a work that was accepted for publication in Inorganic Chemistry Communications. Changes resulting from the publishing process, such as peer review, editing, corrections, structural formatting, and other quality control mechanisms may not be reflected in this document. Changes may have been made to this work since it was submitted for publication. A definitive version was subsequently published in Inorganic Chemistry Communications 27 (2013): 5-8 DOI http://dx.doi.org/10.1016/j.inoche.2012.10.022Reaction of 2,6-diacetylpyridine bis(4N-o- tolylthiosemicarbazone), H2L1, with K2PtCl 4 and further recrystallization in DMSO/MeOH of the [PtL1] complex obtained, led to the isolation of the novel platinum complex, [PtL 2], which was structurally characterized by single crystal X-ray diffraction. The molecular structure shows that the ligand has undergone an unexpected chemical transformation viz. reduction of one of the terminal phenyl rings into cyclohexyl. The resulted asymmetrical ligand acts a dianionic tetradentate donor, coordinating to the platinum (II) center in a square planar geometry through the Npyridinic atom and the Niminic and the S atoms from one thiosemicarbazone arm, the fourth coordination position is occupied by the Nhydrazinic atom of the other armWe are grateful to Ministerio de Economía y Competitividad. Instituto de Salud Carlos III of Spain (PI080525 and PI1100659) for financial suppor

α-N-heterocyclic thiosemicarbazone derivatives as potential antitumor agents: A structure-activity relationships approach

α-N-Heterocyclic thiosemicarbazones, (N)-TSCs, are potent inhibitors of ribonucleotide reductase (RR). This enzyme plays a critical role in DNA synthesis and repair, and is a well-recognized target for cancer chemotherapeutic agents. In this review the structural features of (N)-TSCs, required for maximum antitumour activity have been explored. Special attention is given to the mechanisms of action and structure-activity relationshipsThe authors research work presented in this review was supported by Ministerio de Ciencia e Innovación, Instituto de Salud Carlos III (PI040354 and PI080525), Comunidad de Madrid (GR/SAL/0180/2004) and Universidad Autónoma de Madrid-Comunidad de Madrid (CCG08-UAM/SAL-4000) of Spai

New bioactive 2,6-diacetylpyridine bis(p-chlorophenylthiosemicarbazone) ligand and its Pd(II) and Pt(II) complexes: Synthesis, characterization, cytotoxic activity and DNA binding ability

NOTICE: this is the author’s version of a work that was accepted for publication in Journal of Inorganic Biochemistry. Changes resulting from the publishing process, such as peer review, editing, corrections, structural formatting, and other quality control mechanisms may not be reflected in this document. Changes may have been made to this work since it was submitted for publication. A definitive version was subsequently published in Journal of Inorganic Biochemistry 138 (2014): 16-23 DOI http://dx.doi.org/10.1016/j.jinorgbio.2014.04.017Preparation and characterization of 2,6-diacetylpyridine bis(4N-p-chlorophenylthiosemicarbazone) ligand, H2L, and its palladium(II) and platinum(II) complexes [PdL] and [PtL], is described. The molecular structure of the two new complexes has been determined by single crystal X-ray diffraction. The ligand acts as dianionic tetradentate donor coordinating to the metal center in a square planar geometry through the pyridine nitrogen atom and the azomethine nitrogen and thione sulfur atoms from one thiosemicarbazone arm, the fourth coordination position is occupied by the hydrazine nitrogen atom of the other arm. New free ligand and its metal complexes have been evaluated for antiproliferative activity in vitro against NCI-H460, T-47D, A2780 and A2780cisR human cancer cell lines. The cytotoxicity data suggest that these compounds may be endowed with important antitumor properties, especially H2L and [PtL] since they are capable of not only circumvent cisplatin resistance in A2780cisR cells but also exhibit high antiproliferative activity in breast cancer T-47D cells. The interaction of H2L with calf thymus DNA was also investigated and its binding constant (Kb) determinedWe are grateful to Ministerio de Economía y Competitividad, Instituto de Salud Carlos III of Spain (PI1100659) for financial suppor

Palladium(II) and platinum(II) bis(thiosemicarbazone) complexes of the 2,6-diacetylpyridine series with high cytotoxic activity in cisplatin resistant A2780cisR tumor cells and reduced toxicity

NOTICE: this is the author’s version of a work that was accepted for publication in Journal of Inorganic Biochemistry. Changes resulting from the publishing process, such as peer review, editing, corrections, structural formatting, and other quality control mechanisms may not be reflected in this document. Changes may have been made to this work since it was submitted for publication. A definitive version was subsequently published in JOURNAL OF INORGANIC BIOCHEMISTRY 125 (2013): 26-31 DOI http://dx.doi.org/10.1016/j.jinorgbio.2013.04.005Preparation and characterization of four novel 2,6-diacetylpyridine bis(4N-tolylthiosemicarbazonato) palladium(II) and platinum(II) complexes, [PdL1-2] and [PtL1-2], are described. All compounds have been characterized by elemental analysis and by IR and NMR spectroscopy, and the crystal and molecular structures of complexes [PdL 2] and [PtL2] have been determined by a single crystal X-ray diffraction. The ligands act as dianionic tetradentate donors coordinating to the metal center in a square planar geometry through the N pyridinic atom and the Niminic and the S atoms from one thiosemicarbazone arm, the fourth coordination position is occupied by the Nhydrazinic of the other arm. The new compounds synthesized have been evaluated for antiproliferative activity in vitro against NCI-H460, HepG2, MCF-7, A2780 and A2780cisR human cancer cell lines. The cytotoxicity data suggest that [PdL1], [PdL2] and [PtL2] may be endowed with important antitumor properties since they are capable of not only circumventing cisplatin resistance in A2780cisR cells but also exhibiting high antiproliferative activity in breast cancer MCF-7 cells. Subsequent toxicity study, in LLC-PK1 cells, has also been carried out and shows that none of these compounds are in vitro toxic in the tested concentration rangeWe are grateful to Ministerio de Economía y Competitividad, Instituto de Salud Carlos III of Spain (PI080525 and PI1100659) for financial suppor

New palladium and platinum complexes with bioactive 3,5-diacetyl-1,2,4- triazol bis(4-cyclohexyl thiosemicarbazone) ligand: Chemistry, antiproliferative activity and preliminary toxicity studies

Dalton Transactions 41.40 (2012): 12538-12547. Reproduced by permission of The Royal Society of ChemistryThe preparation and characterization of the new 3,5-diacetyl-1,2,4-triazol bis(4-cyclohexyl thiosemicarbazone) ligand, H5L1, is described. Treatment of H5L1 with K2PtCl 4 gave the dinuclear complex [Pt(H3L1)] 2, 1, but using MCl2(PPh3)2 where M = Pd or Pt, mononuclear complexes 2 and 3, of general formula [M(H 3L1)PPh3], were obtained. Subsequent reaction of the [Pd(H3L1)PPh3] complex with PdCl 2(PPh3)2 yielded a new dinuclear complex [(PPh3)Pd(H2L1)PdCl], 4. All compounds have been characterized by elemental analysis and FAB+ spectrometry and by IR and NMR spectroscopy. The molecular structures of mononuclear complexes 2 and 3 and dinuclear complex 4 have been determined by X-ray crystallography. The new compounds synthesized have been evaluated for antiproliferative activity in vitro against NCI-H460, HepG2, MCF-7, A2780 and A2780cisR human cancer cell lines. The cytotoxicity data suggest that the H5L1 ligand and [Pt(H3L1)]2, complex 1, may be endowed with important cytotoxic properties since they are capable of not only circumventing cisplatin resistance in A2780cisR but also exhibit antiproliferative activity in NCI-H460. The interactions of these compounds with calf thymus DNA were investigated by UV-vis absorption and a nephrotoxic study, in LLC-PK1 cells, has also been carried outWe are grateful to Ministerio de Economía y Competitividad, Instituto de Salud Carlos III (PI080525 and PI1100659), of Spain for financial suppor

Synthesis and structural characterization of a disulphide-bridged tetranuclear palladium(II) complex derived from 3,5-diacetyl 1,2,4-triazole bis(4-ethylthiosemicarbazone)

NOTICE: this is the author’s version of a work that was accepted for publication in Inorganic Chemistry Communications. Changes resulting from the publishing process, such as peer review, editing, corrections, structural formatting, and other quality control mechanisms may not be reflected in this document. Changes may have been made to this work since it was submitted for publication. A definitive version was subsequently published in Inorganic Chemistry Communications 10.1 (2007): 97-100 DOI http://dx.doi.org/10.1016/j.inoche.2006.09.016A novel tetranuclear [Pd4(μ2-η2-S2)(H2L1)2] complex, where H2L1 is the anion of 3,5-diacetyl-1,2,4-triazole bis(4-ethylthiosemicarbazone), was synthesized and structurally characterized by single crystal X-ray diffraction. The molecular structure shows an unexpected μ2-η2-S2 bridge, which is shared by all the four palladium atoms. Each trideprotonate 3,5-diacetyl-1,2,4-triazole bis(4-ethylthiosemicarbazone) ligand acts as a hexadentate in a symmetrical manner bridging two metal ions through the two adjacent nitrogen atoms of the central triazole ring. The molecular packing is characterized by hydrogen bond interactions to form a 3D supramolecular architecture with channels running down the c* axis in which the lattice water molecules are encapsulatedWe are grateful to Ministerio de Sanidad y Consumo, Instituto de Salud Carlos III (PI040354) and Comunidad Autónoma de Madrid (GR/SAL/0180/2004) of Spain for financial suppor

Novel bis(thiosemicarbazones) of the 3,5-diacetyl-1,2,4-triazol series and their platinum(ii) complexes: chemistry, antiproliferative activity and preliminary nephrotoxicity studies

Dalton Transactions 40.21 (2011): 5738-5745. Reproduced by permission of The Royal Society of ChemistryThe preparation and characterization of three novel 4N- monosubstituted bis(thiosemicarbazone) ligands of 3,5-diacetyl-1,2,4-triazol series and their dinuclear platinum complexes are described. The crystal and molecular structure of the [Pt(μ-H3L3)]2 complex derived of 3,5-diacetyl-1,2,4-triazol bis(4N-p- tolylthiosemicarbazone), H5L3, has been resolved by single crystal X-ray diffraction. The ligands coordinate, in an asymmetric dideprotonate form, to the platinum ions in a tridentate fashion (NNS) and S-bridging bonding modes. Thus the molecular units of the platinum complexes are stacked as dimers. The new compounds synthesized have been evaluated for antiproliferative activity in vitro against NCI-H460, A2780 and A2780cisR human cancer cell lines. The cytotoxicity data suggest that these compounds may be endowed with important antitumour properties since are capable of not only circumventing cisplatin resistance in A2780cisR cells but also exhibit high antiproliferative activity in human non-small cell lung cancer NCI-H460 cells. The interactions of these compounds with calf thymus DNA was investigated by UV-vis absorption and a nephrotoxic study, in LLC-PK1 cells, has also been carried outWe are grateful to Ministerio de Ciencia e Innovación, Instituto de Salud Carlos III (PI080525), Universidad Autónoma de Madrid and Comunidad de Madrid (CCG08-UAM/SAL-4000) of Spain for financial suppor

3,5-Diacetyl-1,2,4-triazol bis( 4N-substituted thiosemicarbazone) palladium(II) complexes: Synthesis, structure, antiproliferative activity and low toxicity on normal kidney cells

this is the author’s version of a work that was accepted for publication in Journal of Inorganic Biochemistry. Changes resulting from the publishing process, such as peer review, editing, corrections, structural formatting, and other quality control mechanisms may not be reflected in this document. Changes may have been made to this work since it was submitted for publication. A definitive version was subsequently published in Journal of Inorganic Biochemistry 105.12 (2011): 1613-1622 DOI http://dx.doi.org/10.1016/j.jinorgbio.2011.08.014Treatment of 4N-monosubstituted bis(thiosemicarbazone) ligands of 3,5-diacetyl-1,2,4-triazol series with lithium tetrachloridopalladate gave the dinuclear complexes of general formula [Pd(μ-H 3L 1-5)] 2, but using dichloridobistriphenylphosphinepalladium(II) salt, the first mononuclear bis(thiosemicarbazone)-palladium-triphenylphosphine complexes of the 3,5-diacetyl-1,2,4-triazol series, [Pd(H 3L 1-5)PPh 3], have been obtained. All the compounds have been characterized by elemental analysis and by IR and NMR spectroscopy, and the crystal and molecular structures of dinuclear complexes [Pd(μ-H 3L 3)] 2 and [Pd(μ-H 3L 5)] 2 as well as mononuclear complexes [Pd(H 3L 1)PPh 3], [Pd(H 3L 2)PPh 3], [Pd(H 3L 3)PPh 3] and [Pd(H 3L 4)PPh 3] have been determined by X-ray crystallography. The new compounds synthesized have been evaluated for antiproliferative activity in vitro against NCI-H460, A2780 and A2780cisR human cancer cell lines. Subsequent toxicity study, on normal renal LLC-PK1 cells, shows that all compounds investigated exhibit very low toxicity on kidney cells with respect to cisplatinWe are grateful to Ministerio de Ciencia e Innovación, Instituto de Salud Carlos III (PI080525), Universidad Autónoma de Madrid and Comunidad de Madrid (CCG08-UAM/SAL-4000) of Spain for financial suppor

Portrayal of caesarean section in Brazilian women’s magazines: 20 year review

Objective To assess the quality and comprehensiveness of the information on caesarean section provided in Brazilian women’s magazines

O brincar na educação infantil

Orientadora : Marcia B. SoczekMonografia (especialização) - Universidade Federal do Paraná, Setor de Educação, Curso de Especialização em Coordenação PedagógicaInclui referênciasResumo : Este artigo pretende abordar o brincar na Educação Infantil, tem como objetivo possibilitar reflexões sobre a função da brincadeira no processo educativo das crianças de zero a cinco anos. Partindo da metodologia da pesquisa bibliográfica serão abordados estudos sobre o brincar e o processo educativo na Educação Infantil, a brincadeira como uma influência decisiva do ensino aprendizagem da criança enquanto o ser único, através da integração de seu aspecto físico, emocional, afetivo e social. Também são apresentados estudos sobre as diferentes formas de brincar e como elas estão presentes na educação infantil. A justificativa para a realização desta pesquisa se dá pela necessidade de compreender a importância do brincar no desenvolvimento infantil e no trabalho pedagógico a ser realizado com as crianças de zero a cinco anos. Após estudos realizados foi possível chegar as seguintes conclusões que na Educação Infantil o brincar precisa ser visto como elemento fundamental na Proposta Pedagógica das Instituições, pois desenvolve as capacidades motoras, cognitivas, sociais e culturais das crianças