A autoxidação dos complexos de Ni(II) e Co(II) com tetra, penta e hexaglicina, em meio de tampão borato, é acelerada por espécies de enxofre (IV) (H2S0<SUB3, HS03-e SO32-). A formação dos complexos de Ni(III) e Co(III) foi acompanhada espectrofotometricamente em 325 e 265 nm, respectivamente. A velocidade da reação de autoxidação do complexo de Ni(II)/Gn aumenta com a concentração de S(IV) e é máxima em pH &#926;8,5. O processo é autocatalítico com Ni(III)ou Co(III)atuando como iniciadores, forma~os pela oxidação espontânea de Ni(II) ou Co(II) pelo oxigênio molecular. A dependência da constante de velocidade observada com a oncentração de S(IV) evidenciou possíveis reações paralelas com formação de um complexo com ligantes mistos antes da etapa da oxidação. A autoxidação dos complexos de Cu(II)com penta e hexaglicina em pH =9 é muito lenta, na presença e na ausência de S(IV).A presença de S(IV) e de traços de Ni(II)ou Co(II) aumenta significativamente a velocidade e a eficiência da reação (período de indução de 0,5 s). O mecanismo envolve uma cadeia de reações e um ciclo redox dos complexos. Acetaldeído e formaldeído inibem parcialmente a reação de autoxidação de Ni(II)/G4 na presença de S(IV) e luminol.O método quimiluminescente desenvolvido pode ser empregado para determinação de formaldeído [(5,0.10-5 - 1,0.10-2) mol L-1] e acetaldeído [(1,0.10-4 - 0,10) mol L-1], não sendo possível detectar separadamente cada um desses aldeídos. Na autoxidação de Ni(OH)2 induzida por S(IV) na presença de luminol ocorre emissão de radiação, possibilitando a detecção de S(IV) na faixa de 5,0.10-8 a 1,0.10-5 mol L-1, com limite de detecção estimado de 1,3.10-8 mol L-1. / The autoxidation of Ni(lI) and Co(lI) complexes with tetra, penta and hexaglycine, in borate medium, is accelerated by sulfur (IV) species (H2S03, HS03- and SO32-). The formation of Ni(llI) and Co(lIl) complexes was followed spectrophotometrically at 325 and 265 nm, respectively. The autoxidation rate of Ni(II)/Gn complex increases with S(IV) concentration and is maximum at pH ~ 8.5. The process is autocatalytic with Ni(lIl) or Co(llI) acting as initiators, formed by spontaneous oxidation by oxygen. The dependence of the observed rate constant with S(IV) concentration showed evidences of back or parallel reactions with formation of mixed ligand complex prior to the oxidation step. The autoxidation of Cu(II)/penta and hexaglycine complexes at pH = 9, in the presence and absence of S(IV), is very slow. The presence of S(IV) and of small amounts of Ni(lI) or Co(lI) increases significantly the effectiveness and reaction rate (induction period = 0.5 s). The mechanism involves a radical chain and redox cycling of the metal íon complexes. Acetaldehyde and formaldehyde partially inhibit the autoxidation reaction of Ni(II)/G4 in the presence of S(IV) and luminol. The developed chemiluminescent method can be used for determination of formaldehyde [(5.0.10-5 - 1.0.10-2) mol L-1] and acetaldehyde [(1.0.10-4 - 0.10) mol L-1), being not possible their isolated detection. The S(IV) induced autoxidation of Ni(OH)2 in the presence of luminol, occurs with radiation emission, allowing S(IV) detection in the range 5.0.10-8 to 1.0.10,-5 mol L-1, with detection limit of 1.3.10-8 mol L-1.

Neste trabalho estudou-se os complexos formados pelo íon cobre (II) com o dipeptides triptofilglicina na faixa de pH=3,0 a 13,5. A caracterização dos mesmos foram realizadas através das técnicas de Ressonância Paramagnética Eletrônica (RPE) em duas temperaturas (ambiente e nitrogênio líquido) e Absorção Ótica no visível (350 a 1000 nm). As amostras em solução aquosa obedeceram a relação de 10 ligantes para 1 metal. Caracterizou-se três tipos de complexos nas faixas pHs: 4.0 a 6,0; 6,0 a 12,0 e acima de 12,0. Estes complexos foram propostos com base nos dados espectroscópicos e um conhecimento prévio dos pKs dos grupos desprotonáveis, são eles: CuL2, CuL(H2O) e CuL(OH) (H2O). Estudou-se a influência da cadeia lateral pesada nos parâmetros espectroscópicos e comparativamente ao complexo Gliciltriptofano estudado por Nascimento (1985) no mesmo intervalo de pH, foi possível mostrar que o modelo de não covalência (Brill e Bryce (1968)), é o mais adequado em explicar a diminuição da constante hiperfina Az, constatado em Ph elevado. O complexo tridentado CuL(H2O) foi cristalizado e medidas de RPE no monocristal permitiram obter o tensor giromagnético molecular. Interação de exchange e/ou dipolar, não permitiram a determinação do tensor hiperfino no complexo. Através das direções principais e valores das direções das componentes do tensor cristalino e as direções das normais aos planos de coordenação, foi possível detectar uma forte interação de exchange entre dois íons vizinhos. / In this work was studied the complex made by the ion copper(II) with the dipeptide tryptophilglicine in the area of pH between 3,0-13,5. The cacacterizations of them were realized by the electron paramagnet resonance (ERP) in two temperatures (room and liquid nitrogen) and Optics Absorption in the visible (between 350 - 1100 nm). The samples in aqueous solution got the rate of 10 ligand to one metal. Three species of complex were characterized: pHs between 4,0-6,0; 6,0-12,0 and above 12,0. These complexes were proposed with foundation in the spectroscope informations and a previous know of the pKs of the deprotanatable groups, they are: CuL2; CuL(H2O) and CuL(OH) (H2O). The influency of the lateral chain weighed in the spectroscopies parameter was studied, and in compere with the glyciltryptophan complex studied by Nascimentoi (1985) in the same intermission of the pH, it was possible to show that the model of no covalente (Brill and Bryce-1968) is the adequader to explain the hiperfine constant Az diminution, evidenced in heigh pH. The tridentate complex CuL(H2O) was crystallized and EPR mensures in the monocrystal allowed to get the molecular gyromagnetic tensor. Exchange and/or dipolar interaction didn\'t allow the determination of the hyperfine tensor of the complex. By the main directions and values of the component parts of the tensor g crystalline and the normal directions to the plans of coordination, it was possible to detect a strong interaction of exchange between to neighbour ions.

Ce travail de thèse visait à développer une nouvelle famille de ligands de type bispidines pour la complexation du cuivre(II) en vue d’applications en tomographie par émission de positrons(TEP). En effet, le cuivre 64 est un radioélément dont l’étude dans le cadre de l’imagerie TEP est en plein essor. Les bispidines, quant à elles, présentent l’intérêt de posséder une structure rigide et pré-organisée permettant la complexation de nombreux métaux de transitions.Nous présentons ici la synthèse et l’optimisation de nouveaux ligands dont les propriétés structurales et physico-chimiques ont été étudiées. Un ligand a montré de très bons résultats puisqu’il possède tous les paramètres cinétiques et thermodynamiques nécessaires à un chélatant utilisé en imagerie TEP. Différentes voies de fonctionnalisation ont ensuite été étudiées afin d’obtenir divers chélatants bifonctionnels. Un ligand comportant une lysine a pu être couplé à une fonction maléimide (régiosélective des cystéines), à une biotine (possédant une forte interaction pour la streptavidine) ou encore à un motif Bodipy pour l’obtention d’une sonde bimodale (UV-visible et TEP). Enfin, nous présentons l’extension de cette famille de bispidines par l’augmentation du nombre de fonctions de coordination présentes ou encore par l’obtention de ligands tricycliques en vue de moduler la sélectivité de ces molécules. / This work aimed to develop a new family of bispidine-type ligands for copper(II) complexation with applications in Positron Emission Tomography (PET). Indeed, copper 64 is a radioelement whose study in PET imaging is booming. Bispidines have the benefit of having a rigid and preorganized structure for complexation of a large number of transition metals. In this work we present the synthesis and optimization of new ligands whose structural and physico-chemical properties have been studied. One ligand showed very good results because it possesses all of kinetic and thermodynamic parameters which are necessary for its application to PET imaging. Different strategies of functionalization have been studied to obtain bifunctional chelates. A lysine derivative has been coupled to a maleimide function (regioselective of cysteins), to abiotine (which displays a strong affinity for streptavidin) or to a Bodipy pattern for obtaining a bimodal probe (UV-visible and PET). Finally, we present an extension of this bispidine family by increasing the number of coordination functions or by synthesizing tricyclic compounds to modulate the selectivity of these molecules.

Ce travail de thèse avait pour objectif de développer de nouveaux chélatants du cuivre(II) de type bispidine pour des applications en Tomographie à Emission de Positrons. Le 64Cu est un radioisotope métallique dont les propriétés sont intéressantes pour la TEP. Les bispidines sont des chélatants dont la structure est préorganisée et rigide. Cette propriété confère au bispidine de bonnes propriétés de coordination vis-à-vis des métaux de transition, en particulier le cuivre(II). Ce travail présente le développement d’un ligand de type bispidine possédant un groupement phosphonate ainsi que le développement de bispidines permettant la synthèse de nouvelles familles de chélatants pour le cuivre(II). La bispidine phosphonatée a ensuite fait l’objet d’une étude physico-chimique par différentes techniques, révélant ainsi qu’elle possède les caractéristiques requises pour des applications en TEP. Le radiomarquage en présence de 64Cu a été étudié pour une sélection de plusieurs chélatants et montre le fort potentiel des ligands de type bispidine pour la complexation du 64Cu. Enfin, diverses stratégies de fonctionnalisation ont été étudiées pour l’obtention d’un chélatant bifonctionnel basé sur la bispidine phosphonatée. Ces stratégies démontrent la possibilité d’obtenir deux ligands bifonctionnels. De surcroît, deux plateformes bifonctionnelles peuvent faire l’objet de point de départ pour le développement de nouvelles familles de bispidines bifonctionnelles. / This PhD work aimed at developing new bispidine-based copper(II) chelating agents for applications in Positron Emission Tomography (PET). On one hand, 64Cu is a metallic radioisotope which possesses interesting properties for PET imaging and on the other hand, bispidines have a pre-organized and rigid structure. This property makes them good chelating agents for numerous transition metals, particularly copper(II). This work presents the development of a new bispidine-based ligand having a phosphonate pendant arm as well as the development of bispidines allowing the synthesis of new chelating agents for copper(II). The physico-chemical properties of the phosphonated bispidine were thoroughly studied by different techniques, showing that it would be adequat for PET applications. Radiolabeling experiments were also done in the presence of 64Cu for various bispidines and show the high potential of bispidine ligands for the complexation of 64Cu. Finally, several functionalization strategies were studied in order to get bifunctional chelates based on the phosphonated bispidines. This study proved the possibility to develop two bifunctional bispidines based on the phosphonated one and also it allowed us to develop two bifunctional bispidines as synthon for the synthesis of new families of bifunctional bispidines.

A series of dihydroxy bridged copper(II) complexes of the type [(L)Cu(OH)₂Cu(L)]x₂ * nH₂0, where L is 2,2'-bipyridine, 4,4'-dimethyl-2,2'-bipyridine or 1,10-phenanthroline, x is a counter ion, and n is the number of water molecules, was synthesized. In the case of monohydroxy bridged copper(II) complexes, we have found a new method of synthesis for [ (L)₂Cu(OH)Cu(L)₂ ] (ClO₄)₃, where L is 2,2'-bipyridine or 1,10-phenanthroline. We have synthesized five new monohydroxy bridged copper(II) complexes, thus increasing the number of monohydroxy bridged copper(II) complexes to nine. All complexes have been characterized by infrared spectroscopy, UV-visible spectroscopy, magnetic moments, and elemental analysis. The electron spin resonance results establish that the fulvic acids contain organic free radicals as an internal part of their molecular structure. The concentration of unpaired electrons will increase by increasing the pH. The unpaired electron in fulvic acid interacts with the unpaired electron on copper(II) through the Π system, and this will decrease the spin concentration of fulvic acid complexed with copper(II). The displacement of titration curve from a free ligand (fructose-1,6-diphosphate, ribulose-1,5-diphosphate, phospherine, phosphothreonine, and 3-phosphoglyceric acid, to a ligand plus copper(II) (1:1 ratio) shows there is a strong interaction between copper(II) and the corresponding ligand. All complexes absorb UV-visible at 250-300 nm. The absorption intensity changes as a function of pH. Copper (II) forms a complex with fructose-1,6-diphosphate, ribulose-1,5-diphosphate, phosphoserine, phosphothreonine, and 3-phosphoglyceric acid by the ratio of 1:3, 1:3, 1:1, 1:1, and 1:2, respectively.

Orientadores: Fernando Aparecido Sígoli, Italo Odone Mazali / Dissertação (mestrado) - Universidade Estadual de Campinas, Instituto de Química / Made available in DSpace on 2018-08-22T05:10:39Z (GMT). No. of bitstreams: 1 Belini_TabitaCristina_M.pdf: 4357833 bytes, checksum: f01ca369956da0ce911ee6541c29da11 (MD5) Previous issue date: 2012 / Resumo: Nanopartículas de sílica foram obtidas, via método sol-gel, a partir de silicato de sódio em pH alcalino. A reação de precipitação foi conduzida por 24 h, mediante aquecimento sob refluxo, obtendo-se assim um sol de sílica 1 % m/v, podendo ser concentrado a 3 % m/v mediante destilação. Amostras em fase sólida foram preparadas removendo-se a água da suspensão com o auxílio de um spray dryer. As partículas presentes nos sóis apresentam morfologia esferoidal, diâmetro médio de 15 nm e potencial zeta de -28 mV. Já as amostras secas em spray dryer foram caracterizadas como não-cristalinas, o potencial zeta variou para -33,5 mV sendo observado a possibilidade de aglomeração de partículas. A distribuição de tamanho de partículas mostrou-se bimodal, com a primeira população centrada em aproximadamente 15 nm e a segunda, em 100 nm. O processo de adsorção dos íons cobre(II) foi conduzido a partir da suspensão de nanopartículas de sílica 1 % m/v. Adicionou-se cloreto de cobre(II) à suspensão de modo a se obter as concentrações de 1 e 5 mol % de íons cobre(II) em relação à sílica. Esta suspensão final foi processada em spray dryer, obtendo-se amostras em fase sólida. Estas são não-cristalinas, apresentam morfologia esferoidal, potencial zeta de -43 mV para as amostras contendo 1 mol % de íons cobre(II), e -33,7 mV, para 5 mol % de íons cobre(II). A ação biológica das nanopartículas de sílica contendo íons cobre(II) teve foi testada com relação as bactérias Xanthomonas axonopodis e Ralstonia solanacearum e nos fungos Alternaria solani e Colletotrichum gloeosporioides, mostrando eficácia no controle destes quatro patógenos. / Abstract: Silica nanoparticles were obtained by sol-gel method from sodium silicate in alkaline medium. The precipitation reaction was conducted by heating the solution under reflux for 24 h, obtaining a silica sol 1 % w/v, that may be concentrated to 3 % w/v by distillation. Dried samples were obtained removing water in a spray-dryer equipment. The obtained nanoparticles are spheroidal, with an average size of 15 nm and zeta potential of -28 mV. The dried samples were characterized as noncrystalline, the zeta potential of re-dispersed have changed to -33,5 mV and its possible to observe some agglomerated particles after drying. The size distribution is bimodal, being the first population around 15 nm and the second one around 100 nm. The adsorption of copper(II) ions was conducted from 1 % w/v the silica sol. Copper(II) chloride was added silica nanoparticles suspension in order to achieve the concentrations of 1 and 5 mol % of copper(II) ions by silica mol. This final suspension was dried in spray-dryer to obtain solid samples. The latter are noncrystalline, spheroidal, with a zeta potential around -43 mV (samples with copper(II) 1 mol %) and -33,7 mV (samples with copper(II) 5 mol %). The biological activities of the silica nanoparticles containing copper(II) ions were tested against the bacterias, Xanthomonas axonopodis and Ralstonia solanacearum and the fungus, Alternaria solani and Colletotrichum gloeosporioides showing efficacy against these four targets. / Mestrado / Quimica Inorganica / Mestra em Química

This diploma thesis deals with copper(II) ions diffusion in the humic hydrogels. The hydrogels were prepared from several samples of humic acids using different method and their isolation conditions from the original matrix. A selective blocking of functional groups (COOH, OH) was performed in the selected samples of humic acids. These reactive groups were selectively blocked using methylation agent trimethylsilyl-diazomethane. The success of performed methylation and functional groups blocking was verified using a FT-IR spectroscopy. There was carried out the set of diffusion experiments. The experimental arrangement was selected to enable an instantaneous planar source met-hod for data processing. The basis of this method was to determine the copper(II) ions con-centration distribution in the hydrogels. The method consists of slicing of the hydrogels after the diffusion experiments, extraction of the copper ions in the solution and determina-tion of concentration in the extracts from individual slices using UV-VIS spectroscopy. Based on the experimental data the effective diffusion coefficients were determined. The resulting values include both the effect of hydrogels structure and the effect of the reaction between Cu(II) ions and humic acids. There were prepared gels with defined portion of blocked functional groups for selected samples, which allowed to investigate the effect of reactivity on the copper ions diffusion without the significant changes in the gel structure (porosity). The blocking of functional groups reflected in a lower values of diffusion coefficients in comparison to the gels prepared from unmodified humic acids as follows. There was also confirmed the effect of humic acids isolation procedure and their properties on the diffusivity.

Previous studies involving copper (II) complexed with a dissymmetric Schiff base and imidazole derivatives had identified catalase activity of these complexes towards H2O2. Reactions such as this are of great interest due to the important role of copper-based complexes in biological systems. Our research has been conducted to add to the base of knowledge regarding the efforts of other researchers to investigate copper complexes that exhibit similar reactivity as copper-based proteins towards dioxygen. The copper complex chosen for this study contained a tri-dentate Schiff base adduct which, when complexed with an imidazole derivative, limited the manner in which peroxo adducts could bind while providing distinct spectral peaks which were used to conduct kinetic studies. Our results indicate a reaction mechanism by which the role of the complexed copper (II) ion is to activate the peroxo adduct for decomposition through reactions with other peroxide molecules, dioxygen, and water.

The quenching of the [Ru(bipy)3]2+ by Cu2L2+ was studied and the data were plotted with the Stern-Volmer equation. The plot showed a break and was divided into 2 regions, <0.5 and >0.5 Cu2L2+: [Ru(bipy)3]2+ molar ratio. Quenching above the 0.5 Cu2L2+: [Ru(bipy)3]2+ molar ratio was slower (330 x 10-6 M-1s-1) than the quenching rate reaction below 0.5 ratio (387 x 10-6 M-1s-1). With Cu2L2+ being a dimeric complex the break and differences in the quenching reaction rates can be explained in terms of the stoichiometry. When the Cu2L2+: [Ru(bipy)3]2+ ratio is < 0.5, then each [Ru(bipy)3]2+ can interact with 1 Cu2L2+ dimer. At 0.5 then there is exactly a 1:1 ratio RuII : CuII. Above the 0.5 ratio the [Ru(bipy)3]2+ can interact with maybe only one of the Cu2L2+'s in the dimer, or with a [Ru(bipy)3]2+: Cu2L2+ unit, so the quenching is less efficient.

Many new instrumentation and different instrumental techniques have been developed to deal with increasing complexity of samples encountered. Many researchers also have coupled these instrumental techniques with chemometric algorithms to assist in the quantitative analysis of multi-component samples in the hope of alleviating the need of tedious separation and cleanup procedures. These newer chemometric procedures tend to be complex and difficult to understand and implement and are successful under different circumstances and conditions. In this study, we start from the very simple beginning and examine the factors that can present difficulties with obtaining the correct results and observe how the system behaves so as to find a better and simpler chemometric procedure to perform mixture quantitative analysis. We have used simulated and actual experimental data obtained from a UV-VIS spectrophotometric measurement of metal complexes to conduct the study. Well understood and defined systems tend to give good results. The main obstacle has been, and still is, interferences in spectral information one gets from the measurement.