Made available in DSpace on 2014-06-11T19:26:42Z (GMT). No. of bitstreams: 0 Previous issue date: 2007-06-05Bitstream added on 2014-06-13T19:13:53Z : No. of bitstreams: 1 rocha_mc_me_arafcf.pdf: 757379 bytes, checksum: f386cabb4d38b8f9552bfba42f8b50aa (MD5) / Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq) / Universidade Estadual Paulista (UNESP) / O câncer destaca-se pela alta incidência e mortalidade. O tratamento do câncer compreende cada vez mais a quimioterapia combinada, ou seja, substâncias antitumorais agindo conjuntamente com as células do sistema imune, potencializando-as ou apenas mantendo-as viáveis para exercerem sua função. Dentre os tipos celulares que constituem o sistema imunológico, os macrófagos são apontados como os principais elementos do organismo de combate aos tumores. Os macrófagos ativados agem liberando produtos tais como radicais de oxigênio (H2O2) e nitrogênio (NO), interleucina-1ß (IL-1ß) e fator de necrose tumoral (TNF-a), que são prejudiciais às células tumorais dependendo da concentração, além de sua ação indireta através da secreção de interferon-gama (IFN-.). Complexos de paládio(II) são investigados há décadas, destacando-se por sua potencialidade como agente antitumoral. Neste trabalho avaliou-se a ação dos compostos [Pd(dmba)(X)(dppp)] (X= SCN, NCO, N3 ou Cl) sobre as células tumorais de Ehrlich e macrófagos in vitro, utilizando como padrão a cis-platina (cis-Pt). Para tanto, foram realizados ensaios para determinação do índice de citotoxicidade mediano, o IC50, para cada composto pelos períodos de 24 e 48h e com base em tais concentrações investigadas para os macrófagos verificou-se a produção e/ou inibição de NO e H2O2, além das citocinas TNF-a, IFN-. e IL-1 bem como a atividade citotóxica/citolítica. Os compostos demonstraram ser agentes promissores por seus efeitos sobre as células tumorais e imunes, muitas vezes de forma igual ou superior à cis-Pt, droga de uso corrente na quimioterapia do câncer. / The cancer is a disease with high incidence and mortality. The cancer treatment involves the combinated chemotherapy wich one involves antitumour substances acting along with the immune cells, stimulating or only keeping them able to act in the immune response. Between the cell types that belong to the immunological system, the macrophages are considered the main elements of the body that can act against tumours. The activated macrophages act releasing substances like oxygen (H2O2) and nitrogen (NO) radicals, interleukin-1 (IL-1) and tumour necrosis factor alpha (TNF-á), wich are not beneficial to the tumour cells in some concentrations, besides its indirect action towards interferon-gama (IFN-ã) release. Palladium(II) complexes are employed in many studies to verify its antitumour properties. For example we can describe the four following compounds: [Pd(dmba)(X)(dppp)], X= SCN, NCO, N3 or Cl. This work had as goal the evaluation of the action of such compounds towards Ehrlich tumour cells, macrophages and lymphocytes in vitro, employing cis-platin (cis-Pt) as standard. The following parameters were evaluated: the cytotoxic index (IC50) of each compound after 24 and 48h incubation for Ehrlich tumour cells, macrophages and lymphocytes; the immunological behaviour of the compounds in the concentrations previously determined such as NO and H2O2 production or inhibition, besides the cytokines TNF-á, IFN-ã and IL-1 as well as the cytotoxic/cytolitic activity. The compounds presented a good behaviour, based on their efects towads tumour and immune cells, many times like or even better than cis-Pt, standard drug in cancer chemotherapy.

En esta tesis se han sintetizado pirazoles 1,3,5-sustituidos con grupos fenilo, piridilo y metilo en las posiciones 3,5 y grupos alquilalcohol y alquilpoliéter en la posición N1 (CH2CH2OH, (CH2CH2O)nCH3; n=3,4).Se ha estudiado la complejación de algunos de los ligandos 1,3,5-sustituidos, previamente sintetizados, con MCl2(CH3CN)2, (M= Pd(II), Pt(II)) y Pd(CH3COO)23. Se ha estudiado la reactividad de algunos de los complejos de Pd(II) y Pt(II) sintetizados, con distintas sales de Ag(I), a fin de obtener diferentes entornos para estos metales. El conjunto de ligandos y complejos sintetizados se han caracterizado por análisis elemental, conductividad, espectroscopia de IR y RMN de 1H, 13C1H, MC, COSY, NOESY, espectrometría de masas, espectroscopia UV-Vis y difracción de Rayos X en monocristal siempre que sea posible.Aplicaciones:Se han realizado estudios con algunos de los ligandos pirazólicos 1,3,5-sustituidos con el fin de evaluarlos como ionóforos, formando parte de Electrodos Selectivos a Iones (Pb2+, Cd2+, Cu2+).Además, se han estudiado algunos complejos de Pd(II) y Pt(II) como nuevos anticancerígenos, a fin de evaluar la influencia del metal así como de los diferentes entornos del metal. / In this thesis, several ligands have been synthesized, including pyrazole derived ligands with phenyl, pyridyl, and methyl moieties in 3 and 5 positions of the pyrazole ring and alkyl-alcohol and alkyl-polyether moieties in position N1 (CH2CH2OH, (CH2CH2O)nCH3; n = 3, 4).Complexation of some of these ligands has been studied towards Pd(II) and Pt(II). Initial complexes used were MCl2(CH3CN)2, (M = Pd(II), Pt(II)) and Pd(CH3COO)23.Reactivity on some of these Pd(II) and Pt(II) complexes has been performed, forcing the precipitation of the chloride ligands with several Ag(I) complexes.All the ligands and complexes obtained in this thesis were characterized by elemental analyses, conductivity measurements, spectroscopy of UV-vis, IR and NMR (1H, 13C, HMQC, COSY, NOESY...), mass spectrometry, and X-ray crystal diffraction (when possible).Some of the ligands have been used as ionopheres in Ion Selective Electrodes (Pb2+, Cd2+, and Cu2+).Furthermore, some of the Pd(II) and Pt(II) complexes were studied as potential anti-carcinogenic, with special attention to the influence of the metal complex.

Made available in DSpace on 2014-06-11T19:29:09Z (GMT). No. of bitstreams: 0 Previous issue date: 2008-08-15Bitstream added on 2014-06-13T19:38:13Z : No. of bitstreams: 1 souza_ra_me_araiq.pdf: 2538432 bytes, checksum: 3b82e3741e1179ffc530cdc631ba9c10 (MD5) / Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES) / O presente trabalho trata da síntese, caracterização estrutural e aplicações biológicas de quatro complexos de paládio(II), de fórmula trans-[PdX2(isn)2], X = Cl (1), N3 (2), SCN (3) e NCO (4), isn= isonicotinamida. Os compostos foram preparados em mistura de CHCl3/ CH3OH (1:1), partindo-se do precursor [PdCl2(CH3CN)2] que reagiu com a isn e sais de pseudohaletos: NaN3, KNCO e NaSCN. A caracterização destes complexos, no estado sólido, se deu pelas técnicas de análise elementar, espectroscopia de absorção no infravermelho, análise térmica e difração de raios X de monocristal do composto 2, possibilitando sugerir estruturas monoméricas, com a isn coordenada ao Pd pelo nitrogênio piridínico. Cloro e os pseudohaletos acham-se coordenados de modo terminal, via nitrogênio em 2 e em 4 e pelo átomo de enxofre em 3. As curvas TG substanciaram as propostas estequiométricas e permitiram estabelecer, com base na temperatura inicial de decomposição, a seguinte ordem de estabilidade térmica para esta série: trans-[PdCl2(isn)2] > trans-[Pd(SCN)2(isn)2] > trans- [Pd(NCO)2(isn)2] > trans-[Pd(N3)2(isn)2]. A estrutura do complexo 2 foi resolvida por difração de raios X de monocristal, e apresenta uma geometria quadrado-planar ao redor do Pd e estereoquímica trans. Nota-se ainda, que a estrutura se estende por ligações intermoleculares de hidrogênios, formando arranjos supramoleculares bidimensionais via N– H...O e arranjos tridimensionais, decorrentes de interações C–H...Nazida. Os dados de RMN em solução confirmam a formação dos complexos, constatando-se, além disso, a presença de outras espécies químicas em solução. A ação antiproliferativa dos compostos contra células tumorais de mama, LM3, e pulmão, LP07, foi investigada. A atividade da isn foi desprezível e os valores de IC50 dos complexos foram maiores que os apresentados pela cisplatina... / The present work deals with the synthesis, structural characterization and biological applications of four palladium(II) complexes, of formula trans-[PdX2(isn)2], X = Cl (1), N3 (2), SCN (3), and NCO (4), isn = isonicotinamide. The compounds were prepared in mixture of CHCl3/ CH3OH (1:1), from precursor [PdCl2(CH3CN)2] that reacted with isn and pseudohalide salts: NaN3, KNCO e NaSCN. The characterization of these complexes, in solid state, occurred by techniques of elemental analysis, infrared spectroscopy absorption, thermal analysis, and X-rays diffraction of single crystal of the compound 2, making possible to suggest monomeric structures containing the isn coordinated to Pd by pyridinic nitrogen. Chlorine and pseudohalides are coordinated of terminal way, by nitrogen in 2 and 4, and by sulphur atom in 3. The TG curves substantiated the stoichiometric proposals and made possible to establish, based on initial temperature of decomposition, the following order of thermal stability to this series: trans-[PdCl2(isn)2] > trans-[Pd(SCN)2(isn)2] > trans- [Pd(NCO)2(isn)2] > trans-[Pd(N3)2(isn)2]. The structure of the complex 2 was solved by Xrays diffraction of single crystal, and shows a square-planar geometry around Pd and trans stereochemistry. It is even noticed that the structure is prolonged to hydrogen intermolecular bonds, forming bidimensional supramolecular arrays by N–H...O and tridimensional arrays, resulting from C–H...Nazide interactions. NMR data in solution confirm the formation of the complexes, noticing as well as the presence of other chemical species. It was investigated the antiproliferactive action of compounds against breast tumor cells, LM3, and lung tumor cells, LP07. The activity of isn was irrelevant and IC50 values of the complexes were higher than the ones showed by cisplatin. However, the complexes showed to be more selective than cisplatin when tested... (Complete abstract click electronic access below)

Resumo: A quimioterapia é uma das principais formas de combate ao câncer. Sendo assim, muitas pesquisas vêm sendo feitas com o objetivo de desenvolver compostos que solucionem, ou minimizem, os problemas decorrentes deste tipo de tratamento, como os efeitos colaterais e a resistência que as células desenvolvem aos medicamentos. Os pirazóis e seus complexos são conhecidos por possuírem atividade antitumoral, antiinflamatória, antibacteriana e antipirética. Tendo em vista estas propriedades, ligantes pirazólicos foram utilizados na síntese de complexos de paládio(II) com a finalidade de obter compostos com atividade antitumoral. A escolha deste metal foi baseada na similaridade entre sua química de coordenação e a da platina(II), cujos complexos, como a cisplatina e a carboplatina, são amplamente utilizados como agentes antitumorais. Neste contexto, o presente trabalho descreve a síntese, caracterização e avaliação da atividade antitumoral de duas séries de compostos paládio(II) de fórmula geral [PdX2(HdmIPz)2] {HdmIPz = 3,5-dimetil-4-iodopirazol; X = Cl (1), Br (2), I (3), SCN (4)} e [PdX2(HmPz)2] {HmPz =4-metilpirazol; X = Cl (5), Br (6), I (7), SCN (8)}. Os compostos foram caracterizados por análise elementar, espectroscopia vibracional na região do infravermelho, ressonância magnética nuclear de 1 H e 13 C{ 1 H}, termogravimetria e análise térmica diferencial. Os complexos sintetizados e os ligantes livres foram submetidos a testes de atividade citotóxica frente a células tumorais murinas. A cisplatina foi usada como droga padrão, sendo submetida às mesmas condições. A citotoxicidade dos compostos 1-4 também foi avaliada frente a macrófagos peritoneais de camundongos / Abstract: Chemotherapy is one of the main methods of treating cancer. Thus, much research has been undertaken with the aim of developing compounds that can solve or minimize the problems caused by this type of treatment, as the side effects and cell resistance. Pyrazoles and their complexes are known to possess antitumor, anti-inflammatory, antiamoebic, antibacterial, antipyretic activities. Considering these properties, pyrazole ligands were used in the synthesis of palladium(II) complexes with the aim to obtain compounds displaying antitumor activity. The choice for using this metal was based on the similarity of its coordination chemistry to that of platinum(II) whose compounds, such as cisplatin and carboplatin, are widely used as antitumor agents. In this context, this work describes the synthesis, characterization and investigation of the antitumor activity of two series of palladium(II) complexes of general formulae [PdX2(HdmIPz)2] {HdmIPz = 3,5-dimethyl-4-iodopyrazole; X = Cl (1), Br (2), I (3), SCN (4)} e [PdX2(HmPz)2] {HmPz =4-methylpyrazole; X = Cl (5), Br (6), I (7), SCN (8)}. The compounds were characterized by elemental analysis, infrared vibrational spectroscopy, 1 H and 13 C{ 1 H} nuclear magnetic resonance, thermogravimetry and differential thermal analysis. The complexes and the free ligands were tested for cytotoxic activity against murine tumor cells. Cisplatin was used as standard drug, being subject to the same conditions. The cytotoxicity of compounds 1-4 was also evaluated towards peritoneal macrophages of mice / Orientador: Adelino Vieira de Godoy Netto / Coorientador: Antonio Eduardo Mauro / Banca: Pedro Paulo Corbi / Banca: Wagner Ferraresi de Giovani / Mestre

Resumo: O presente trabalho trata da síntese, caracterização estrutural e aplicações biológicas de quatro complexos de paládio(II), de fórmula trans-[PdX2(isn)2], X = Cl (1), N3 (2), SCN (3) e NCO (4), isn= isonicotinamida. Os compostos foram preparados em mistura de CHCl3/ CH3OH (1:1), partindo-se do precursor [PdCl2(CH3CN)2] que reagiu com a isn e sais de pseudohaletos: NaN3, KNCO e NaSCN. A caracterização destes complexos, no estado sólido, se deu pelas técnicas de análise elementar, espectroscopia de absorção no infravermelho, análise térmica e difração de raios X de monocristal do composto 2, possibilitando sugerir estruturas monoméricas, com a isn coordenada ao Pd pelo nitrogênio piridínico. Cloro e os pseudohaletos acham-se coordenados de modo terminal, via nitrogênio em 2 e em 4 e pelo átomo de enxofre em 3. As curvas TG substanciaram as propostas estequiométricas e permitiram estabelecer, com base na temperatura inicial de decomposição, a seguinte ordem de estabilidade térmica para esta série: trans-[PdCl2(isn)2] > trans-[Pd(SCN)2(isn)2] > trans- [Pd(NCO)2(isn)2] > trans-[Pd(N3)2(isn)2]. A estrutura do complexo 2 foi resolvida por difração de raios X de monocristal, e apresenta uma geometria quadrado-planar ao redor do Pd e estereoquímica trans. Nota-se ainda, que a estrutura se estende por ligações intermoleculares de hidrogênios, formando arranjos supramoleculares bidimensionais via N- H...O e arranjos tridimensionais, decorrentes de interações C-H...Nazida. Os dados de RMN em solução confirmam a formação dos complexos, constatando-se, além disso, a presença de outras espécies químicas em solução. A ação antiproliferativa dos compostos contra células tumorais de mama, LM3, e pulmão, LP07, foi investigada. A atividade da isn foi desprezível e os valores de IC50 dos complexos foram maiores que os apresentados pela cisplatina... (Resumo completo, clicar acesso eletrônico abaixo) / Abstract: The present work deals with the synthesis, structural characterization and biological applications of four palladium(II) complexes, of formula trans-[PdX2(isn)2], X = Cl (1), N3 (2), SCN (3), and NCO (4), isn = isonicotinamide. The compounds were prepared in mixture of CHCl3/ CH3OH (1:1), from precursor [PdCl2(CH3CN)2] that reacted with isn and pseudohalide salts: NaN3, KNCO e NaSCN. The characterization of these complexes, in solid state, occurred by techniques of elemental analysis, infrared spectroscopy absorption, thermal analysis, and X-rays diffraction of single crystal of the compound 2, making possible to suggest monomeric structures containing the isn coordinated to Pd by pyridinic nitrogen. Chlorine and pseudohalides are coordinated of terminal way, by nitrogen in 2 and 4, and by sulphur atom in 3. The TG curves substantiated the stoichiometric proposals and made possible to establish, based on initial temperature of decomposition, the following order of thermal stability to this series: trans-[PdCl2(isn)2] > trans-[Pd(SCN)2(isn)2] > trans- [Pd(NCO)2(isn)2] > trans-[Pd(N3)2(isn)2]. The structure of the complex 2 was solved by Xrays diffraction of single crystal, and shows a square-planar geometry around Pd and trans stereochemistry. It is even noticed that the structure is prolonged to hydrogen intermolecular bonds, forming bidimensional supramolecular arrays by N-H...O and tridimensional arrays, resulting from C-H...Nazide interactions. NMR data in solution confirm the formation of the complexes, noticing as well as the presence of other chemical species. It was investigated the antiproliferactive action of compounds against breast tumor cells, LM3, and lung tumor cells, LP07. The activity of isn was irrelevant and IC50 values of the complexes were higher than the ones showed by cisplatin. However, the complexes showed to be more selective than cisplatin when tested... (Complete abstract click electronic access below) / Orientador: Antonio Eduardo Mauro / Coorientador: Adelino Vieira de Godoy Netto / Banca: Luiz Antonio Andrade de Oliveira / Banca: Denise de Oliveira Silva / Mestre

The objective of this thesis is to examine the photophysical and structural properties of Cu(I) complexes of 2-(2’-pyridyl)benzimidazolyl based ligands and Cu(I), Pd(II) and Pt(II) complexes of 2-(2’-pyridyl)indolyl based ligands, for possible use as phosphorescent emitters in OLEDs. The discovery of the atropisomeric 3,3’-bis(2-(2’-pyridyl)indolyl based ligands led to the examination of C-C coupling reactions and the investigation of the new chiral ligands with transition metal ions. Cu(I) complexes of 2-(2’pyridyl)benzimidazolyl-benzene with varying phosphine ligands were prepared. The structures were studied with X-ray crystallography and NMR. Experimental and computational results established that steric and electronic properties of the phosphine ligands influence the photophysical properties of the Cu(I) complexes. Polynuclear Cu(I) complexes with 2-(2’-pyridyl)benzimidazolyl based ligands and two PPh3 ancillary ligands were synthesized, the photoluminescent and electroluminescent properties were examined. A series of 2-(2’-pyridyl)indolyl based ligands; 2-(2’-pyridyl)indolyl-benzene (pib), 1,4-bis[2-(2’-pyridyl)indolyl]benzene (bib) and 1,3,5-tris[2-(2’-pyridyl)indolyl]benzene) (tib) and the corresponding C-C coupled dimers bis[3,3’(2-(2’-pyridyl)indolyl-benzene)] (bpib), bis[3,3’(1,4-bis[2-(2’-pyridyl)indolyl]benzene (bbib) and bis[3,3’(1,3,5-tris[2-(2’-pyridyl)indolyl]benzene)] (btib) were synthesized in a one-pot reaction with the formation of both C-N and C-C bonds. The photophysical properties of these new molecules were investigated. The dimers display intramolecular exciplex formation. The rotation barrier around the C-C bond in the 3 position of the bis-indole was calculated using DFT which support that bpib is an atropisomeric ligand. Cu(I), Pd(II) and Pt(II) complexes were synthesized with pib and bpib. [Cu(pib)(PPh3)2]+ contains a three-coordinate Cu(I) ion and doesn’t display MLCT but rather 3π-1π phosphorescence. In Pd(pib)(acac) and Pt(pib)(DMSO)Cl the pib ligand forms C,N chelated neutral complexes that display red emission in frozen solution and in solid state. The X-ray crystal structure for [Cu(bpib)2]+ revealed a homo-chiral crystal and for Pd(bpib)Cl2 and Pt(bpib)Cl¬2 show a trans-chelating geometry around the metal centre. Frozen solutions of [Cu(bpib)2]+ and Pd(bpib)Cl2 display MCLT phosphorescence. Finally the atropisomeric ligands bpib and bbib were examined as sensors to determine the enantiomeric excess of Zn(2-bromo-3-methylbutyrate)2 by CD spectroscopy. CD and fluorescent titration experiments verified that these ligands have selective interactions with different Zn(II) carboxylates. DFT computations showed that diastereomeric excess caused by chiral discrimination leads to the CD spectral-response of the atropisomeric ligands toward chiral Zn(II) carboxylates. / Thesis (Ph.D, Chemistry) -- Queen's University, 2008-09-25 09:54:21.464

Made available in DSpace on 2014-06-11T19:29:09Z (GMT). No. of bitstreams: 0 Previous issue date: 2010-02-22Bitstream added on 2014-06-13T19:38:14Z : No. of bitstreams: 1 barra_cv_me_araiq.pdf: 3280115 bytes, checksum: d562dbced1d24167c8d53a0a9e51c447 (MD5) / Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq) / Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES) / A quimioterapia é uma das principais formas de combate ao câncer. Sendo assim, muitas pesquisas vêm sendo feitas com o objetivo de desenvolver compostos que solucionem, ou minimizem, os problemas decorrentes deste tipo de tratamento, como os efeitos colaterais e a resistência que as células desenvolvem aos medicamentos. Os pirazóis e seus complexos são conhecidos por possuírem atividade antitumoral, antiinflamatória, antibacteriana e antipirética. Tendo em vista estas propriedades, ligantes pirazólicos foram utilizados na síntese de complexos de paládio(II) com a finalidade de obter compostos com atividade antitumoral. A escolha deste metal foi baseada na similaridade entre sua química de coordenação e a da platina(II), cujos complexos, como a cisplatina e a carboplatina, são amplamente utilizados como agentes antitumorais. Neste contexto, o presente trabalho descreve a síntese, caracterização e avaliação da atividade antitumoral de duas séries de compostos paládio(II) de fórmula geral [PdX2(HdmIPz)2] {HdmIPz = 3,5-dimetil-4-iodopirazol; X = Cl (1), Br (2), I (3), SCN (4)} e [PdX2(HmPz)2] {HmPz =4-metilpirazol; X = Cl (5), Br (6), I (7), SCN (8)}. Os compostos foram caracterizados por análise elementar, espectroscopia vibracional na região do infravermelho, ressonância magnética nuclear de 1 H e 13 C{ 1 H}, termogravimetria e análise térmica diferencial. Os complexos sintetizados e os ligantes livres foram submetidos a testes de atividade citotóxica frente a células tumorais murinas. A cisplatina foi usada como droga padrão, sendo submetida às mesmas condições. A citotoxicidade dos compostos 1-4 também foi avaliada frente a macrófagos peritoneais de camundongos / Chemotherapy is one of the main methods of treating cancer. Thus, much research has been undertaken with the aim of developing compounds that can solve or minimize the problems caused by this type of treatment, as the side effects and cell resistance. Pyrazoles and their complexes are known to possess antitumor, anti-inflammatory, antiamoebic, antibacterial, antipyretic activities. Considering these properties, pyrazole ligands were used in the synthesis of palladium(II) complexes with the aim to obtain compounds displaying antitumor activity. The choice for using this metal was based on the similarity of its coordination chemistry to that of platinum(II) whose compounds, such as cisplatin and carboplatin, are widely used as antitumor agents. In this context, this work describes the synthesis, characterization and investigation of the antitumor activity of two series of palladium(II) complexes of general formulae [PdX2(HdmIPz)2] {HdmIPz = 3,5-dimethyl-4-iodopyrazole; X = Cl (1), Br (2), I (3), SCN (4)} e [PdX2(HmPz)2] {HmPz =4-methylpyrazole; X = Cl (5), Br (6), I (7), SCN (8)}. The compounds were characterized by elemental analysis, infrared vibrational spectroscopy, 1 H and 13 C{ 1 H} nuclear magnetic resonance, thermogravimetry and differential thermal analysis. The complexes and the free ligands were tested for cytotoxic activity against murine tumor cells. Cisplatin was used as standard drug, being subject to the same conditions. The cytotoxicity of compounds 1-4 was also evaluated towards peritoneal macrophages of mice

Conselho Nacional de Desenvolvimento Científico e Tecnológico / This study shows the triazenes ligands and complexes Pd(II), K+ and Au(I) obtained from reactions of the ligands with fragments para-sulfonamidephenyl, comprising triazene ligand 1,3-bis (4 - sulfonamidephenyl) (1) and the complex {trans-Bis[1,3-bis(4-sulfonamidephenyl)triazenide-κN1]bis(pyridine-κN)palladium(II)}{tetra(pyridine-κN)palladium(II)}bis(potssium)·water (2) and for compounds containing orto-halophenyl fragments represented by [1,3-bis(2-fluorophenyl)triazenide-κN1](triphenylphosphine- κP)gold(I) (3), [1,3-bis(2-chlorinephenyl)triazenide-κN1](triphenylphosphine-κP)gold(I) (4), [1,3-bis(2-bromidephenyl)triazenide-κN1](triphenylphosphine-κP)gold(I) (5) and [1,3-bis(2-iodinephenyl)triazenide-κN1](triphenylphosphine - κP)gold(I) (6) complexes. The compounds reported were characterized by X-ray diffraction on single crystal, and their structures in solid state are formed through supramolecular arrangements via classical and non-classical hydrogen bonding, as in the case of the compounds with the sulfonamide grouping, one can observe the formation of supramolecular synthons. In complexes 4, 5 and 6 it is observed to occur interactions halogen···halogen characterized by the formation of dimeric units associated by a center of inversion, besides having geometries classified by the angle of the links formed between the halogen and carbon atoms. Compounds 1, 2, 3, 4, 5 and 6 were subjected to evaluation front of biological activity, such as plasmidial DNA cleavage studies, evaluation of cytotoxicity and antibacterial activity, showing promising results. / Este trabalho apresenta o estudo de ligantes triazenos e complexos de Pd(II), K+ e Au(I) obtidos a partir de reações com os ligantes com fragmentos para-sulfonamidafenila compreendendo o ligante 1,3-bis-(4-sulfonamidafenil)triazeno (1) e o complexo {trans-Bis[1,3-bis(4-sulfonamidafenil)triazenido-κN1]bis(piridina-κN)paládio(II)}{tetra(piridina-κN)paládio(II)}bis(potássio)·água (2) e para compostos contendo fragmentos orto-halofenila representados pelos complexos [1,3-bis(2-fluorofenil)triazenido-κN1](trifenilfosfina- κP)ouro(I) (3), [1,3-bis(2-clorofenil)triazenido-κN1](trifenilfosfina- κP)ouro(I) (4), [1,3-bis(2-bromofenil)triazenido-κN1](trifenilfosfina- κP)ouro(I) (5) e [1,3-bis(2-iodofenil)triazenido-κ-N1](trifenilfosfina- κP)ouro(I) (6). Os compostos relatados foram caracterizados por difração de raios X em monocristal, e suas estruturas no estado sólido são formadas através de arranjos supramoleculares via ligações de hidrogênio clássicas e não clássicas, como no caso dos compostos com o grupamento sulfonamida, pode-se observar a formação de synthons supramoleculares. Nos complexos 4, 5 e 6 é observada a ocorrência de interações halogênio···halogênio caracterizadas pela formação de unidades díméricas associadas por um centro de inversão, além de apresentarem geometrias classificadas pelo ângulo de ligações formado entre os átomos de halogênio e carbono. Os compostos 1, 2, 3, 4, 5 e 6 foram submetidos a avaliação frente a atividade biológica, como estudos na clivagem do DNA plasmidial, avaliação da citotoxicidade e atividade antibacteriana, mostrando resultados promissores.

Submitted by isabela.moljf@hotmail.com (isabela.moljf@hotmail.com) on 2017-05-08T11:42:32Z No. of bitstreams: 1 diegofernandodasilvapaschoal.pdf: 9955630 bytes, checksum: a25cace9c9785b91c273376bf940d222 (MD5) / Approved for entry into archive by Adriana Oliveira (adriana.oliveira@ufjf.edu.br) on 2017-05-17T13:42:19Z (GMT) No. of bitstreams: 1 diegofernandodasilvapaschoal.pdf: 9955630 bytes, checksum: a25cace9c9785b91c273376bf940d222 (MD5) / Made available in DSpace on 2017-05-17T13:42:19Z (GMT). No. of bitstreams: 1 diegofernandodasilvapaschoal.pdf: 9955630 bytes, checksum: a25cace9c9785b91c273376bf940d222 (MD5) Previous issue date: 2014-08-26 / CAPES - Coordenação de Aperfeiçoamento de Pessoal de Nível Superior / Um estudo sistemático a respeito da importância do nível de teoria e do conjunto de funções de base no cálculo de propriedades moleculares foi conduzido. Foram realizados estudos a respeito das propriedades ópticas lineares (OL) e não-lineares (ONL) de moléculas diatômicas, pequenas moléculas poliatômicas e moléculas orgânicas conjugadas com grupos doadores e retiradores de elétrons. Além disso, foi avaliada a estrutura e reatividade de complexos de Pt(II) e Pd(II). Por fim, um estudo a respeito do deslocamento químico de 195Pt foi conduzido, onde diversos parâmetros que influenciam em tal propriedade foram extensivamente analisados. Para cada trabalho proposto um novo conjunto de funções de base foi desenvolvido. Foram propostas as bases D10 (BH), P3 (CO), F3 (CS), J5 (N2), NLO (H,C,N,O,F,S), NLO-X (X=I,II,III,V,aV) (H,B-F,Si-Cl), mDZP (Pd,Pt), kPd-ADZP(Pd) e NMR-TZPP-DKH (H-He, Li-Ne, Na-Ar, K-Ca, Ga-Kr, Rb-Sr, In-Xe e Pt). Previsões das propriedades OL e ONL de diversas moléculas foram realizadas. Para um conjunto de moléculas com valores de primeira hiperpolarizabilidade (β) variando de 0 a 190 esu um desvio médio absoluto de 13,2 esu foi encontrado no nível cam-B3LYP/NLO-V em comparação com um desvio de 27,2 esu com a base da literatura 6-31G(2d). Além disso, foram realizados estudos de estrutura e reatividade da cisplatina e do cispaládio. Para a reação de hidrólise da cDDPt foi prevista uma barreira de energia no nível B3LYP/mDZP/6-31+G(d) de 22,8 kcal.mol-1 que está em excelente acordo com o valor experimental de 22,±0,4 kcal.mol-1. Considerando a mesma reação, porém para o análogo de Pd, um valor de 17,11 kcal.mol-1 no nível B3LYP/mDZP/6-31+G(d) e de 16,94 kcal.mol-1 no nível B3LYP/kPd-ADZP/6-31+G(d) foram previstos e estão em bom acordo com o valor esperado de 16,34 kcal.mol-1. Somado a isso, uma análise a respeito do deslocamento químico de 195Pt foi abordada, onde para uma ampla faixa de 73 complexos de Pt(II) um desvio absoluto médio de apenas 156 ppm foi encontrado no nível GIAO-B3LYP(DKHSO)/NMR-TZPP-DKH/IEFPCM-UFF. Todas as bases aqui propostas foram testadas de forma sistemática e, no geral, bons resultados foram encontrados para as propriedades analisadas e com custos computacionais altamente acessíveis. / A systematic study about the importance of the level of theory and the basis sets in the calculation of molecular properties was conducted. It performed studies on the linear and nonlinear optical properties of diatomic molecules, small polyatomic molecules and conjugated donor/acceptor organic molecules. In addition, the structure and reactivity of Pt(II) and Pd(II) complexes were evaluated. Finally, a study about the 195Pt chemical shift was conducted, where various parameters that influence such property have been extensively analyzed. For each work proposed a new basis set was developed. The following basis sets were proposed: D10 (BH), P3 (CO), F3 (CS), J5 (N2), NLO (H,C,N,O,F,S), NLO-X (X=I,II,III,V,aV) (H,B-F,Si-Cl), mDZP (Pd,Pt), kPd-ADZP(Pd) and NMR-TZPP-DKH (H-He, Li-Ne, Na-Ar, K-Ca, Ga-Kr, Rb-Sr, In-Xe e Pt). Estimates of L-NLO properties of several molecules were performed. For a set of molecules with values of first hyperpolarizability (β) ranging from 0 to 190 esu, an average absolute deviation of 13,2 esu was found at cam-B3LYP/NLO-V level compared with 27,2 esu with the standard basis set 6-31G(2d). Furthermore, studies of structure and reactivity of cisplatin and cispalladium were performed. For the aquation reaction of cisplatin an energy barrier of 22.8 kcal.mol-1 was predicted at B3LYP/mDZP/6-31+G(d) level, which it is in excellent agreement with the experimental value of 22.9±0.4 kcal.mol-1. Considering the same reaction, but for Pd analogous, a value of 17.11 kcal.mol-1 at B3LYP/mDZP/6-31+G(d) level and 16.94 kcal.mol-1 at B3LYP/kPd-ADZP/6-31+G(d) level were predicted and these values are in good agreement with the expected value of 16.34 kcal.mol-1. Added to this, an analysis about the 195Pt chemical shift was addressed, where for a wide range of 73 Pt(II) complexes and average absolute deviation of only 156 ppm was found at GIAO-B3LYP(DKHSO)/NMR-TZPP-DKH/IEFPCM-UFF level. All basis sets proposed here were systematically tested and, in general, good results were found for the properties of interest and highly affordable computational costs.

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