Materiais de Referência (MR) de substâncias químicas têm ampla aplicação, sobretudo na área analítica, servindo de referência para validação de métodos, calibração de instrumentos e controle de qualidade, estabelecendo a comparabilidade de resultados analíticos em escala global e permitindo a transferência da exatidão entre métodos, laboratórios e padrões. Norteado por essas necessidades, o trabalho apresenta uma proposta para certificação de MR baseada nas orientações preconizadas por diretrizes e normas internacionais, principalmente as que seguem o ISO Guia 34, para estabelecer as propriedades certificadas através de técnicas analíticas de Espectrometria de Massas de Alta Resolução, Ressonância Magnética Nuclear, de ¹H e de ¹³C, e de Análise Elementar CHN. A certificação contemplou as caracterizações qualitativa e quantitativa, ensaio de estabilidade e o cálculo da estimativa da incerteza da medição. Como resultado, foi produzido e certificado um lote piloto de MR de β-N-metilamino-alanina (BMAA), uma toxina obtida in-house através de síntese química e purificação, cujos valores de propriedades certificadas foram rastreáveis ao SI e acompanhadas da estimativa da incerteza da medição. / Reference Materials (RM) of chemicals have wide application, particularly in the analyses, providing a reference for validation of methods, instrument calibration and quality control, establishing the comparability of analytical results on a global scale and enabling the transfer of accuracy between methods, laboratories and standards. Guided by these requirements, the paper presents a proposal for certification of MR based on the guidelines recommended by international guidelines and standards, especially those which follow the ISO Guide 34, to establish the certified properties through analytical techniques of mass spectrometry High resolution Nuclear Magnetic Resonance, ¹H and ¹³C, and CHN elemental analysis. The certification included qualitative and quantitative characterization, stability test and the calculation of the estimate of measurement uncertainty. As a result, was produced and certified a pilot batch of RM β-N-methylamino-alanine (BMAA), a toxin obtained in-house via chemical synthesis and purification, whose property values are certified and traceable to the SI accompanied by an estimative of the uncertainty of measurement.

Materiais de Referência (MR) de substâncias químicas têm ampla aplicação, sobretudo na área analítica, servindo de referência para validação de métodos, calibração de instrumentos e controle de qualidade, estabelecendo a comparabilidade de resultados analíticos em escala global e permitindo a transferência da exatidão entre métodos, laboratórios e padrões. Norteado por essas necessidades, o trabalho apresenta uma proposta para certificação de MR baseada nas orientações preconizadas por diretrizes e normas internacionais, principalmente as que seguem o ISO Guia 34, para estabelecer as propriedades certificadas através de técnicas analíticas de Espectrometria de Massas de Alta Resolução, Ressonância Magnética Nuclear, de ¹H e de ¹³C, e de Análise Elementar CHN. A certificação contemplou as caracterizações qualitativa e quantitativa, ensaio de estabilidade e o cálculo da estimativa da incerteza da medição. Como resultado, foi produzido e certificado um lote piloto de MR de β-N-metilamino-alanina (BMAA), uma toxina obtida in-house através de síntese química e purificação, cujos valores de propriedades certificadas foram rastreáveis ao SI e acompanhadas da estimativa da incerteza da medição. / Reference Materials (RM) of chemicals have wide application, particularly in the analyses, providing a reference for validation of methods, instrument calibration and quality control, establishing the comparability of analytical results on a global scale and enabling the transfer of accuracy between methods, laboratories and standards. Guided by these requirements, the paper presents a proposal for certification of MR based on the guidelines recommended by international guidelines and standards, especially those which follow the ISO Guide 34, to establish the certified properties through analytical techniques of mass spectrometry High resolution Nuclear Magnetic Resonance, ¹H and ¹³C, and CHN elemental analysis. The certification included qualitative and quantitative characterization, stability test and the calculation of the estimate of measurement uncertainty. As a result, was produced and certified a pilot batch of RM β-N-methylamino-alanine (BMAA), a toxin obtained in-house via chemical synthesis and purification, whose property values are certified and traceable to the SI accompanied by an estimative of the uncertainty of measurement.

Submitted by Marco Antônio de Ramos Chagas (mchagas@ufv.br) on 2017-07-19T11:04:46Z No. of bitstreams: 1 texto completo.PDF: 604848 bytes, checksum: 7c25bf32f62cf32aaf0bfa931de7d9bd (MD5) / Made available in DSpace on 2017-07-19T11:04:46Z (GMT). No. of bitstreams: 1 texto completo.PDF: 604848 bytes, checksum: 7c25bf32f62cf32aaf0bfa931de7d9bd (MD5) Previous issue date: 2001-11-30 / Coordenação de Aperfeiçoamento de Pessoal de Nível Superior / As áreas de vegetação rupestres de altitude são ecossistemas bastante peculiares que ocorrem nas posições mais elevadas das principais sistemas montanhosos do Brasil. A flora é marcada por alto grau de endemismo e uma grande quantidade de espécies adaptadas morfológica e fisiologicamente as condições edafo climáticas locais. A vegetação apresenta diferenças florísticas de acordo com a litologia predominante podendo ser individualizados as áreas sobre quartzito daquelas sobre rochas ígneas e sobre concreções lateríticas. As tipologias vegetais ocorrentes nas áreas de vegetação rupestre de altitude foram individualizadas em estrato rupícola, estrato herbáceo (campos) e estrato arbustivo-arbóreo (matas e escrubes), sendo observado o controle edáfico sobre cada uma destas tipologias. Os solos nesse ecossistema são rasos, arenosos, pobres em nutrientes e ricos em ferro e alumínio trocáveis. Por estas razões, associadas às baixas temperaturas médias diárias, a decomposição da matéria orgânica é lenta, ocorrendo grandes acúmulos de substâncias húmicas no solo. Estas por sua vez passam a desempenhar um importante papel na retenção de umidade e de nutrientes, e na complexação de Fe e Al. A movimentação de matéria orgânica associada a Fe e Al, que caracteriza o processo de podzolização, ocorre com freqüência nos Complexos Rupestres de Altitude. Ocorrem Neossolos Litólicos, Organossolos, Cambissolos Húmicos e Hísticos, e Espodossolos. Grande parte destes solos não têm classificação definida pelo Sistema Brasileiro de Classificação de Solo nos níveis categóricos inferiores, sendo neste trabalho propostas emendas ao sistema. Observou-se o predomínio das frações humificadas na matéria orgânica do solo sendo grande parte desta composta por ácidos húmicos e fúlvicos. As características físico-químicas destes compostos revelaram sua natureza fortemente aromática e condensada, indicando um alto grau de humificação, características estas relacionadas a forte estabilidade destes compostos, o que resultou no acúmulo de matéria orgânica no solo. Algumas amostras assemelharam-se a ácidos húmicos extraídos de carvão, indicando um histórico de ação do fogo nestas áreas. As técnicas de espectroscopia no UV-visivel, termogravimetria e análise elementar condensada resultaram das em substâncias variáveis indicadoras húmicas, da produzindo natureza aromática e informação correlata e consistente. Substâncias húmicas extraídas de horizontes espódicos puderam ser discriminadas das demais, apresentando alta aromaticidade, indicada por baixas razões atômicas H:C, elevados índices termogravimétricos, e alta absorvância de luz na faixa de UV e visível. Pela análise discriminante dos ácidos húmicos, extraídos de solos sob diferentes tipologias vegetais e litologias, observaram-se diferenças significativas entre grupos, indicando o efeito da cobertura vegetal, como matéria prima, e do tipo de rocha, como condicionador das características da matriz mineral, nas características fisico quimicas destas substâncias. / The areas of altitude field vegetation are very peculiar ecosystems that occur at the upper most Brazilian mountain ranges. It ́s flora is marked by a high number of endemic species with morphological and physiological adaptations to pedological and climatic conditions. It ́s peculiar vegetation presents floristic variations according to the dominant lithology making it possible to distinguish quartizitic areas from those on crystalline igneous rocks and lateritic pisolithes. The vegetation rupicolous, types occurring herbaceous in (grassland) Brazilian and Highlands arboreal-shrubby were separated (shrubs into and trees) formation, themselves strongly controlled by edaphic characteristics. The soils in these ecosystems are normally shallow, coarse textured, nutrient poor and rich in exchangeable iron and aluminium. These characteristics, associated with decomposition low annual favour the temperatures accumulation of substances in the soil. These humic substances and reduced significant organic amounts matter of humic have an important role in nutrient and water retention, and in the formation of Al and Fe complexes. The movement of organic matter associated with Fe and Al, which characterises the podzolization process, is frequently observed in these areas. According to the Brazilian Soil Classification System the main soil classes observed are the “Neossolos Litólicos”, “Organossolos”, “Cambissolos Húmicos” and “Cambissolos Hísticos”, and “Espodossolos”. Due to the lack of appropriate criteria for the classification at lower levels some proposal to the actual classification system were made. The humified fraction of soil organic matter were dominant in these soils, being composed mainly of humic and fulvic acids. The physical and chemical characteristics of these compounds revealed a strongly aromatic and condensed nature, indicating a high humification degree. These characteristics are related to the high stability of these substances, resulting in the accumulation of organic matter in soils. Some humic substances were similar to “Black Carbon”, indicating a historic fire occurrence in these areas. The visible-UV spectroscopy, termogravimetry and elemental analysis resulted in consistent and correlated information, corroborating the aromatic and condensed nature of the humic substances. It was possible to separate humic substances of spodic horizons from others due to their high aromatic character, indicated by low H:C atomic ratios, high termogravimetric indexes and high absorption in the UV and visible spectra. Through the discriminant analysis of humic acids extracted from soils on different vegetation and geologic areas, significant differences amongst groups were observed indicating the effect of the vegetation type and of the rock type to the mineral matrix characteristics, as well as to the physical and chemical characteristics of the humic substances. / Tese importada do Alexandria

Surface functionalised silica materials have been prepared, followed by the extensive testing of their ability to remove metal ions from aqueous solutions. Modifications include ligand attachment and polymer grafting from the silica surface whilst the metals tested range from first row transition metals right through to the lanthanides and actinides. Characterisation of the materials produced has been of paramount importance for the understanding of the modification process and this is also extensively discussed. Atom transfer radical polymerisation (ATRP) has been used as the primary polymerisation method. Following polymerisation of 2-hydroxyethyl methacrylate (HEMA), post functionalisation was attempted. However, this was found to cause severe cross-linking and all attempts to attach ligands to this failed. Nonetheless, this process was transferred to grafting from silica surfaces and a novel approach to the characterisation of this material was implemented. (3-aminopropyl) triethoxysilane (APTES) was reacted with multiple forms of silica, primarily ZEOprep silica (average particle size 71.48 πm) and fumed silica (0.007 μm). This produced an amine coated surface to which 2-bromoisobutyryl bromide (BIBB) was attached, providing the required surface for radical polymerisation to proceed with a selected monomer. Solid State Nuclear Magnetic Resonance (SSNMR) has been utilised as the major characterisation technique for each step, leading to significant understanding of how this occurs. Thermogravimetric Analysis (TGA) and elemental analysis has supported this method at each stage whilst also enabling one to calculate the moles of APTES present, per gram of APTES-functionalised silica. For the ZEOprep silica this was calculated to be at up to 1.51 x 10-3 mol g-1 and for the fumed silica 1.63 x 10-3 mol g-1. As well as testing the selective nature of these materials, solutions of individual ions and radionuclides were used to measure the effectiveness of the materials for a specific ion. Rd values for these metals ions including solutions of Co(II), Ni(II), Cu(II), Cd2+, Eu(III) and [UO2]2+ have reached values ranging from 7.49 x 104 mL g-1 to as high as 2.17 x 109 mL g-1. These values are regarded as outstanding by other groups that have reported similar results and these are discussed in the report. This range includes values that were observed when competing Na+ and Ca2+ ions were present at 0.5 % and 1 % (w/w). pH testing was also investigated with the materials using a solution of europium ions to determine the most effective range and this was found to fall between pH 4 and 5. X-ray Photoelectron Spectroscopy (XPS) has been utilised to help gain an understanding of the binding between Cu(II) ions and APTES, suggesting that copper ions bind with oxygen atoms closer to the silica surface as well as the nitrogen atoms at the end of the ligand. Meanwhile STEM (Scanning Transmission Electron Microscope) has been used to show how effectively the surface area of the material is used by imaging the europium ions over a sample of APTES-functionalised fumed silica. Ligands and polymers have been focussed on to build a catalogue of functional materials and this has been achieved in collaboration with PhosphonicS Ltd. The most significant finding from these selective investigations was that uranyl ions were found to be the most readily removed. Cu(II) and Eu(III) ions were also removed relatively effectively whilst Co(II), Ni(II), Zn2+ and Cd2+ proved the most challenging but certainly not impossible. [UO2]2+ concentrations were reduced from 17.1 ppm to 1.6 ppm after 4 weeks with use of the ligand SEA (2-aminoethyl sulfide ethyl silica), even with six other metal ions present at similar initial concentrations and a starting pH of 4.67 by adding just 50 mg of the material to a 45 mL solution.