Les condensations iconographiques de l'entrée d'Henri II à Paris

Mémoire numérisé par la Division de la gestion de documents et des archives de l'Université de Montréal

First Example of Organocatalysis by Polystyrene-Supported PAMAM Dendrimers: Highly Efficient and Reusable Catalyst for Knoevenagel Condensations

This paper describes the first use of polystyrene-supported poly(amidoamine) (PAMAM) dendrimers as heterogeneous basic organocatalysts for carbon–carbon bond formation. Polystyrene-supported PAMAM dendrimers of first, second and third generations have been used as reusable base catalysts in Knoevenagel condensations of carbonyl compounds with active methylene compounds. The reactions proceed in short periods of time and with 100% selectivity. This novel catalyst eliminates the use of aromatic and halogenated solvents, as well as complex purification processes. The catalysts can be recycled ten times.

Some new condensations with para-para-bis (dimethylamino)--benzohydrol (Michler's hydrol) ...

Mode of access: Internet.

Uber Formaldehyd- oder Methylen-Derivate der Sauren der Zuckergruppe und uber die quantitative Bestimmung der Methylen-Gruppen in den Formaldehyd-Condensations-Produkten.

Thesis (doctoral)--Georg-Augusts-Universitat, Gottingen.

Contribution a l'etude des condensations de l'ether cetipique.

Thesis (doctoral)--

N-Aryl stilbazolium dyes as sensitizers for solar cells

Eight new N-arylstilbazolium chromophores with electron donating –NR2 (R = Me or Ph) substituents have been synthesized via Knoevenagel condensations and isolated as their PF6− salts. These compounds have been characterized by using various techniques including 1H NMR and IR spectroscopies and electrospray mass spectrometry. UV–vis absorption spectra recorded in acetonitrile are dominated by intense, low energy π → π* intramolecular charge-transfer (ICT) bands, and replacing Me with Ph increases the ICT energies. Cyclic voltammetric studies show irreversible reduction processes, together with oxidation waves that are irreversible for R = Me, but reversible for R = Ph. Single crystal X-ray structures have been determined for three of the methyl ester-substituted stilbazolium salts and for the Cl− salts of their picolinium precursors. Time-dependent density functional theory calculations afford reasonable predictions of ICT energies, but greater rigour is necessary for –NPh2 derivatives. The four new acid-functionalized dyes give moderate sensitization efficiencies (ca. 0.2%) when using TiO2-based photoanodes, with relatively higher values for R = Ph vs Me, while larger efficiencies (up to 0.8%) are achieved with ZnO substrates.

Defect-Free Hyperbranched Polydithioacetal via Melt Polymerization

Degree of branching (DB) describes the level of structural perfection of a hyperbranched polymer when compared to its defect-free analogue, namely the dendrimer. The strategy most commonly used to achieve high DB values, specifically while using AB(2) type self-condensations, is to design an AB2 monomer wherein the reaction of the first B-group leads to an enhancement of the reactivity of the second one. In the present study, we show that an AB2 monomer carrying a dimethylacetal unit and a thiol group undergoes a rapid self-condensation in the melt under acid-catalysis to yield a hyperbranched polydithioacetal with no linear defects. NMR studies using model systems reveal that the intermediate monothioacetal is relatively unstable under the polymerization conditions and transforms rapidly to the dithioacetal; because this second step occurs irreversibly during polymer formation, it leads to a defect-free hyperbranched polydithioacetal. TGA studies of the polymerization process provided some valuable insights into the kinetics of polymerization. An additional virtue of this approach is that the numerous terminal dimethylacetal groups are very labile and can be quantitatively transformed by treatment with a variety of functional thiols; the terminal dimethylacetals were, thus, reacted with various thiols, such as dodecanethiol, benzyl mercaptan, ethylmercaptopropionate, and so on, to demonstrate the versatility of these systems as sulfur-rich hyperscaffolds to anchor different kinds of functionality on their periphery.

Heterogeneous catalytic activity on Mn, Fe and Co-based metalloporphyrinic Solid Coordination Frameworks (SCFs)

Comunicación al congreso 1st European Conference on Metal Organic Frameworks and Porous Polymers, celebrado en Postdam del 11 al 14 de octubre de 2015

HI observations of the high-velocity cloud in the direction of M 92

We present wide-field neutral hydrogen (H I) Lovell telescope multibeam, and Dominion Radio Astrophysical Observatory Hi synthesis observations, of the high velocity cloud (HVC) located in the general direction of the globular cluster M92. This cloud is part of the larger Complex C and lies at velocities between similar to -80 and -130 km s(-1) in the Local Standard of Rest. The Lovell telescope observations, of resolution 12 arcmin spatially and 3.0 km s(-1) in velocity, fully sampling a 3.1 degrees x 12.6 degrees RA-Dec grid, have found that this part of HVC Complex C comprises two main condensations, lying approximately north-south in declination, separated by similar to2 degrees and being parallel to the Galactic plane. At this resolution, peak values of the brightness temperature and Hi column density of similar to1.4 K and similar to5 x 10(19) cm(-2) are determined, with relatively high values of the full width half maximum velocity (FWHM) of similar to 22 km s(-1) being observed, equivalent to a gas kinetic temperature, in the absence of turbulence and geometric effects of similar to 10 000 K. Each of these properties, as well as the sizes of the clouds, are similar in the two components. The DRAO observations, towards the Northern HVC condensation, are the first high-resolution Hi spectra of Complex C. When smoothed to a resolution of 3 arcmin, they identify several Hi intensity peaks with column densities in the range 4-7 x 10(19) cm(-2). Further smoothing of these data to 6 arcmin resolution tentatively indicates that parts of the HVC consist of two velocity components, of similar brightness temperature, separated by similar to7 km s(-1) in velocity, and with FWHM velocity widths of similar to5-7 km s(-1). No IRAS 60 or 100 micron flux is associated with the M92 HVC. Cloud properties are briefly discussed and compared to previous observations of HVCs.

Hα and EUV observations of a partial CME

We have obtained H$\alpha$ high spatial and time resolution observations of the upper solar chromosphere and supplemented these with multi-wavelength observations from the Solar Dynamic Observatory (SDO) and the {\it Hinode} ExtremeUltraviolet Imaging Spectrometer (EIS). The H$\alpha$ observations were conducted on 11 February 2012 with the Hydrogen-Alpha Rapid Dynamics Camera (HARDcam) instrument at the National Solar Observatory's Dunn Solar Telescope. Our H$\alpha$ observations found large downflows of chromospheric material returning from coronal heights following a failed prominence eruption. We have detected several large condensations ("blobs") returning to the solar surface at velocities of $\approx$200 km s$^{-1}$ in both H$\alpha$ and several SDO AIA band passes. The average derived size of these "blobs" in H$\alpha$ is 500 by 3000 km$^2$ in the directions perpendicular and parallel to the direction of travel, respectively. A comparison of our "blob" widths to those found from coronal rain, indicate there are additional smaller, unresolved "blobs" in agreement with previous studies and recent numerical simulations. Our observed velocities and decelerations of the "blobs" in both H$\alpha$ and SDO bands are less than those expected for gravitational free-fall and imply additional magnetic or gas pressure impeding the flow. We derived a kinetic energy $\approx$2 orders of magnitude lower for the main eruption than a typical CME, which may explain its partial nature.

Calix[4]pirróis: síntese e aplicação como sensores de aniões

A presente dissertação descreve, essencialmente, o desenvolvimento de novos métodos de funcionalização de calix[4]pirróis. O uso desses calix[4]pirróis, bem como o de porfirinas e ftalocianinas, como sensores de aniões, incluindo a determinação das suas constantes de afinidade é igualmente discutido. Esta dissertação encontra-se dividida em três partes distintas. Na primeira é feita uma revisão bibliográfica acerca das metodologias de síntese dos calix[4]pirróis, bem como das suas características e aplicações. A segunda parte encontra-se subdividida em diversos pontos de acordo com o tipo de funcionalização realizada nos calix[4]pirróis. No primeiro ponto desta parte encontram-se discutidos a síntese e a caracterização do mesooctametilcalix[ 4]pirrol-2-carbaldeído e do 3-(meso-octametilcalix[4]pirrol-2- il)propenal bem como os resultados obtidos da funcionalização destes aldeídos por reacções de cicloadição 1,3-dipolar. Esses aldeídos foram usados para gerar iletos de azometino, os quais foram “apanhados” com diversos dipolarófilos, tais como o fumaronitrilo, o fumarato de dimetilo, a N-(4- metoxifenil)maleimida, a 1,4-benzoquinona e a 1,4-naftoquinona. Ambos os calixpirróis com grupo formilo deram origem a aductos de cicloadição 1,3- dipolar com rendimentos moderados ou bons, principalmente quando se utilizou fumaronitrilo, fumarato de dimetilo ou N-(4-metoxifenil)maleimida como dipolarófilos. Neste estudo verificou-se que quando as quinonas eram utilizadas como dipolarófilos apenas eram obtidos os cicloaductos do 3-(mesooctametilcalix[ 4]pirrol-2-il)propenal. No segundo ponto descrevem-se as reacções de condensação aldólica e de Knoevenagel do mesooctametilcalix[ 4]pirrol-2-carbaldeído e do 3-(meso-octametilcalix[4]pirrol-2- il)propenal. Verificou-se a ausência de resultados para as reacções de condensação aldólica mas resultados muito satisfatórios para as reacções de Knoevenagel. Foram utilizados como compostos metilénicos activados a indano-1,3-diona, o 1,3-bis(dicianometilideno)indeno, o malononitrilo, o cianoacetato de etilo, o malonato de dietilo e o ácido de Meldrum. No penúltimo ponto encontram-se discutidas as reacções dos dois aldeídos com aminas bem como a sua redução e posterior tentativa de funcionalização dos calixpirróis com grupo hidroxilo. Em ambas as tentativas os resultados foram pouco satisfatórios. No último ponto da segunda parte descrevem-se, pormenorizadamente, os métodos de síntese, purificação e caracterização estrutural dos diversos compostos sintetizados. Na terceira parte são descritos os testes dos novos calix[4]pirróis sintetizados e também de outros derivados tetrapirrólicos, nomeadamente porfirinas e ftalocianinas, com aniões. Os calix[4]pirróis sintetizados demonstraram capacidade de interagir com diferentes aniões, e a sua capacidade de interacção é dependente dos grupos funcionais introduzidos. Verificou-se que os compostos com grupos ciano conjugados com um anel pirrólico do macrociclo apresentam constantes de afinidade mais elevadas para os aniões. A concluir esta dissertação encontra-se uma revisão da literatura sobre a utilização de porfirinas como sensores de aniões. Apresentam-se também os resultados obtidos com duas porfirinas e uma ftalocianina em tal aplicação. As porfirinas testadas apresentam elevadas constantes de afinidade com os iões fluoreto e di-hidrogenofosfato. No caso da ftalocianina verificou-se que esta interage com vários aniões, bem como com metanol e sulfóxido dimetílico, originando soluções de cores muito diferentes.

Expanded porphyrins and their evaluation as anion chemosensors

Expanded porphyrins are synthetic analogues of porphyrins, differing from the last ones and other naturally occurring tetrapyrrolic macrocycles by containing a larger central core, with a minimum of 17 atoms, while retaining the extended conjugation features that are a tremendous feature of these biological pigments. The core expansion results in various systems with novel spectral and electronic features, often uniques. Most of these systems can also coordinate cations and/or anions, and in some cases they can bind more than one of these species. In many cases, these molecules display structural features, such as non-planar structures, that have no antecedents in the chemistry of porphyrins or related macrocyclic compounds. This work will discuss several synthetic approaches for the synthesis of expanded porphyrins, namely the construction of new building blocks by Michael addition, as well as potential synthetic routes towards expanded porphyrins. The synthesis of smaller oligopyrrolic compounds namely, bipyrroles and dipyrromethanes, not only were developed for the synthesis of expanded porphyrins as they were also used in Knoevenagel condensations furnishing chromogenic compounds able to recognize different anions in solution. Also, an approach to the synthesis of novel expanded porphyrins namely sapphyrins has been done by aza-Michael additions. Several synthetic routes towards the synthesis of pyridyl and pyridinium N-Fused pentaphyrins and hexaphyrins have been explored in order to achieve compounds with potential applications in catalysis and PDI, respectively. Studies on the synthesis of compounds with potential anion binding properties, led to the structural characterization and NMR anion binding studies of [28]hexaphyrins functionalized with several diamines in the para position of their pentafluorophenyl groups. These compounds allow NH hydrogen bond interactions with various anions. All synthesized compounds were fully characterized by modern spectroscopic techniques.

“Should we all be on Marx’s side?” Contributions of post-marxist discourse theory to the historiography of communism

Drawing on post-marxist discourse theory inspired by the writings of Ernesto Laclau and Chantal Mouffe, this article puts the case for a literature on communism situated at the crossroads of critical theory, cultural studies and historiography. Specific illustration is provided by the author's own research on British communism and the Spanish Civil War. However, the scope of the article is much broader and it is intended as a contribution to the theoretical discussion of future possibilities for communist history-writing. The article concludes that discourse should be regarded neither as a flat surface of tightly knit signifiers nor as an impenetrable monolith of meaning systems. Rather, it should be seen as an inherently dynamic phenomenon, with its own condensations and dispersions along the historical continuum. In this lies its significance for historians of communism.

Reabilitação térmica de fachadas

As fachadas são um elemento da envolvente que faz a interface entre o ambiente exterior e o interior. Do conjunto das suas características mais relevantes, existe uma, cuja importância tem vindo a aumentar devido à conjuntura ambiental e económica atual: o desempenho energético. Assim, é importante analisar as características do comportamento térmico dos elementos da fachada, com base na respetiva regulamentação em vigor (REH – D.L. n.º 118/2013 de 20 de Agosto) e analisar o contributo da sua eventual reabilitação para uma melhor qualidade térmica da fachada e por consequente uma melhor qualidade de conforto dos utentes do edificio, não desprezando o aspeto arquitetónico do mesmo. Esta monografia baseia-se na análise de casos práticos de diferentes soluções construtivas e avaliação das vantagens e desvantagens dos sistemas propostos, conferindo a possibilidade de optar pelo sistema mais eficaz de acordo com as necessidades exigidas. Assim, e com base no principal objetivo, que é o de melhorar o desempenho térmico das fachadas recorrendo à reabilitação, o enfoque é sobre a redução do consumo energético dos edificios, nomeadamente através do contributo térmico dos elementos das fachadas para a redução das necessidades energéticas por climatização.

ETICS como sistema de reabilitação de fachadas

O presente relatório retrata o estágio curricular desenvolvido no segundo ano do Mestrado em Engenharia Civil - Ramo de Construções do Instituto Superior de Engenharia do Porto. O relatório fará primeiramente uma abordagem às principais tarefas desempenhadas durante o estágio bem como uma abordagem à empresa adjudicatária da obra em análise. Seguidamente apresenta-se a obra em que se desenvolveu o estágio, “Requalificação e Reabilitação de Vila D’ Este Fase II”, onde será feita uma descrição do estado em que se encontravam os edifícios antes de serem intervencionados, bem como das intervenções efetuadas. Na sequência da apresentação da obra, será feita uma abordagem ao tema de estudo deste relatório, o Sistema ETICS. Este sistema com crescente procura no mercado, tem muitos parâmetros aos quais deve obedecer, pelo que neste relatório serão apresentados todos os aspetos considerados relevantes à sua correta execução. Para terminar serão verificadas as melhorias impostas por este Sistema. Inicialmente com uma abordagem em termos energéticos e depois uma abordagem ao controlo da humidade e prevenção das condensações.