The analysis of metals is now a major application area for ICP-AES, however, the technique suffers from both spectral and non-spectral interferences. This thesis details the application of univariate and multivariate calibration methods for the prediction of Pt, Pd, and Rh in acid-digested and of Au, Ag and Pd in fusion-digested autocatalyst samples. Of all the univariate calibration methods investigated matrix matching proved the most accurate method with relative root mean square errors (RRMSEs) for Pt, Pd and Rh of 2.4, 3.7, and 2.4 % for a series of synihelic lest solutions, and 12.0, 2.4, and 8.0 % for autocatalyst samples. In comparison, the multivariate calibration method (PLSl) yielded average relative errors for Pt, Pd, and RJi of 5.8, 3.0, and 3.5 % in the test solutions, and 32.0, 7.5, and 75.0 % in the autocatalyst samples. A variable selection procedure has been developed enabling multivariate models to be built using large parts of the atomic emission spectrum. The first stage identified and removed wavelengths whose PLS regression coefficients were equal to zero. The second stage ranked the remaining wavelengths according to their PLS regression coefficient and estimated standard error ratio. The algorithms were applied to the emission spectra for the determination of Pt, Pd and Rh in a synthetic matrix. For independent test samples variable selection gave RRMSEs of 5.3, 2.5 and 1.7 % for Pt, Pd and Rh respectively compared with 8.3, 7.0 and 3.1 % when using integrated atomic emission lines. Variable selection was then applied for the prediction of Au, Ag and Pd in independent test fusion digests. This resulted in RRMSEs of 74.2, 8.8 and 12.2 % for Au, Ag and Pd respectively which were comparable to those obtained using a more traditional univariate calibration approach. A preliminary study has shown that calibration drift can be corrected using Piecewise Direct Standardisation (PDS). The application of PDS to synthetic test samples analysed 10 days apart resulted in RRMSEs of 4.14, 3.03 and 1.88%, compared to 73.04, 44.39 and 28.06 % without correction, for Pt, Pd, and Rh respectively.

No description available.

No description available.

O objetivo desta pesquisa consiste em analisar através da caracterização química de fases cristalinas a composição e estrutura; e com a caracterização física a densidade, porosidade e área superficial dos seguintes cimentos endodônticos: MTA Fillapex, AH Plus, Sealer 26 e o Endofill. Para tal, foram realizadas análises dos cimentos antes da manipulação (pó e pastas) e depois da manipulação (corpos de prova). Empregando-se as técnicas de caracterização química: DRX e FRX e como técnicas de caracterização física: Picnometria de Hélio, a porosimetria de mercúrio, distribuição granulométrica e área superficial pela metodologia de BET. A caracterização química detalhou a composição dos cimentos sendo compatível com a descrição do fabricante e forneceu a quantificação das suas fases. A caracterização física mostrou que o MTA Fillapex apresentou os melhores resultados: a menor porosidade, o menor volume médio e o menor diâmetro do poro, o Sealer 26 dentre os cimentos resinosos apresentou o pior resultado, o Endofill mostrou-se melhor que o Sealer 26 tendo a maior densidade, o menor diâmetro das partículas, a distribuição granulométrica mais homogênea comparando-se a este. Os cimentos a base de resina mostraram um diâmetro do poro menor que o Endofill. Estes resultados podem estar ligados diretamente aos requisitos de um material obturador ideal. A metodologia utilizada produziu um detalhamento das características químicas e físicas dos cimentos estudados, mostrando um caminho para novas pesquisas na área. / The objective of this research is to examine through characterization chemical composition and crystallographic phase structure and the physical density, porosity and surface area of root canal sealers: MTA Fillapex, AH Plus, Sealer 26 and Endofill. To this end, we performed analysis of cements before handling (powder or paste) and after manipulation (specimens), employing the techniques of chemical characterization: DRX and FRX and physical characterization: Helium Picnometry, mercury porosimetry, granulometric distribution and surface area by BET method. The chemical characterization detailed the composition of the cements being compatible with the description of the manufacturers and provided the quantification of the phases. The physical characterization showed that MTA Fillapex presented the best results: the lowest porosity, the smallest average volume and the smallest pore diameter; Sealer 26 among the resinous cements presented the worst result; Endofill proved to be better than Sealer 26 having the highest density, the smallest diameter of the particles , and homogeneous granulometric distribution equal to it. The resin-based cements showed a pore diameter smaller than Endofill. These results may be connected directly to the requirements of an ideal endodontic filling material. The methodology used outlined the physical and chemical characteristics of the cements studied, laying the ground to new researches in the area.

Made available in DSpace on 2014-10-09T12:37:04Z (GMT). No. of bitstreams: 0 / Made available in DSpace on 2014-10-09T13:56:36Z (GMT). No. of bitstreams: 1 01914.pdf: 2808501 bytes, checksum: 4602fce3510951b557ac48e622edb655 (MD5) / Tese (Doutoramento) / IPEN/T / Instituto de Pesquisas Energeticas e Nucleares - IPEN/CNEN-SP

Submitted by TIAGO SILVA DA FONSECA (tiago.odonto@hotmail.com) on 2018-08-15T13:52:28Z No. of bitstreams: 1 Tese - Tiago Silva da Fonseca.pdf: 3116289 bytes, checksum: 5bc17261ff2e5cf870764bac9df08bbb (MD5) / Approved for entry into archive by Ana Cristina Jorge null (anacris@fclar.unesp.br) on 2018-08-15T17:23:42Z (GMT) No. of bitstreams: 1 Fonseca_ts_dr_arafo_int.pdf: 3077264 bytes, checksum: 45ffe1976b230616d3be8df487229be6 (MD5) / Made available in DSpace on 2018-08-15T17:23:42Z (GMT). No. of bitstreams: 1 Fonseca_ts_dr_arafo_int.pdf: 3077264 bytes, checksum: 45ffe1976b230616d3be8df487229be6 (MD5) Previous issue date: 2018-03-28 / Fundação de Amparo à Pesquisa do Estado do Amazonas (FAPEAM) / Biodentine é um cimento reparador à base de silicato tricálcico com indicações semelhantes ao MTA. O objetivo deste estudo foi avaliar a resposta do periodonto ao selamento de perfurações de furca em molares de ratos com Biodentine ou MTA e as possíveis alterações séricas em marcadores de atividade hepática e renal. As perfurações realizadas nos primeiros molares da maxila direita de 60 ratos foram preenchidas com Biodentine, MTA ou algodão (Sham). As maxilas contralaterais do grupo Sham foram utilizadas como grupo Controle. Após 7, 15, 30 e 60 dias, o sangue foi coletado e as maxilas foram fixadas e incluídas em parafina (n=5). A partir do soro foram mensurados ou níveis de transaminase glutâmico-oxalacética (TGO), transaminase glutâmico-pirúvica (TGP), ureia e creatinina. O sangue de 5 animais sem qualquer procedimento foi coletado para mensurar os padrões sorológicos de referência. O espaço periodontal (EP), densidade de volume de células inflamatórias (VvCI) e de fibroblastos (VvFb) e o número de osteoclastos TRAP-positivos foram obtidos. Interleucina-6 (IL-6) e osterix foram detectados por imuno-histoquímica. O conteúdo de colágeno birrefringente foi quantificado a partir de cortes corados com picrosirius. Os dados foram submetidos à ANOVA e ao teste Tukey (p≤0,05). Diferenças significantes nos níveis séricos de TGO (p≥0,1258) e TGP (p≥0,5827) não foram detectadas nos grupos Biodentine, MTA e Sham em comparação aos níveis de referência. Aos 7 dias, a concentração de ureia sérica foi significantemente maior nos grupos Biodentine e MTA em comparação aos níveis de referência (p=0,0166). Um nível mais alto de creatinina sérica no grupo Biodentine aos 60 dias foi detectado em comparação aos valores de referência (p=0,0222). Aos 7 dias, os altos valores de VvCI, células IL-6-positivas e número de osteoclastos foram acompanhados por reduzido conteúdo de colágeno no EP alargado dos grupos experimentais. Em todos os períodos, VvCI, número de osteoclastos e de células IL-6-positivas e EP foram significantemente maiores em Sham que nos grupos Biodentine e MTA (p<0,0001). Do 7º ao 60º dia, significante redução de VvCI, expressão de IL-6 e osteoclastos foi acompanhada por significante aumento de VvFb, osteoblastos e conteúdo de colágeno nos grupos Biodentine e MTA. Aos 60 dias, diferenças significantes em VvCI, espessura do LP, imunoexpressão de IL-6 e número de osteoclastos e osteoblastos não foram detectadas entre Biodentine e MTA (p≥0,3255). Aos 30 e 60 dias, o número de osteoblastos osterix-positivos foi significantemente mais alto nos grupos Biodentine e MTA que no grupo controle (p<0,0001) enquanto diferenças significantes no número de osteoclastos não foram observadas (p≥0,8933). A análise bioquímica sugere que Biodentine e MTA não induzem mudanças hepáticas no decorrer do tempo. No entanto, é possível que mudanças renais sejam promovidas por Biodentine. Apesar da reação inflamatória e reabsorção óssea iniciais, o selamento de perfurações de furca com Biodentine e MTA promovem condições para o reparo periodontal. / Biodentine is a calcium silicate-based cement with similar indications of MTA. The aim of this study was to evaluate the periodontium response in the sealing of furcation perforations in rat molars with Biodentine and MTA, and its potential systemic effects in serum levels of hepatic and renal functions. The pulp chamber floor of right upper first molars of 60 rats were perforated and filled with Biodentine, MTA or sterile cotton pellet (Sham); the left first molars were used as control. After 7, 15, 30 and 60 days, the blood was collected and serum glutamic-oxaloacetic transaminase (GOT), glutamic-pyruvic transaminase (GPT), creatinine and urea levels were measured. The blood of 5 rats without any treatment was collected to measure serum reference levels. The maxillary fragments were fixed and processed for paraffin-embedding. The periodontal space (PS), volume density of inflammatory cells (VvIC) and of fibroblasts (VvFb), and number of TRAP-positive osteoclasts were obtained. Interleukin-6 (IL-6), a pro-inflammatory cytokine, and osterix, an osteoblast marker, were detected by immunohistochemistry. The birefringent collagen content was quantified from picrosirius-stained sections. Data were submitted to ANOVA and Tukey test (p≤0.05). Significant differences in GOT (p≥0.1258) and GPT (p≥0.5827) serum levels were not observed in the Biodentine, MTA and Sham groups in comparison with reference levels. At 7 days, the concentration of serum urea increased significantly in the Biodentine and MTA groups compared with reference levels (p=0.0166). A higher concentration of serum creatinine in Biodentine group than reference level (p=0.0222) was detected at 60 days. At 7 days, the high values in VvIC, IL-6-immunolabelled cells and number of osteoclasts were accompanied by reduced collagen content in the enlarged PS of experimental groups. In all periods, VvIC, number of osteoclasts and IL-6, and PS were significantly higher in Sham than Biodentine and MTA groups (p<0.0001). From 7 to 60 days, significant reduction in VvIC, IL-6 immunoexpression and osteoclasts was accompanied by significant increase in VvFb, osteoblasts and collagen content in Biodentine and MTA groups. At 60 days, significant differences in VvIC, width of PS, IL-6 immunoexpression, in the number of osteoclasts and osteoblasts were not found between Biodentine and MTA (p≥0.3255). At 30 and 60 days, the number of osterix-immunolabelled osteoblasts was significantly higher in Biodentine and MTA than control group (p<0.0001) while significant differences in the number of osteoclasts were not observed (p≥0.8933). The biochemical analyses suggest that Biodentine and MTA did not induce changes in the liver over time. However, it is possible that kidney changes may be promoted by Biodentine. Despite the initial inflammatory reaction and bone resorption, the sealing of furcation perforations with Biodentine or MTA provide conditions to the periodontium repair. / FAPEAM 117/2014

Novel applications for calix[4]recorcinarene (C[4]RA) sensing membranes have been investigated. A comprehensive deposition study was carried out, encompassing casting, spin coating and Langmuir Blodgett (LB) deposition. The spin coating thickness depended on the angular velocity w, following the description of d = c.wx with coefficients of x - 0.44 and - 0.48 for concentrations of 1 mg/ml and 2mg/ml respectively. The analysis of the LB deposited films established a thickness of 0.95 nm for a monolayer. Furthermore the C[4]RA, was successfully employed as a deposition matrix for a non surface active polymer, poly-ortho-methoxy aniline (POMA), which can otherwise not be deposited by LB. The composite film showed good homogeneity and based on thickness and UV measurements a structural model for it was developed, in which two polymer strands aligned themselves per C[4]RA layer, resulting in a monolayer thickness of 2.1 - 2.2 nm. The response of the C[4]RA and the composite membranes to a variety of organic and inorganic gaseous pollutants was investigated by Surface Plasmon Resonance studies, conductivity and capacitance measurements and UV spectroscopic studies. The integration of cast films into the gate of a charge flow transistor, is the first application of pure calixarenes in a conduction based sensor. The turn on response of the transistor is modulated by a variety of organic vapours, at the saturation vapour pressure, showing selectivity between polar and non-polar solvents, i.e. chloroform, methanol, acetone and hexane, with no cross sensitivity to water vapour. The modulation lies within factors of 45 for CHCI3 and 13 for CH3OH. The conductivity increase is partially attributed to micro-condensation of the vapours inside the micro-porous membrane. A successful application of this implementation as an explosion guard sensor for acetone is demonstrated. Gold electrodes with and without C[4]RA LB films have been characterised using impedance spectroscopy and cyclic voltammography. The modification of the gold electrodes by the C[4]RA film changes their constant phase element impedance, given by 1/(w.Q)" with w being the angular velocity. The observed values were from Q =0.725-10 -5 Farad and n = 0.87 to Q = 0.828-10-6 Farad and n = 0.82. Organic analyteslike, chloroform and acetone in water can be successfully detected with these electrodes. It is shown by cyclic voltammetry, that the permeability of the C[4]RA LB films is modulated by the organic solvents.

Orientador: Paulo Sérgio Cerri / Resumo: Biodentine é um cimento reparador à base de silicato tricálcico com indicações semelhantes ao MTA. O objetivo deste estudo foi avaliar a resposta do periodonto ao selamento de perfurações de furca em molares de ratos com Biodentine ou MTA e as possíveis alterações séricas em marcadores de atividade hepática e renal. As perfurações realizadas nos primeiros molares da maxila direita de 60 ratos foram preenchidas com Biodentine, MTA ou algodão (Sham). As maxilas contralaterais do grupo Sham foram utilizadas como grupo Controle. Após 7, 15, 30 e 60 dias, o sangue foi coletado e as maxilas foram fixadas e incluídas em parafina (n=5). A partir do soro foram mensurados ou níveis de transaminase glutâmico-oxalacética (TGO), transaminase glutâmico-pirúvica (TGP), ureia e creatinina. O sangue de 5 animais sem qualquer procedimento foi coletado para mensurar os padrões sorológicos de referência. O espaço periodontal (EP), densidade de volume de células inflamatórias (VvCI) e de fibroblastos (VvFb) e o número de osteoclastos TRAP-positivos foram obtidos. Interleucina-6 (IL-6) e osterix foram detectados por imuno-histoquímica. O conteúdo de colágeno birrefringente foi quantificado a partir de cortes corados com picrosirius. Os dados foram submetidos à ANOVA e ao teste Tukey (p≤0,05). Diferenças significantes nos níveis séricos de TGO (p≥0,1258) e TGP (p≥0,5827) não foram detectadas nos grupos Biodentine, MTA e Sham em comparação aos níveis de referência. Aos 7 dias, a concentração de urei... (Resumo completo, clicar acesso eletrônico abaixo) / Abstract: Biodentine is a calcium silicate-based cement with similar indications of MTA. The aim of this study was to evaluate the periodontium response in the sealing of furcation perforations in rat molars with Biodentine and MTA, and its potential systemic effects in serum levels of hepatic and renal functions. The pulp chamber floor of right upper first molars of 60 rats were perforated and filled with Biodentine, MTA or sterile cotton pellet (Sham); the left first molars were used as control. After 7, 15, 30 and 60 days, the blood was collected and serum glutamic-oxaloacetic transaminase (GOT), glutamic-pyruvic transaminase (GPT), creatinine and urea levels were measured. The blood of 5 rats without any treatment was collected to measure serum reference levels. The maxillary fragments were fixed and processed for paraffin-embedding. The periodontal space (PS), volume density of inflammatory cells (VvIC) and of fibroblasts (VvFb), and number of TRAP-positive osteoclasts were obtained. Interleukin-6 (IL-6), a pro-inflammatory cytokine, and osterix, an osteoblast marker, were detected by immunohistochemistry. The birefringent collagen content was quantified from picrosirius-stained sections. Data were submitted to ANOVA and Tukey test (p≤0.05). Significant differences in GOT (p≥0.1258) and GPT (p≥0.5827) serum levels were not observed in the Biodentine, MTA and Sham groups in comparison with reference levels. At 7 days, the concentration of serum urea increased significantly in the B... (Complete abstract click electronic access below) / Doutor

O objetivo desta pesquisa consiste em analisar através da caracterização química de fases cristalinas a composição e estrutura; e com a caracterização física a densidade, porosidade e área superficial dos seguintes cimentos endodônticos: MTA Fillapex, AH Plus, Sealer 26 e o Endofill. Para tal, foram realizadas análises dos cimentos antes da manipulação (pó e pastas) e depois da manipulação (corpos de prova). Empregando-se as técnicas de caracterização química: DRX e FRX e como técnicas de caracterização física: Picnometria de Hélio, a porosimetria de mercúrio, distribuição granulométrica e área superficial pela metodologia de BET. A caracterização química detalhou a composição dos cimentos sendo compatível com a descrição do fabricante e forneceu a quantificação das suas fases. A caracterização física mostrou que o MTA Fillapex apresentou os melhores resultados: a menor porosidade, o menor volume médio e o menor diâmetro do poro, o Sealer 26 dentre os cimentos resinosos apresentou o pior resultado, o Endofill mostrou-se melhor que o Sealer 26 tendo a maior densidade, o menor diâmetro das partículas, a distribuição granulométrica mais homogênea comparando-se a este. Os cimentos a base de resina mostraram um diâmetro do poro menor que o Endofill. Estes resultados podem estar ligados diretamente aos requisitos de um material obturador ideal. A metodologia utilizada produziu um detalhamento das características químicas e físicas dos cimentos estudados, mostrando um caminho para novas pesquisas na área. / The objective of this research is to examine through characterization chemical composition and crystallographic phase structure and the physical density, porosity and surface area of root canal sealers: MTA Fillapex, AH Plus, Sealer 26 and Endofill. To this end, we performed analysis of cements before handling (powder or paste) and after manipulation (specimens), employing the techniques of chemical characterization: DRX and FRX and physical characterization: Helium Picnometry, mercury porosimetry, granulometric distribution and surface area by BET method. The chemical characterization detailed the composition of the cements being compatible with the description of the manufacturers and provided the quantification of the phases. The physical characterization showed that MTA Fillapex presented the best results: the lowest porosity, the smallest average volume and the smallest pore diameter; Sealer 26 among the resinous cements presented the worst result; Endofill proved to be better than Sealer 26 having the highest density, the smallest diameter of the particles , and homogeneous granulometric distribution equal to it. The resin-based cements showed a pore diameter smaller than Endofill. These results may be connected directly to the requirements of an ideal endodontic filling material. The methodology used outlined the physical and chemical characteristics of the cements studied, laying the ground to new researches in the area.

No description available.