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Mémoire numérisé par la Direction des bibliothèques de l'Université de Montréal.

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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.

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In the Introduction part of this thesis, the chemistry of organo-fluorine compounds including the electronic properties that fluorine impacts onto organic molecules, steric effects, lipophilicity and other characteristics as well as applications and important features of organo-fluorine compounds are briefly discussed. Moreover, summary of the methods for their preparation, modern methods for fluorinations and enantioselective fluorinations, and fluoroalkylation methodologies in organic synthesis are described. Additionally, the chemistry of fluorinated phosphonates including their preparations, important applications and the chemistry of α,α-difluorophosphonates are discussed. The Results and discussion part describes nucleophilic trifluoromethylation of various electrophilic substrates using diethyl trifluoromethylphosphonate. Furthermore, efficient stereoselective synthesis of fluorovinylphosphonates by a base-induced HF elimination of α,α-difluorophosphonates is explained. In addition, synthesis of number of new, structurally diverse compounds, having a difluorophosphonate moiety using the reaction of diethyl difluoromethylphosphonate with various α,β-unsaturated carbonyl compounds, Michael acceptors and imines are reported. Also, preliminary experiments dealing with nucleophilic reactions of...

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STOCKHOLM Roofscape Revisited is the vision of a vertical densification and continuation of the 19th century city. A translation that negotiates the historicity of Stockholm´s cityscape with a contemporary approach, drawing on the existing while projecting forward. Starting from the specific characteristics of  each building that I´ve worked with, the continuation materializes through vertical additions that aim at being playful amplifications of each building´s stylistic language, adhering to the past wile suggesting something new.   THE PROJECT deals with our relation to the architecture of the 19th century city as a central bearer of western history and identity. It investigates the possibility of negotiating the formal diversity and richness of Stockholms historicistic and eclectic styles with a contemporary approach that uses the dreamscapes and fictional imagery from to the world of comics and film, as reference and speculative tool. / STOCKHOLM Roofscape Revisited är en vision om Stockholms fortsatta tillväxt och förtätning. En strategi som använder Stockholms stadssiluett och stenstadens arkitektoniska formrikedom som utgångspunkt för en vertikal förtätning av staden, genom tillbyggnader som utgör ett eko av Stockholms sekelskiftsarkitektur. Förslaget arbetar med ett scenario där fem byggnader runt Danderydsplan från kvarteren, Sädesärlan, Vakteln, Tallkotten, Näktergalen och Domherren, har byggts till med fem våningar. Tillbyggnaderna kan ses som samtida översättningar av byggnaden på vilken de star. En fortsättning som lyfter fram och förstärker specifika detaljer och formmässiga aspekter av ursprunget. Resultatet är tillbyggnader som å ena sidan utgör ett brott med det befintliga, å andra sidan är i tydlig dialog med den historiistiska kontext som stenstaden utgör.