Functional water-soluble polymers find applications in a variety of fields including waste-water treatment, pharmaceuticals, cosmetics, drug delivery, and hygiene. Despite the increased demand for these products, understanding of their synthesis by free-radical aqueous-phase polymerization has lagged behind that of polymers produced in organic solvents. In this doctoral work, the free-radical batch and semibatch aqueous-phase polymerization of N-vinylpyrrolidone (NVP), N-vinylformamide (NVF), N-vinylimidazole (NVI) and quaternized vinylimidazole (QVI), as well as NVP polymerized in n-butanol, has been studied. Kinetic models are developed to describe monomer conversion and polymer molecular weight (MW) behaviour of these systems. The expressions developed from independent pulsed-laser studies for propagation (kp) and termination (kt) rate coefficients, including their variation with monomer concentration and conversion, are shown to provide an excellent description of aqueous-phase NVP polymerization. Polymerization of NVP in butanol and of NVF in water are well-represented by the base NVP model, with differences in polymerization rate and polymer MWs simply accounted for by the differences in kp for the systems, indicating that the kt behaviour must be quite similar. The NVI/QVI study demonstrates the importance of a pH-dependent degradative addition reaction to monomer for NVI, with polymerization behaviour identical to that of QVI for pH 1, an effect captured in the model developed to describe the system. The aqueous-phase copolymerization of NVP and NVF was also studied, and reactivity ratios were determined to be very close to unity. This information was combined with the kp and kt expressions used to describe NVP and NVF homopolymerizations, with no other additional parameters required to model the copolymerization rate, copolymer composition and copolymer MW. This result demonstrates that the improved homopolymerization knowledge of these water-soluble monomers can be easily extended to understand their behaviour in copolymerization. / Thesis (Ph.D, Chemical Engineering) -- Queen's University, 2011-12-21 16:05:14.904

Les Offices, monument emblématique de la Renaissance florentine, restent, malgré leur célébrité, encore curieusement méconnus. Considérés comme l’ancêtre des musées européens, ils sont construits par Giorgio Vasari pour accueillir les magistratures de Cosimo I, puis partiellement transformés en galerie par Francesco I. Si la présence d’ateliers d’artistes y est attestée dès 1586, on sait peu de choses sur leur nature et rien sur leur organisation ou leur raison d’être. Fondée sur le dépouillement systématique des archives florentines, notre thèse se propose de retracer l’histoire des ateliers des Offices sous le règne de Ferdinando 1(1587-1609). L’étude combinée des documents, des plans inédits et des oeuvres conservées nous a permis de reconstituer la structure et le fonctionnement des Offices. Grâce à ces sources, nous avons défini et expliqué l’emplacement des ateliers d’artistes et de savants dans le bâtiment, qui était auparavant inconnu : nous avons ainsi pu déterminer plusieurs pôles d’activités, répartis dans tout le bâtiment. En effet, comme dans la ville, les ateliers sont placés, selon leur discipline, dans des quartiers bien distincts. L’identité de ces artistes et savants, ainsi que leurs conditions de travail, ont été établis à l’aide d’une documentation administrative complexe. Nous avons également examiné leur production: objets d’art, remèdes pharmacologiques et instruments scientifiques se caractérisent tous par leur innovation technique. Cette production est en grande partie employée à servir les intérêts politiques du grand-duc, puisqu’elle est envoyée à travers toute l’Europe comme cadeaux attestant du prestige médicéen. Le succès de cette politique provoque d’ailleurs une certaine émulation auprès des cours européennes. En examinant les cas de Pesaro, de Prague et de Paris, au Louvre, nous montrons que les princes européens cherchent à importer le modèle des Offices, en l’adaptant à leurs propres intérêts. / The Uffizi, emblematic monument of the Florentine Renaissance, are still, in spite of their fame, oddly unknown. Considered as the ancestor of the European museums, they were built by Giorgio Vasari to cater for Cosimo I’s public offices, then were partly transformed into a gallery by Francesco I. Even if the presence of workshops is attested ever since 1586, very few about their nature and nothing about their organisation or their purpose is known. Our thesis, based on a comprehensive assimilation of the Florentine archives, intends to recount the history of the Uffizi workshops during Ferdinando I’s reign (1587-1609). The combined study of the documents, the unpublished maps and of the preserved pieces, has enabled us to piece together again the structure and the functioning of the Uffizi. Thanks to these sources, we have defined and explained the location of the artists’ workshops and of scientists inside the building which was unknown before : so we could determine several functional skill areas shared out through the whole building. Indeed, as in town, die workshops are located, depending on their discipline, in separate districts. The identity of these artists and scientists as well as their working conditions, have been set up thanks to a complicated administrative documentation. We have also looked over their production : art objects, pharmacological medicines and scientific instruments are all characterised by their technical innovation. This production is to a great part used to serve die grand-duke’s politica interests because it is sent throughout all Europe as gifts showing the Medicean prestige. The success of this policy causes moreover some emulation in the European courts. By studying Pesaro’s case, in Prague and Paris, we show that die European princes try to introduce the example of die Uffizi, adapting it in their own interests.

Made available in DSpace on 2014-06-11T19:23:11Z (GMT). No. of bitstreams: 0 Previous issue date: 2010-06-28Bitstream added on 2014-06-13T20:10:45Z : No. of bitstreams: 1 godoi_lm_me_jabo.pdf: 221877 bytes, checksum: d6a13644f869b633dd790316dd00f0f4 (MD5) / Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq) / Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES) / Para conhecer o potencial de plantas de cobertura no fornecimento de nitrogênio para o milho, em sistema de plantio direto, foi avaliado o N potencialmente mineralizável (N0) do solo por meio de ensaio de incubação aeróbia de longa duração e o N disponível por meio dos extratores químicos KCl a quente, Dakota do Sul modificado e tampão fosfato borato a pH 11,2. Foram utilizadas amostras de solo de experimento a campo, instalado em área de Latossolo Vermelho argiloso e conduzido em delineamento em blocos casualizados, com cinco tratamentos: testemunha com vegetação espontânea, sorgo, milheto, mucuna-preta e feijão-de-porco, e cinco repetições. A coleta de solo nas parcelas foi feita após a dessecação das plantas de cobertura e antes do cultivo de milho, nos anos agrícolas de 2007/2008 e 2008/2009. O solo coletado, representativo da profundidade de 0 a 10 cm, foi utilizado no ensaio de incubação aeróbia, em experimento em vasos, com milho, e para as análises químicas. A eficiência dos extratores foi avaliada por meio de testes de correlação, empregando como variáveis de referência o N0 e o N mineralizado acumulado por 30 semanas, obtidos no ensaio de incubação aeróbia, e a produção de matéria seca e o N acumulado na parte aérea do milho, obtidos no experimento em vasos. As plantas de cobertura não diferem entre si quanto ao potencial de fornecimento de N para o milho. O método do KCl a quente é capaz de predizer a mineralização de N, porém os métodos químicos avaliados para predizer o N disponível não são eficientes / Aiming to determine the potential of cover crops to supply nitrogen for corn in no-tillage system, it was evaluated the soil potentially mineralizable N (N0) by long-term aerobic incubation and available N by chemical extractants (hot KCl, modified South Dakota and pH 11.2 phosphate-borate buffer). Soil samples were collected from a field experiment, installed in an Udox and carried out in a randomized block design with five treatments (control with spontaneous vegetation, Sorghum bicolor, Pennicetum glaucum, Mucuna aterrima and Canavalia ensiformis) and five replications. Plots soil sampling was made after the cover crops desiccation and before growing the corn in the agricultural seasons of 2007/2008 and 2008/2009. Soil samples collected from 0 to10 cm depth were used for long-term aerobic incubation, pots experiment with corn, and for soil chemical analysis. Extractants efficiency was evaluated by correlation tests, using as reference the N0 and the mineralized accumulated N over 30 weeks obtained from long-term aerobic incubation, dry matter production and N accumulated in maize shoots, obtained from pots experiment. Cover crops do not differ in their potential to supply nitrogen for corn. Hot KCl is able to predict the N mineralization but the chemical methods evaluated to predict the available nitrogen are not efficients

<p> Variational calculations for hypernuclei and their corresponding nuclear cores have been performed with phenornenological effective Ʌ -N and N-N interactions. Effects of deformation and Majorana exchange on the Ʌ binding energies have been studied. The influence of density dependence in both the Ʌ-N and N-N force has been investigated . The three-body ɅNN interaction has also been considered qualitatively. All these effects help to reduce the Ʌ binding energies in hypernuclei. </p> <p> In addition to the variational calculations, the rigid alpha model has been used to determine the Ʌ binding energy in (5 Ʌ - He). A comparison of the methods is given. </p> Finally, excited states of some hypernuclei have been calculated using the variational ground state equilibrium size. </p> / Thesis / Doctor of Philosophy (PhD)

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No description available.

In this paper, some of the work by Talbott has been repeated and other reactions of 4-picoline and pyridine N-oxides with aromatic halogen compounds have been investigated.

Gegenstand der vorliegenden Arbeit ist die Untersuchung der kationisch initiierten Oligomerisation von N-Vinylformamid mit Iod, Brom, Trifluormethansulfonsäure und Trifluormethansulfonsäure-trimethylsilylester. Quantenchemische Berechnungen zur Konformation und zur Elektronendichteverteilung von N-Vinylformamid, sowie zu seiner Reaktion mit Elektrophilen werden vorgestellt. Die Struktur der erhaltenen Oligomere wird mittels 1H- und 13C-NMR-Spektroskopie, MALDI-TOF-MS, GPC, IR-Spektroskopie, Thermogravimetrie und quantitativer Elementaranalyse untersucht. Die Abhängigkeit von Ausbeute, mittleren Polymerisationsgrad und Kopfgruppenfunktionalität der erhaltenen Oligo(N-vinylformamide) vom Initiator, sowie von der Polarität des Lösemittels, dem eingesetzten Monomer/Initiator-Verhältnis und der Reaktionstemperatur wird vorgestellt. Im Vergleich zum N-Vinylformamid werden N-Vinylacetamid, N-Methyl-N-vinylformamid, N-Methyl-N-vinylacetamid und N-Vinylpyrrolidon auf ihre Fähigkeit untersucht, mit Initiatoren der kationischen Polymerisation Oligomere zu bilden. Mit N-Deutero-N-vinylformamid als Monomer und der 2H-NMR-Analyse der erhaltenen Oligomere wird der Einfluß der NH-Eliminierung während der Oligomerisation von N-Vinylformamid untersucht. Ausgehend von den experimentellen Ergebnissen wird ein für die Vinylpolymerisation neuer Mechanismus für die Oligomerisation von N-Vinylformamid vorgeschlagen und diskutiert. / The topic of the dissertation is the survey of the cationically initiated oligomerization of N-vinylformamide with iodine, bromine, trifluoromethanesulfonic acid, and trifluoromethanesulfonic acid trimethylsilylester as initiators. Quantum chemical calculations on the conformation and the electron density of N-vinylformamide, as well as on its reaction with electrophiles are presented. The structure of the obtained oligomers is investigated with 1H- and 13C NMR spectroscopy, MALDI-TOF-MS, GPC, IR spectroscopy, thermal decomposition, and quantitative combustion analysis. The influence of the polarity of the solvent, of the initiator, of the reaction temperature, and of the monomer/initiator ratio on yield, degree of polymerization, head group functionality, and chain structures of the obtained oligo(N-vinylformamide) is investigated. In comparison with N-vinylformamide, the ability of N-vinylacetamide, N-methyl-N-vinylformamide, N-methyl-N-vinylacetamide, and N-vinylpyrrolidone in undergoing a cationically induced polymerization to oligomeric products is investigated. The influence of the NH-elimination on the oligomerization process is investigated with N-deutero-N-vinylformamide as monomer and the 2H NMR analysis of the obtained oligomers. From the results, a new mechanism for the oligomerization of N-vinylformamide is proposed and discussed.

Gegenstand der vorliegenden Arbeit ist die Untersuchung der kationisch initiierten Oligomerisation von N-Vinylformamid mit Iod, Brom, Trifluormethansulfonsäure und Trifluormethansulfonsäure-trimethylsilylester. Quantenchemische Berechnungen zur Konformation und zur Elektronendichteverteilung von N-Vinylformamid, sowie zu seiner Reaktion mit Elektrophilen werden vorgestellt. Die Struktur der erhaltenen Oligomere wird mittels 1H- und 13C-NMR-Spektroskopie, MALDI-TOF-MS, GPC, IR-Spektroskopie, Thermogravimetrie und quantitativer Elementaranalyse untersucht. Die Abhängigkeit von Ausbeute, mittleren Polymerisationsgrad und Kopfgruppenfunktionalität der erhaltenen Oligo(N-vinylformamide) vom Initiator, sowie von der Polarität des Lösemittels, dem eingesetzten Monomer/Initiator-Verhältnis und der Reaktionstemperatur wird vorgestellt. Im Vergleich zum N-Vinylformamid werden N-Vinylacetamid, N-Methyl-N-vinylformamid, N-Methyl-N-vinylacetamid und N-Vinylpyrrolidon auf ihre Fähigkeit untersucht, mit Initiatoren der kationischen Polymerisation Oligomere zu bilden. Mit N-Deutero-N-vinylformamid als Monomer und der 2H-NMR-Analyse der erhaltenen Oligomere wird der Einfluß der NH-Eliminierung während der Oligomerisation von N-Vinylformamid untersucht. Ausgehend von den experimentellen Ergebnissen wird ein für die Vinylpolymerisation neuer Mechanismus für die Oligomerisation von N-Vinylformamid vorgeschlagen und diskutiert. / The topic of the dissertation is the survey of the cationically initiated oligomerization of N-vinylformamide with iodine, bromine, trifluoromethanesulfonic acid, and trifluoromethanesulfonic acid trimethylsilylester as initiators. Quantum chemical calculations on the conformation and the electron density of N-vinylformamide, as well as on its reaction with electrophiles are presented. The structure of the obtained oligomers is investigated with 1H- and 13C NMR spectroscopy, MALDI-TOF-MS, GPC, IR spectroscopy, thermal decomposition, and quantitative combustion analysis. The influence of the polarity of the solvent, of the initiator, of the reaction temperature, and of the monomer/initiator ratio on yield, degree of polymerization, head group functionality, and chain structures of the obtained oligo(N-vinylformamide) is investigated. In comparison with N-vinylformamide, the ability of N-vinylacetamide, N-methyl-N-vinylformamide, N-methyl-N-vinylacetamide, and N-vinylpyrrolidone in undergoing a cationically induced polymerization to oligomeric products is investigated. The influence of the NH-elimination on the oligomerization process is investigated with N-deutero-N-vinylformamide as monomer and the 2H NMR analysis of the obtained oligomers. From the results, a new mechanism for the oligomerization of N-vinylformamide is proposed and discussed.

Three advanced methodologies for the preparation of extremely sterically hindered tertiary alkyl amines have been developed. The syntheses of 28 novel tertiary alkylamines that accommodate unusual steric hindrance are detailed. The electrophilic amination of alkyl Grignard reagents with N-chlorodialkylamines, in the presence of N,N,N′,N′-tetramethylethylenediamine (TMEDA) as a key additive, gives a variety of unprecedentedly sterically hindered tertiary alkylamines in good yields. Alternative strategy to 1-adamantyl-substituted (1-Ad) sterically hindered tertiary amines, which involved instead an SN1 reaction between 1-Ad cation with various secondary amines, is described. A complementary strategy to 1-Ad-based sterically hindered tertiary amines, which involves an iminium salt intermediate, is also reported. Salient features of the three protocols that are detailed here include unusual tolerance of steric hindrance, mild reaction conditions employed, ease of product isolation-purification, and absence of catalysts/transition metals. The molecular structures of two faithful examples of extremely sterically hindered tertiary alkylamines were determined by single crystal X-ray diffraction, and the height “h” of nitrogen pyramid of these compounds were measured. The NMR spectra show a restriction in rotation at room temperature among many hindered tertiary amines, and some of them exhibit two complete sets of peaks for two non-equivalent rotamers at room temperature. 15N NMR has been applied to study the structural changes in highly sterically hindered tertiary amines. Most of these compounds have been shown to undergo Hofmann type elimination reaction upon thermolysis at 100 degree in inert solvents, like toluene. / In der vorliegenden Arbeit wurden drei Methoden zur Synthese von tertitären Aminen mit extremer sterischer Hinderung entwickelt und zur Synthese von 28 neuen tertiären Alkylaminen mit entsprechender sterischer Hinderung angewendet. Die elektrophile Aminierung von Grignard-Reagenzien mit N-Chlordialkylaminen, unter Zusatz von N,N,N′,N′-Tetramethylethylendiamin (TMEDA) als Schlüsselkomponente, ermöglicht einen einfachen Zugang zu einer Vielzahl von tertiären Aminen mit extremer sterischer Hinderung mit guten Ausbeuten. Eine alternative Synthesestrategie unter SN1-Bedingungen führt zu sterisch-gehinderten 1-Adamantyl-substituierten (1-Ad) tertiären Aminen durch die Reaktion eines 1-Ad-Kations mit unterschiedlichen sterisch-gehinderten sekundären Aminen. Angelehnt an die zuvor beschriebene Reaktion können auch sterisch gehinderte Imine über eine Iminium-Salz-Zwischenstufe zu sterisch-gehinderten 1-Ad-substituierten tertiären Aminen umgesetzt werden. Auch in diesen Fall zeichnet sich die Reaktion durch eine bemerkenswerte Toleranz gegenüber sterischer Hinderung, milden Reaktionsbedingungen, leichte Produktisolierbarkeit und die Abwesenheit von Übergangsmetallkatalysatoren aus. Die molekulare Struktur zweier repräsentativer tertiärer Alkylamine mit extremer sterischer Hinderung wurde mittels Röntgeneinkristallstrukturanalyse untersucht und die Höhe “h” ihrer Stickstoff-Pyramide bestimmt. Die NMR-Spektren zeigen bei RT eine Einschränkung der freien Rotation um die N-C-Bindungsachse, teilweise führt dies zu vollständig getrennten Signalsätzen für die einzelnen Rotamere. 15N-NMR-Spektroskopie wurde ebenfalls zur Untersuchung von Strukturveränderungen genutzt. In inerten Lösungsmitteln, wie Toluol, zeigen die Verbindungen bei 100 °C in den meisten Fällen eine Hofmann-Eliminierung.