The use of hydroxyl radical based reaction (Fenton reaction) for the destruction of organic pollutants has been widely reported in the literature. However, the low pH requirement and rapid hydrogen peroxide consumption rate make the application of conventional Fenton reaction difficult for in-situ treatment. In this study, we conducted a modified Fenton reaction by introducing a chelating agent into the reaction system that could prevent Fe(OH)3 (s) precipitation even at a neutral pH condition and reduce the H2O2 consumption rate by controlling the Fe2+ concentration. A chelating agent (mono-chelate or poly-chelate) combines with Fe2+ or Fe3+ to form stable metal-chelate complexes in solution. This decreases the concentration of Fe2+ in the solution so that reactions can be carried for longer contact times. Experimental results (citrate was the chelating agent) for 2,4,6-trichlorophenol (TCP) showed that TCP degradations were greater than 95% after 2.5 h and 24 h reaction times at fixed pH 5 and 6, respectively. For the same reaction time, the normalized chloride formations were 85% at pH 5 and 88% at pH 6. Several other chlorinated organic compounds were also chosen as the model compounds for detoxification studies because of their chemical structures: trichloroethylene (unsaturated hydrocarbon), carbon tetrachloride (highly oxidized compound), 2,2-dichlorobiphenyl, and biphenyl (a dual-aromatic ring structure). Poly-chelating agents (such as polyacrylic acid-PAA) provide multiple Fe2+/Fe3+ binding sites in the modified Fenton reaction for the oxidation of contaminants (2,2-dichlorobiphenyl, and biphenyl) at a neutral pH environment. Numerical simulation based on the kinetic model developed from the well known Fenton reaction and iron-chelate chemistry fits experiment data well for both standard and chelate modified Fenton reactions. In this dissertation, it was proven that both monomeric (citrate) and polymeric (PAA) chelate modified Fenton reactions were effective for dechlorination of carbon tetrachloride from aqueous phase by the superoxide radical anion. On the other hand, PAA (a poly-chelating agent) can also be used for solid surface modification by polymerization of acrylic acid (monomer). The successful degradations of biphenyl and trichloroethylene by the PAA functionalized silica particles/membrane demonstrate the versatile applications of the chelate modified Fenton reaction.

Dissolved and Colloidal substances (DisCo) and metals are released from wood during thermomechanical pulp (TMP) production. The mechanical treatment causes that these components have a tendency to accumulate in process waters, as the water circulation systems in integrated paper mills are being closed. Disturbances such as pitch depositions on the paper machine (pitch problems), specks in the paper, decreased wet and dry strength, interference with cationic process chemicals, and impaired sheet brightness and friction properties appear in the presence of DisCo substances. The presence of transition metal ions such as manganese results in higher consumption of bleaching chemicals (hydrogen peroxide) and lowers the optical quality of the final product, and addition of complexing agents, such as EDTA or DTPA, to prevent this is needed. The never ending trends to decrease water consumption and increase process efficiency in pulp and paper production stress that it is very important both to know the effects of wood substances on pulping and papermaking and to be able to remove them in an efficient way. Carried out investigations presented in this thesis show that the lipophilic extractives can be removed from TMP press water to high extent. A 90% decrease in turbidity and a 91% removal of lipophilic extractives from TMP press water can be obtained by addition of a cationic surfactant as foaming agent during flotation. Additionally, fibres located in TMP press water are not removed with the foam fraction but purified. A retained concentration of hydrophilic extractives in the process water indicates that the flotation is selective. Moreover, by introduction of a new recoverable surface active complexing agent, a chelating surfactant, manganese ions in the form of chelates can be successfully removed from the pulp fibres and separated from the process water in the same flotation process. iii The findings presented above indicate new possibilities for internal water cleaning and decreased emissions to water if flotation technology is applied in an integrated mechanical pulp mill. / ReGain/FORE

The well-defined ruthenium-carbene complexes reported by Grubbs and co-workers were the first ruthenium catalysts to show good activity and selectivity in metathesis of acyclic and cyclic olefins. Unfortunately the use of the Grubbs type catalysts is limited to the small scale synthesis of polymers and essential organic reactions, due to cost and instability of the catalyst at elevated temperatures. Some of the most successful Grubbs-type catalysts included hemilabile ligands. By releasing a free coordination site (the so-called "on-demand-open-site") for an incoming nucleophile, hemilabile ligands have the ability to increase the thermal stability and activity of a catalytic system, by stabilization of the transition metal centre. Previous studies indicated that the incorporation of a sterically hindered N and 0 chelating ligand increased the stability, activity and selectivity of Grubbs type complexes and increasing the electron density of the complex can influence the stability of a complex and therefore the catalytic performance. In this study alicyclic, bidentate N and 0 chelating ligands (16-19) were modelled in order to evaluate the hemilability of these ligands. The modelling was used as a comer stone from which the synthesis was conducted. Molecular modelling showed that of the four ligands identified only two (16 and 18) could potentially be hemilabile. 17 would rather form a transaunular ether compound. The modelling results were incondusive for ligand 19 and further investigation is necessary for this compound… / Thesis (M.Sc. (Chemistry))--North-West University, Potchefstroom Campus, 2010.

The well-defined ruthenium-carbene complexes reported by Grubbs and co-workers were the first ruthenium catalysts to show good activity and selectivity in metathesis of acyclic and cyclic olefins. Unfortunately the use of the Grubbs type catalysts is limited to the small scale synthesis of polymers and essential organic reactions, due to cost and instability of the catalyst at elevated temperatures. Some of the most successful Grubbs-type catalysts included hemilabile ligands. By releasing a free coordination site (the so-called "on-demand-open-site") for an incoming nucleophile, hemilabile ligands have the ability to increase the thermal stability and activity of a catalytic system, by stabilization of the transition metal centre. Previous studies indicated that the incorporation of a sterically hindered N and 0 chelating ligand increased the stability, activity and selectivity of Grubbs type complexes and increasing the electron density of the complex can influence the stability of a complex and therefore the catalytic performance. In this study alicyclic, bidentate N and 0 chelating ligands (16-19) were modelled in order to evaluate the hemilability of these ligands. The modelling was used as a comer stone from which the synthesis was conducted. Molecular modelling showed that of the four ligands identified only two (16 and 18) could potentially be hemilabile. 17 would rather form a transaunular ether compound. The modelling results were incondusive for ligand 19 and further investigation is necessary for this compound… / Thesis (M.Sc. (Chemistry))--North-West University, Potchefstroom Campus, 2010.

Diss. (sammanfattning) Linköping : Univ., 2003. / Härtill 5 uppsatser.

Thesis (Ph. D.)--University of Missouri--Columbia, 1998. / Typescript. Vita. Includes bibliographical references (leaves: 157-166). Also available on the Internet.

Made available in DSpace on 2014-10-09T12:27:46Z (GMT). No. of bitstreams: 0 / Made available in DSpace on 2014-10-09T14:05:01Z (GMT). No. of bitstreams: 0 / Tese (Doutoramento) / IPEN/T / Instituto de Pesquisas Energeticas e Nucleares - IPEN-CNEN/SP

Nesta dissertação, duas resinas reticuladas comerciais (denominadas, AmberliteGT73 e AmberliteIRC748) foram empregadas para suportar partículas de prata. Os grupos tiol da GT73 e ácido iminodiacético da IRC748 presentes nessas resinas foram empregados para a fixação de íons Ag+ a partir de solução aquosa. Posteriormente, os íons Ag+ foram reduzidos pelo emprego de três redutores diferentes em pH alcalino, denominados hidrazina, hidroxilamina e formaldeído (pH  12). A morfologia e a impregnação de prata dos materiais binários assim obtidos foram avaliadas por meio de microscópio eletrônico de varredura equipado com detector de elétrons retro-espalhados (SEM-BSE). O detector de espectrometria de energia dispersiva de raios-X (EDAX) acoplado ao SEM permitiu a observação de partículas de prata. Os espectros de raios-X revelaram a presença do metal nas superfícies interna e externa das microesferas dos compósitos. A quantidade de prata incorporada foi determinada pelo método titulométrico, empregando solução padrão de tiocianato de potássio. As características antibactericidas dos compósitos foram avaliadas em colunas contendo pérolas de resina por onde foram percoladas suspensões da bactéria Escherichia coli auxotrópica AB1157 (tipo selvagem) nas concentrações de 103 a 107 células/mL. A avaliação biocida mostrou que estes materiais foram completamente bactericidas, sendo efetivos na eliminação da bactéria em poucos minutos. Esta ação biocida foi atribuída à combinação da atuação da prata e dos grupos funcionais das resinas / In this work, two different commercial cross-linked resins (namely, Amberlite GT73 and AmberliteIRC748) were employed for anchoring silver. The SH and the N(CH2COOH)2 groups, respectively present on these resins, were used for the Ag+ chelation from aqueous solution. The Ag+ ions were reduced by employing three different reductants, namely hydrazine, hydroxylamine and formaldehyde (under alkaline pH). The produced composites were characterized by thermogravimetry (TG-DTG) and scanning electron microscopy equipped with backscattered scanning electron detector (SEM-BSE). Energy dispersive X-ray spectroscopy (EDS) coupled to SEM allowed the observation of submicron particles of silver and chemical microanalysis of emitted X-rays revealed the presence of metal on the internal and external surfaces of the composite microspheres. The amount of incorporated silver was determined by titration. The antibacterial activity of the silver/resin composites were determined towards 103 to 107 cells/mL dilutions of the auxotrophic AB1157 Escherichia coli strain, showing that the networks containing anchored submicron silver particles were completely bactericidal within a few minutes due to the combined action of silver and functional groups of the resins

Submitted by (lucia.rodrigues@ufrpe.br) on 2016-08-17T11:10:50Z No. of bitstreams: 1 William Ramos da Silva.pdf: 1949081 bytes, checksum: c61378bed7319d565cc47084de59c025 (MD5) / Made available in DSpace on 2016-08-17T11:10:50Z (GMT). No. of bitstreams: 1 William Ramos da Silva.pdf: 1949081 bytes, checksum: c61378bed7319d565cc47084de59c025 (MD5) Previous issue date: 2016-07-29 / Conselho Nacional de Pesquisa e Desenvolvimento Científico e Tecnológico - CNPq / The generation of residues through mining is a potential risk of contamination of soil, water, plants and animals. For decades, the municipality of Santo Amaro da Purificação - BA has suffered the impacts caused by improper and inadequate release of thousands of tons of siderurgy slag contaminated mainly by Cd and Pb, and exposure of these contaminants to the population through the distribution of this material to landfills in squares, streets and homes. The city is now known for presenting the greatest human contamination by Pb in the world. In order to understand the impacts of residues in soil and the risk of human contamination from contaminated soil, this study investigated the phytoextraction by maize and castor as a technique for remediation of these soils and to evaluate the risk of human contamination by heavy metals added to the soil by waste. For this, an experiment was conducted in a greenhouse with the use of the two plant species and soil application of inducing agents Phytoextraction (NTA and citric acid). After the cultivation, they evaluated the levels of As, Cd, Pb and Zn in soil and plant to evaluate the potential remediation technique. Fractionation of metals in the soil and bioaccessibility tests to assess the risk of contamination were also performed. The application of chelating agents citric acid and NTA and increased absorption of heavy metals by maize and castor. Despite the removal of metals by application of citric acid is smaller, this is more suitable due to its higher degradability and assist in inhibiting the phytotoxicity of the metals. Corn showed better phytoextraction ability to As, Cd, Pb and Zn in the study. The castor, despite having high concentrations of metals translocated, presented accumulation in roots, can be used as phytoextabiletion plant and generating economic benefits for the production of non-edible vegetable oil. The presence of metal contaminants from the ground indiscriminately in the area of the former COBRAC presents a high risk of contamination of humans through exposure of metals. / A geração de resíduos através da mineração representa um risco potencial de contaminação do solo, recursos hídricos, plantas e animais. Durante décadas, o município de Santo Amaro da Purificação – BA tem sofrido os impactos causados pela liberação indevida e inadequada de milhares de toneladas de escória de siderurgia, contaminada principalmente por Cd e Pb, e pela exposição destes contaminantes à população através da distribuição desse material para aterros em praças, ruas e residências. A cidade hoje é conhecida por apresentar a maior contaminação humana por Pb no mundo. Com a intenção de entender os impactos causados pelos resíduos nos solos, bem como os riscos de contaminação humana por solo contaminado, o presente trabalho objetivou estudar a fitoextração por milho e mamona como uma técnica para remediação desses solos e avaliar o risco de contaminação humana pelos metais pesados adicionados ao solo pelos resíduos. Para isto, foi realizado um experimento em casa de vegetação com a utilização das duas espécies vegetais e aplicação ao solo de agentes indutores da fitoextração (ácido cítrico e NTA). Após o período de cultivo, foram avaliados os teores de As, Cd, Pb e Zn no solo e na planta para avaliar o potencial da técnica de remediação. Fracionamento dos metais no solo e testes de bioacessibilidade para avaliar o risco de contaminação foram também efetuados. A aplicação dos agentes quelantes ácido cítrico e NTA aumentou a absorção de metais pesados por milho e mamona. Apesar da remoção dos metais com aplicação de ácido cítrico ser menor, este é mais indicado por apresentar maior degradabilidade e auxiliar na inibição da fitotoxicidade dos metais. O milho apresentou melhor capacidade fitoextratora para As, Cd, Pb e Zn no solo em estudo. A mamona, apesar de não ter translocado concentrações altas dos metais, apresentou acúmulo nas raízes, podendo ser utilizada como planta fitoestabilizadora e geradora de benefícios econômicos pela produção de óleo vegetal não comestível. A presença de metais contaminantes do solo de forma indiscriminada na área da antiga COBRAC apresenta risco elevado de contaminação dos seres humanos através da exposição dos metais.

Made available in DSpace on 2014-10-09T12:27:46Z (GMT). No. of bitstreams: 0 / Made available in DSpace on 2014-10-09T14:05:01Z (GMT). No. of bitstreams: 0 / A radiomarcação de biomoléculas específicas com o tecnécio-99m 99mTc utilizando agentes quelantes bifuncionais é um campo em crescimento na Medicina Nuclear. Em especial, a classe de peptídeos regulatórios, como a Neurotensina, participa de processos fisiológicos essenciais no organismo, como o crescimento tumoral. O objetivo do presente trabalho foi o estudo comparativo da influência dos agentes quelantes bifuncionais 6-hidrazinonicotinamida (HYNIC) e S-acetil-mercaptoacetiltriglicina (MAG3), no comportamento in vitro e in vivo do análogo duplamente estabilizado da Neurotensina(8-13) radiomarcado com 99mTc, em células tumorais de mama da linhagem MDA-MB-231. Um elevado rendimento radioquímico (> 97%) e estabilidade frente aos agentes transquelantes foi observado para ambos análogos radiomarcados. Foram também obtidos comportamentos similares in vitro, no que diz respeito à porcentagem de ligação às proteinas plasmáticas (aproximadamente 22%), estabilidade metabólica, ligação aos receptores celulares (intervalo nM) e taxas de internalização/externalização para ambos radiocomplexos. A maior lipofilicidade encontrada para o análogo radiomarcado via MAG3 refletiu nas principais diferenças nos estudos de biodistribuição. A degradação do análogo radiomarcado via HYNIC nos estudos de estabilidade metabólica in vivo aos 90 min levou a menor retenção tumoral (0,44±0,02% DI/g), e consequentemente, às menores razões tumor/órgãos não-alvos (< 5%). Embora a superioridade do traçador marcado via MAG3 tenha sido comprovada no presente estudo, um redesenho estrutural objetivando contornar a alta captação no trato gastrointestinal deve ser realizada a fim de que sua potencial aplicabilidade não seja comprometida. / Tese (Doutoramento) / IPEN/T / Instituto de Pesquisas Energeticas e Nucleares - IPEN-CNEN/SP