Made available in DSpace on 2014-12-17T15:41:55Z (GMT). No. of bitstreams: 1 DanielleOM_DISSERT.pdf: 1963445 bytes, checksum: 143b241474d5026def897c0c4c0d797f (MD5) Previous issue date: 2011-07-12 / Coordena??o de Aperfei?oamento de Pessoal de N?vel Superior / In this work were synthesized and studied the spectroscopic and electrochemical characteristics of the coordination compounds trans-[Co (cyclam)Cl2]Cl, trans- Na[Co(cyclam)(tios)2], trans-[Co(en)2Cl2]Cl and trans-Na[Co(en)2(tios)2], where tios = thiosulfate and en = ethylenediamine. The compounds were characterized by: Elemental Analysis (CHN), Absorption Spectroscopy in the Infrared (IR), Uv-Visible Absorption Spectroscopy, Luminescence Spectroscopy and Electrochemistry (cyclic voltammetry). Elemental Analysis (CHN) suggests the following structures for the complex: trans- [Co(cyclam)Cl2]Cl.6H2O and trans-Na[Co(cyclam)(tios)2].7H2O. The electrochemical analysis, when compared the cathodic potential (Ec) processes of the complexes trans- [Co(cyclam)Cl2]Cl and trans-[Co(en)2Cl2]Cl, indicated a more negative value (-655 mV) for the second complex, suggesting a greater electron donation to the metal center in this complex which can be attributed to a greater proximity of the nitrogen atoms of ethylenediamine in relation to metal-nitrogen cyclam. Due to the effect of setting macrocyclic ring to the metal center, the metal-nitrogen bound in the cyclam are not as close as the ethylenediamine, this fact became these two ligands different. Similar behavior is also observed for complexes in which the chlorides are replaced by thiosulfate ligand, trans-Na[Co(en)2(tios)2] (-640 mV) and trans-Na[Co(cyclam)(tios)2] (-376 mV). In absorption spectroscopy in the UV-visible, there is the band of charge transfer LMCT (ligand p d* the metal) in the trans-Na[Co(cyclam)(tios)2] (350 nm, p tios  d* Co3+) and in the trans-Na[Co(en)2(tios)2] (333 nm, p tios d* Co3+), that present higher wavelength compared to complex precursor trans- [Co(cyclam)Cl2]Cl (318 nm, pCl  d* Co3+), indicating a facility of electron density transfer for the metal in the complex with the thiosulfate ligand. The infrared analysis showed the coordination of the thiosulfate ligand to the metal by bands in the region (620-635 cm-1), features that prove the monodentate coordination via the sulfur atom. The νN-H bands of the complexes with ethylenediamine are (3283 and 3267 cm-1) and the complex with cyclam bands are (3213 and 3133 cm-1). The luminescence spectrum of the trans-Na[Co(cyclam)(tios)2] present charge transfer band at 397 nm and bands dd at 438, 450, 467, 481 and 492 nm. / Este trabalho teve por objetivo sintetizar e estudar as caracter?sticas espectrosc?picas e eletroqu?micas dos compostos de coordena??o trans- Na[Co(cyclam)(tios)2], trans-[Co(cyclam)Cl2]Cl, trans-[Co(en)2Cl2]Cl e trans- Na[Co(en)2(tios)2], em que tios = tiossulfato e en = etilenodiamina. Os compostos obtidos foram caracterizados por: An?lise elementar (CHN), Espectroscopia de Absor??o na Regi?o do Infravermelho (IV), Espectroscopia de Absor??o na Regi?o do UV-Vis?vel, Espectroscopia de Luminesc?ncia e Eletroqu?mica (voltametria c?clica). A an?lise elementar (CHN) sugere as seguintes estruturas para os complexos: trans- [Co(cyclam)Cl2]Cl.6H2O e trans-Na[Co(cyclam)(tios)2].7H2O. Na an?lise eletroqu?mica, ao se fazer uma compara??o dos potenciais cat?dicos (Ec) referentes aos processos de redu??o dos complexos trans-[Co(cyclam)Cl2]Cl e trans-[Co(en)2Cl2]Cl, observa-se valores mais negativos (-655 mV) no segundo complexo, sugerindo uma maior doa??o eletr?nica ao centro met?lico neste complexo o que pode ser atribu?do a uma maior proximidade dos ?tomos de nitrog?nio da etilenodiamina em rela??o a liga??o metal nitrog?nio do cyclam, devido ao efeito do ajuste do anel macroc?clico ao centro met?lico (efeito macroc?clico), o que faz com que a liga??o metal-nitrog?nio n?o seja t?o pr?xima quanto da etilenodiamina, fato que difere os ligantes em estudo. Comportamento similar ? tamb?m observado para os complexos, em que os cloretos s?o substitu?dos pelo ligante tiossulfato, trans-Na[Co(en)2(tios)2] (-640 mV) e trans- Na[Co(cyclam)(tios)2] (- 376 mV). Na espectroscopia de absor??o na regi?o do UVvis?vel observa-se a banda de transfer?ncia de carga LMCT (pdo ligante d* do metal), como sendo a de maior comprimento de onda para o trans- Na[Co(cyclam)(tios)2] (350 nm, ptios d* Co3+) e trans-Na[Co(en)2(tios)2] (333 nm, ptios d* Co3+) comparativamente ao complexo precursor, trans- [Co(cyclam)Cl2]Cl (318 nm, pCl- d* Co3+) indicando uma maior facilidade de transfer?ncia de densidade eletr?nica para o metal nos complexos com o ligante tiossulfato. Na an?lise de infravermelho observou-se a coordena??o do ligante tiossulfato ao metal nos complexos atrav?s de bandas na regi?o de 620-635 cm-1, caracter?sticas que comprovam a forma monodentada de coordena??o via ?tomo de enxofre e a perman?ncia das bandas νN-H para complexos com etilenodiamina, bandas em 3283 e 3267 cm-1, e complexos com o cyclam, bandas em 3213 e 3133 cm-1. Na an?lise de luminesc?ncia foi observada uma banda de transfer?ncia de carga em 397 nm e bandas d-d no espectro de emiss?o do complexo trans-Na[Co(cyclam)(tios)2] em 438, 450, 467, 481 e 492 nm.

Submitted by Automa??o e Estat?stica (sst@bczm.ufrn.br) on 2016-01-04T20:23:54Z No. of bitstreams: 1 WendyMarinaToscanoQueirozDeMedeiros_DISSERT.pdf: 5044518 bytes, checksum: be0ad7506b973125eacfef544d411fd4 (MD5) / Approved for entry into archive by Arlan Eloi Leite Silva (eloihistoriador@yahoo.com.br) on 2016-01-05T21:20:21Z (GMT) No. of bitstreams: 1 WendyMarinaToscanoQueirozDeMedeiros_DISSERT.pdf: 5044518 bytes, checksum: be0ad7506b973125eacfef544d411fd4 (MD5) / Made available in DSpace on 2016-01-05T21:20:21Z (GMT). No. of bitstreams: 1 WendyMarinaToscanoQueirozDeMedeiros_DISSERT.pdf: 5044518 bytes, checksum: be0ad7506b973125eacfef544d411fd4 (MD5) Previous issue date: 2014-07-21 / Coordena??o de Aperfei?oamento de Pessoal de N?vel Superior - CAPES / Com o presente trabalho tem-se como objetivo contribuir para o desenvolvimento da qu?mica de coordena??o de macromol?culas como o resorcinareno, com a s?ntese e caracteriza??o de novos complexos de cobre com os ligantes cloretos, vanilina e resorcinareno, todos eles coordenados ? fenantrolina, uma mol?cula que ? biologicamente ativa e possui importantes propriedades em sistemas biol?gicos. O complexo [(Cu(phen))4(resvan)], sintetizado a partir da rea??o direta do resorcinareno com metais, gera v?rias possibilidades de coordena??o, o que dificulta sua caracteriza??o. Por isso, com o objetivo de limitar os s?tios de coordena??o do ligante, o complexo [(Cu(phen))4(resvan)]Cl4 foi formado a partir de uma nova metodologia de s?ntese. Os complexos cis-[Cu(phen)Cl2], cis-[Cu(phen)(van)]Cl, [(Cu(phen))4(resvan)] e [(Cu(phen))4(resvan)]Cl4 foram caracterizados pelas t?cnicas espectrosc?picas de IV, Uv-Vis e EPR. Atrav?s do infravermelho foi poss?vel comprovar a presen?a do ligante fenantrolina em todos os complexos sintetizados, bem como a presen?a do ligante vanilina no complexo cis-[Cu(phen)(van)]Cl e do ligante resvan no complexo [(Cu(phen))4(resvan)], al?m de indicar a forma??o do resorcinareno no complexo [(Cu(phen))4(resvan)]Cl4. Os espectros eletr?nicos dos compostos de coordena??o obtidos indicaram a presen?a do ligante fenantrolina, atrav?s de suas bandas intensas na regi?o do ultravioleta. Para o complexo cis-[Cu(phen)(van)]Cl esta t?cnica indicou ainda a presen?a do ligante vanilina, a partir das bandas intraligante da vanilina e de transfer?ncia de carga, LMCT. Al?m disso, os espectros apresentaram bandas d-d, confirmando a presen?a de metais nos compostos formados. A quantidade de ?tomos de cobre presentes no complexo [(Cu(phen))4(resvan)]Cl4 foi estimada, a partir da an?lise comparativa das absorb?ncias de solu??es de mesma concentra??o de [(Cu(phen))4(resvan)]Cl4 e cis-[Cu(phen)(van)]Cl, a qual indica que estes compostos possuem em suas estruturas ?tomos de cobre na propor??o 4:1. Os espectros de EPR dos compostos cis-[Cu(phen)Cl2], cis-[Cu(phen)(van)]Cl e [(Cu(phen))4(resvan)]Cl4 apresentaram perfis axiais, enquanto que o complexo [(Cu(phen))4(resvan)] apresentou perfis axial e r?mbico, indicando uma mudan?a no ambiente de simetria do Cu(II) para este complexo. Os ligantes vanilina e resvan foram submetidos a ensaios biol?gicos com resultados satisfat?rios, ambos apresentando atividade antioxidante e baixa toxicidade, al?m da vanilina apresentar certo car?ter antitoxopl?smico. / The main objective of the present work is to contribute to the development of the coordination chemistry of macromolecules such as resorcinarene with the synthesis and characterization of new copper complexes with chloride, vanillin and resorcinarene binders, all coordinated to phenanthroline, a biologically active molecule with important properties in biological systems. The complex [(Cu(phen))4(resvan)], was synthesized from the direct reaction of the metals with resorcinarene and generates several possibilities for coordination, which hinders its characterization. Therefore, in order to limit the coordination sites of the ligand, the complex [(Cu(phen))4(resvan)]Cl4 was formed from a new synthetic methodology. The complex cis-[Cu(phen)Cl2], cis-[Cu(phen)(van)]Cl, [(Cu(phen))4(resvan)] and [(Cu(phen))4(resvan)]Cl4 were characterized by spectroscopic techniques such as IR, UV-vis and EPR. By using infrared it has been possible to demonstrate the presence of the phenanthroline ligand in the synthesized complexes, and vanillin in the complex cis- [Cu(phen)(van)]Cl and resvan ligand in the complex [(Cu(phen))4(resvan)], besides this indicating the formation of resorcinarene in the complex [(Cu(phen))4(resvan)]Cl4. The electronic spectra of these coordination compounds indicated the presence of the phenanthroline ligand, by its intense bands in the ultraviolet region. For the complex cis- [Cu(phen)(van)]Cl it still indicated the presence of the ligand vanillin based on intraligand bands of vanillin and charge transfer, LMCT. Furthermore, the spectra showed d-d bands, confirming the formation of metal compounds. The amount of copper atoms present in the complex [(Cu(phen))4(resvan)]Cl4 was estimated from a comparative analysis of the absorbances of solutions of the same concentration of [(Cu(phen))4(resvan)]Cl4 and cis- [Cu(phen)(van)]Cl, which indicates that these compounds have copper atoms in the ratio 4:1. The EPR spectra of the complex cis-[Cu(phen)Cl2], cis-[Cu(phen)(van)]Cl and [(Cu(phen))4(resvan)]Cl4 showed axial profiles, while the complex [(Cu(phen))4(resvan)] showed of axial and rhombic profiles, indicating a change in the symmetry of the Cu (II) to this complex environment. The binders vanillin and resvan underwent biological assays with satisfactory results, both exhibited antioxidant activity and low toxicity, as well vanillin present antitoxopl?smico character.

Submitted by Automa??o e Estat?stica (sst@bczm.ufrn.br) on 2016-02-05T22:05:48Z No. of bitstreams: 1 LeonardoDeSaCosta_DISSERT.pdf: 2101335 bytes, checksum: ac42734e9bbfbba5815b32c66600ff2b (MD5) / Approved for entry into archive by Arlan Eloi Leite Silva (eloihistoriador@yahoo.com.br) on 2016-02-15T23:04:07Z (GMT) No. of bitstreams: 1 LeonardoDeSaCosta_DISSERT.pdf: 2101335 bytes, checksum: ac42734e9bbfbba5815b32c66600ff2b (MD5) / Made available in DSpace on 2016-02-15T23:04:07Z (GMT). No. of bitstreams: 1 LeonardoDeSaCosta_DISSERT.pdf: 2101335 bytes, checksum: ac42734e9bbfbba5815b32c66600ff2b (MD5) Previous issue date: 2014-02-27 / Coordena??o de Aperfei?oamento de Pessoal de N?vel Superior - CAPES / Este trabalho teve a finalidade de promover a s?ntese, caracteriza??o e de propor uma estrutura molecular para os compostos de coordena??o envolvendo a furosemida (?cido 4- cloro-2-(2-furilmetilamino)-5-sulfamoil-benz?ico), com os ?ons met?licos Ni+2, Zn+2 e Co+2 . Os compostos foram obtidos em meio metan?ico por evapora??o do solvente ap?s o procedimento da s?ntese. Para caracteriza??o dos compostos de coordena??o, foram feitas as determina??es dos teores de metais por complexometria com EDTA, espectroscopia na regi?o do infravermelho (FTIR), solubilidade dos compostos em diversos solventes, an?lise termogravim?trica (TG), calorimetria explorat?ria diferencial (DSC), an?lise t?rmica diferencial (DTA) e a determina??o dos teores de carbono, nitrog?nio e hidrog?nio (CHN). Os resultados da espectroscopia na regi?o do infravermelho sugerem que o ligante se coordene de forma bidentada, com os ?ons met?licos. As intera??es com os centros met?licos ocorrem pela coordena??o do ?tomo de nitrog?nio do grupo amino e pelo ?tomo de oxig?nio do ?cido carbox?lico da estrutura da furosemida. Com os resultados dos teores de metais, an?lise elementar (CHN) e an?lise t?rmica, foram poss?veis propor as estruturas dos complexos. Os valores de condutividade molar em acetonitrila indicam que os complexos apresentam comportamento de n?o eletr?lito em solu??o. Os compostos apresentam alta solubilidade em metanol e acetonitrila, j? em ?gua s?o parcialmente insol?veis. Atrav?s dos resultados das an?lises t?rmicas (TG, DSC, DTA), obteve-se o comportamento t?rmico dos compostos como: etapas de desidrata??o, estabilidade t?rmica, decomposi??o e as energias envolvidas. / This work aimed to promote the synthesis, characterization and propose a plausible molecular structure for coordination compounds involving furosemide (4-Chloro-2-(2- furylmethylamino)-5-sulfamoyl-benzoic acid) with the metal ions Ni+2, Zn+2 and Co+2. The compounds were obtained in methanoic medium by evaporation of the solvent after the synthesis procedure. For characterization of coordination compounds determining the levels of metals by EDTA complexometry, infrared spectroscopy (FTIR), solubility of compounds in various solvents, thermogravimetry (TG), differential scanning calorimetry (DSC), differential thermal analysis were made (DTA), determination of the carbon , hydrogen and nitrogen (CHN). The results of infrared spectroscopy in the region suggest that the organic ligand is coordinated in a bidentate fashion to the metal ions, the metal center interactions to occur by the coordination of the nitrogen atom of the amino group and the oxygen atom of the carboxylic acid of the structure of furosemide. With the results of the levels of metal, elemental analysis (CHN) and thermal analysis has been possible to propose the structure of the ligand. The values of the molar conductivity of the complex in acetonitrile behavior suggest the non acetonitrile electrolyte solution. With the solubility tests it was found that the compounds have high solubility in methanol and acetonitrile, as are partially insoluble in water. From the results of thermal analysis (TG, DSC, DTA), it was possible to obtain the thermal behavior of the compounds as stages of dehydration, thermal stability, decomposition and the energies involved.

Made available in DSpace on 2014-12-17T15:42:17Z (GMT). No. of bitstreams: 1 VeronicaSO_DISSERT.pdf: 3422406 bytes, checksum: d33eed82fa27aa7c5249e32ca3da7fd8 (MD5) Previous issue date: 2014-01-22 / Coordena??o de Aperfei?oamento de Pessoal de N?vel Superior / The present work has as main objective to contribute to the coordination chemistry of the ligand kojic acid, with the synthesis and characterization of the homoleptic compounds [Al(kj)3], [Fe(kj)3], [Fe(kj)2], [Cu(kj)2] e [Ru(kj)3], and the new heteroleptic complexes, trans- K2[Fe(kj)2(CN)2] and trans-Na2[Ru(kj)2(CN)2]. The obtained compounds were characterized by vibrational spectroscopy in the infrared region (IV) and Electronic spectroscopy in the ultraviolet and visible region (Uv-Vis). The infrared results indicated the coordination of the bidentate ligand kojic acid, due to reductions in the values of the stretching frequencies of the carbonyl and double bonds, compared to the free ligand for all complexes obtained. The presence of new vibrational modes indicated the change of symmetry of the molecules in the new compounds synthesized. Additionally, the presence of vibrational modes assigned to metal-oxygen also contributed to confirm the ligand coordinating to the metal ions. Through this technique, was also possible to perform correlations of the numbers of vibrational modes, in the region 1400-900 cm-1 and the compounds geometry. The heteroleptic compounds exhibited υC≡N in 2065 and 2053 cm-1, respectively, for the trans-K2[Fe(kj)2(CN)2] and trans-Na2[Ru(kj)2(CN)2], indicating coordination of the cyano ligand to metal ions FeII e RuII. Comparing the obtained values with literature data was possible to identify the complex isomerism as trans. In relation to the results of electronic spectroscopy, studies of pH variation of kojic acid provided information on the distribution of electron density in the molecule, showing characteristic spectral profile of kojic ion and its protonated form (Hkj, kojic acid), with two bands at 215 and 269 nm, or deprotonated (kj-), with bands at 226 and 315 nm. The electronic spectra obtained for all complexes in aqueous medium, in the ultraviolet region, exhibited variations of the energies assigned to kojic acid intraligand transitions while in the visible region, only transitions assigned to charge transfer of iron and ruthenium complex have been identified / Com o presente trabalho tem-se como objetivo contribuir com a qu?mica de coordena??o do ligante ?cido k?jico, com a s?ntese e caracteriza??o de compostos homol?pticos [Al(kj)3], [Fe(kj)3], [Fe(kj)2], [Cu(kj)2] e [Ru(kj)3], assim como dos novos complexos heterol?pticos, trans-K2[Fe(kj)2(CN)2] e trans-Na2[Ru(kj)2(CN)2]. Os compostos obtidos foram caracterizados atrav?s da espectroscopia vibracional na regi?o do infravermelho e da espectroscopia eletr?nica na regi?o do ultravioleta e vis?vel (Uv-Vis). Os resultados de infravermelho comprovaram a coordena??o do ligante bidentado ?cido k?jico, devido ?s redu??es dos valores das frequ?ncias de estiramento da carbonila e das duplas liga??es, comparativamente ao ligante livre, para todos os complexos obtidos. Assim como a verifica??o de novos modos vibracionais, em decorr?ncia da altera??o de simetria da mol?cula na forma??o de novas estruturas para os compostos sintetizados. Al?m de modos vibracionais atribu?dos aos estiramentos metal-oxig?nio, evidenciando coordena??o dos ?ons met?licos ao ligante. Atrav?s dessa t?cnica, tamb?m foi poss?vel realizar correla??es dos n?meros de modos vibracionais, na regi?o de 1400 a 900 cm-1, com a geometria dos compostos. Adicionalmente aos complexos homol?pticos, os compostos heterol?pticos exibiram frequ?ncias de υC≡N em 2065 e 2053 cm-1, respectivamente, para o trans-K2[Fe(kj)2(CN)2] e o trans-Na2[Ru(kj)2(CN)2], indicando coordena??o do ligante ciano aos ?ons met?licos de FeII e RuII. Comparativamente com dados da literatura, foi poss?vel propor a isomeria, caracterizando os complexos em configura??o trans. E com rela??o aos resultados da espectroscopia eletr?nica, os estudos da varia??o do pH do ?cido k?jico forneceram informa??es sobre a distribui??o de densidade eletr?nica na mol?cula, apresentando perfil espectral caracter?stico do ?on k?jico na sua forma protonada (Hkj, ?cido k?jico), com duas bandas em 215 e 269 nm, ou desprotonada (kj-), com bandas em 226 e 315 nm. E os espectros eletr?nicos obtidos para todos os complexos em meio aquoso, na regi?o do ultravioleta exibiram varia??es das energias atribu?das ?s transi??es intraligantes do ?cido k?jico, e na regi?o do vis?vel, s? foram identificadas transi??es para os complexos de ferro e rut?nio, atribu?das em sua maioria as transfer?ncia de carga