Ces dernières années, la notion de Développement Durable a bouleversé la recherche académique etindustrielle dans le domaine de la chimie. L’utilisation de matières premières issues des ressources renouvelables en constitue l’un des aspects les plus marquants. De même, le développement de procédés originaux, qui s’appuient sur des systèmes catalytiques recyclables, des transformations chimiques innovantes et de nouveaux solvants plus respectueux de l’environnement font l’objet d’un intérêt croissant, en raison des gains environnementaux et économiques. Les travaux de recherche décrits dans cette thèse s’inscrivent dans ce contexte et présentent la mise au point de nouvelles voies d’accès aux éthers de glycérol, des molécules à haute valeur ajoutée. Plusieurs procédés originaux ont été développés en utilisant le glycérol comme substrat biosourcé issu de l’industrie oléo-chimique. Ainsi, l’alkylation réductrice d’acides carboxyliques avec le glycérol en présence de palladium sur charbon et d’une résine acide a permis de préparer une variété de 1-Oalkyléthersde glycérol. Une procédure alternative a été développée à partir des huiles végétales et des esters méthyliques, par transestérification puis réduction de l’ester intermédiaire sous hydrogénation catalytique. Ensuite, un procédé d’alkylation déshydrogénante de dérivés de la cyclohexanone avec le glycérol a donné un nouvel accès aux 1-O-aryléthers de glycérol et a été étendu aux éthers et aux amines aromatiques. Enfin, de nouveaux solvants aprotiques dérivés du glycérol ont été synthétisés par une catalyse de transfert de phase. En particulier, la toxicité du 1,2,3-triméthoxypropane ainsi que son utilisation dans des transformations chimiques comme nouveau solvant ont été évaluées. / In recent years, sustainable development brought unprecedented changes in industrial and academic researches. The use of raw materials from renewable resources is one of the most outstanding aspects of these changes. The development of original processes, with recyclable catalytic systems, new chemical transformations as well as new solvents with a lower environmental impact are of growing interest, because of environmental and economical profits. The research work described in this thesisis focused on the development of new accesses to glyceryl ethers as high value added coumpounds.Thus, several processes were developed by using glycerol as accessible and bio-based starting material from the oleochemical industry. First, we found a benign and eco-friendly process for the synthesis of1-O-alkyl glyceryl ethers by catalytic reductive alkylation of carboxylic acids with a recyclable catalytic system associating palladium on carbon and an acid ion exchange resin. A second two steps procedure was also developed when starting from a vegetable oil or a methyl ester, which was transesterified to the corresponding monoglyceride followed by its reduction by catalytic hydrogenation. We report also a straight forward and palladium catalyzed dehydrogenative alkylation of cyclohexanone derivatives with alcohols, including glycerol, and amines in order to prepare avariety or aryl ethers and aryl amines. Finally, we prepared new aprotic and glycerol-based solvents bya solvent-free phase-transfer catalysis. In particular, the toxicity of 1,2,3-trimethoxypropane and its utilization as alternative solvent in chemical transformations was evaluated.

This diploma thesis deals with senthesis of lactic acid ethyl ester from slats of lactic acid. The literature review has been processed in the theoretical part of the diploma thesis. It is focused on manufacturing technologies of lactic acid esters, mainly on ethyl lactate by conventional and non-conventional ways of producing. Also the literature review involves producing of lactic acid and slats of lactic acid by fermentation because subsequently is possible produce ethyl lactate from that two substances. The laboratory apparatus for preparation of ethyl lactate and methyl lactate has been designed, realized and verificated function of it in the experimental part. There were carried out laboratory experimnets for production ethyl lactate and methyl lactate in this apparaturs.

When exploiting an area, important ecosystem services can be lost, and an ecosystem service analysis gives a clear picture of how a plurality of values are affected. The purpose of this study is to investigate how the detailed development plans for two properties in Laholm municipality will affect the ecosystem services, and what compensation measures that may be implemented. A qualitative method was used where literature search, interviews, question answers, observation and ESTER 2.0 were included. The results suggest that that the supporting ecosystem services on both properties and the cultural ecosystem services on one of the properties will be negatively affected by the exploitation. However, the cultural ecosystem services on one of the properties will be positively affected. Laholm municipality does not actively work with the mitigation hierarchy and compensation measures. Possible compensation measures to create could be ponds and meadow patches, planting of flowering trees and placement of benches and picnic tables. A collaboration with Båstad municipality would further be beneficial for protecting the landscape and promoting biological diversity across municipal borders. / Vid exploatering av ett område kan viktiga ekosystemtjänster gå förlorade och med hjälp av en ekosystemtjänstanalys får man en tydlig bild över de många olika värden som påverkas. Syftet med studien är att ta reda på hur detaljplanerna för två fastigheter i Laholms kommun kommer påverka ekosystemtjänsterna, samt undersöka möjliga kompensationsåtgärder. I studien användes en kvalitativ metod där litteratursökning, intervjuer, frågesvar, observation och ESTER 2.0 inkluderades. Resultatet visar att de stödjande ekosystemtjänsterna på båda fastigheterna och de kulturella ekosystemtjänsterna på en av fastigheterna kommer påverkas negativt av exploateringen. Däremot kommer de kulturella ekosystemtjänsterna på en av fastigheterna påverkas positivt. Skadelindringshierarkin och kompensationsåtgärder är inget Laholms kommun arbetar aktivt med. Möjliga kompensationsåtgärder att skapa skulle kunna vara dammar och ängsplättar, plantering av blommande träd samt utplacering av bänkar och picknickbord. En samverkan med Båstad kommun hade vidare varit fördelaktigt för att skydda landskapsbilden och främja en biologisk mångfald över kommungränserna.

Den här uppsatsen utgår ifrån reportage ur reportageböckerna En piga bland pigor av Ester Blenda Nordström och Ok, amen: Om kärlek och fientlighet i chassidernas New York av Nina Solomin. Syftet är att, i jämförande form, ta reda på hur de gått till väga för att skildra en ny miljö i de utvalda reportagen ur respektive bok. Massmedieretorisk, lingvistisk och narratologisk analys blandas för att sätta ihop ett frågeschema med frågor som behandlar olika dimensioner av texterna. Det som undersöks är framför allt berättarteknik, berättarperspektiv, reporterroll och dolda värderingar, men också, utifrån narratologisk teori, hur olika typer av berättare påverkar texterna. Slutsatserna är att både Nordström och Solomin använder ett rikt bildspråk som förstärker stämningar och känslor och att de båda har tydliga aktörsroller i texterna. De dolda värderingar som visar sig i texterna hos båda reportrarna riktar framför allt kritik mot könsrollerna i de nya miljöerna. Det som skiljer dem åt är att Nordström i större utsträckning använder sig av värderande ord, överdrifter och adjektiv medan Solomin är mer för kontraster, och att Nordströms berättare är mer synlig och värderande än Solomins, vars texter oftare låter läsaren tolka det som händer själv.

Surface-initiated photo-iniferter mediated controlled polymerisation was used as a technique for the development of advanced and smart materials. Molecularly imprinted polymer (MIP) shell nanoparticles (NPs) were synthesised in this way from PAMAM dendrimers, used as a graftable core, in 2 min irradiation time. Surprisingly the so-synthetised NPs were around 200 nm and had a cubic shape. Cont/d.

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

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

Um novo método de dissolução e acilação de celulose no sistema LiCl/N,N-dimetilacetamida (DMAC) foi desenvolvido e aplicado com sucesso nas seguintes celuloses: microcristalina (I), sisal (II), algodão(III) e bagaço de cana de açúcar (IV). O novo método tem as seguintes vantagens: a) uso de sistema acilante simples (anidridos alifáticos sem catalisadores); b) produção direta de ésteres simples (acetatos, propionatos e butiratos) e mistos (acetato/butirato), com eficiente controle do grau de esterificação; c) menor demanda de tempo e reagentes; d) desprezível degradação da celulose; e) eficiente recuperação/reciclagem do solvente e dos demais reagentes. Estudos por microscopia eletrônica de varredura revelam que em II e IV a penetração do solvente é mais lenta que em I devido à diferenças morfológicas. Constantes de velocidade e parâmetros de ativação do processo de descristalização de I e IV, foram determinados sob condições não isotérmicas, a partir do decaimento do índice de cristalinidade (determinado por espectroscopia no infravermelho). O processo de descristalização é globalmente endotérmico e aparentemente não depende do grau de polimerização (GP) da celulose de partida. A diferença na reatividade observada para as celuloses II a IV em relação a I, foi atribuída ao maior GP, maior flexibilidade da cadeia polimérica, além da agregação destas celuloses no sistema. O grau de acetilação individual das posições C6, C3 e C2 na unidade anidra de glicose, determinado por RMN de 13C, revela a seguinte ordem de reatividade para os grupos OH na UAG: C6 > C3 ≈ C2. / A novel procedure for cellulose dissolution and acylation in LiCl/ N,N-dimethylacetamide solvent system has been introduced and successfully applied to the following celluloses: microcrystalline (I), sisal (II), cotton (III) and sugar cane bagasse (IV). The novel procedure has the following attractive features: a) uses acid anhydride and requires no base catalyst; b) can be used for the direct preparation of esters and mixed esters; c) requires less amount of solvent and shorter time; d) causes negligible degradation of cellulose; e) permits recovery/recycling of DMAC and acid anhydride. Scanning electron microscopy studies show that swelling of celluloses II and IV by the solvent is slower than that of I, most probably due to morphological differences. Rate constants and activation parameters for decrystallization of I and IV have been determined from dependence of the index of crystallinity of cellulose, on time, under non-isothermal conditions. The decrystallization was found to be an endothermic process, negligibly dependent on the degree of polymerization (DP) of the starting cellulose. Differences in the reactivities between celluloses are related to GP, polymer chain flexibility and cellulose aggregation. The distribution of the acetyl moiety among the three OH groups was determined by 13C NMR, giving rise to the following order : C6 > C3 and C2.

Foi estudado o mecanismo da hidrólise de benzoatos de fenila substituídos catalisada pela 1-oxi-1,2-benziodoxol-3(1H)-ona (ânion o-iodosobenzoato, IBA-), em microemulsão água/óleo (mE A/O) de cloreto de benzil-hexadecil-dimetil-amônio (CBzCl) em benzeno. Duas séries de ésteres foram utilizadas: 4-X-benzoatos de 4-nitrofenila (X= NO2, CN, Cl e H) e 4-nitrobenzoatos de Y-fenila (Y= 4-NO2, 3-NO2, 4-CN, 3-CN, 4-Cl e H). Os resultados de IV (detecção do intermediário 1-(4-X-benzoiloxi)-1,2-benziodoxol-3(1H)-ona, benzoil-IBA), ausência de catálise pelo grupo abandonador, e efeito isotópico cinético de solvente inverso mostraram que a catálise pelo IBA- é nucleofílica, ocorrendo em duas etapas: - ataque do IBA- sobre o éster produzindo o intermediário benzoil-IBA e o fenol correspondente; - hidrólise desse intermediário formando os produtos finais da reação, ácido benzóico substituído e IBA-. A intensa absorção do solvente (benzeno) no UV impediu a observação do intermediário benzoil-IBA, por isso somente a primeira etapa da reação (ataque do IBA- sobre o éster, formando o intermediário benzoil-IBA) foi estudada nesta Dissertação. A natureza da etapa lenta da reação, o ataque do IBA- para formar o intermediário tetraédrico éster-IBA, foi determinada pela aplicação da equação de Hammett. Uma comparação entre os dados obtidos em mE A/O e em misturas binárias de solventes orgânicos e água mostrou que a reação aparentemente é pouco sensível a efeitos do meio. As constantes catalíticas de velocidade em mE A/O, em 14% CH3CN/H2O, em 35,1% CH3CN/H2O e em 56,5% CH3OH/H2O são similares. A entalpia de ativação para a reação micelar é cerca de 3 kcal.mol-1 menor que para as reações em meio aquoso, mas isso é compensado por uma diminuição da mesma ordem no termo entrópico. A sensibilidade da reação à substituição no grupo acila aumenta ao se transferir a reação das misturas binárias aquosas para a mE A/O, ao passo que aos substituintes no grupo fenila permanece praticamente igual em todos os meios. Esses efeitos aparentemente são ocasionados por uma dessolvatação parcial tanto do IBA- (em maior intensidade) como do estado de transição (em menor intensidade) na região interfacial da mE A/O. O mecanismo de catálise pelo IBA- parece ser o mesmo, com a mesma etapa lenta (ataque do IBA- sobre o éster) em todos os meios estudados. As diferenças observadas para a reação na mE A/O (maior sensibilidade à substituição no grupo acila do éster, entalpias e entropias menores que nos outros meios) devem ser resultantes da dessolvatação parcial do IBA- nesse meio. / The mechanism of hydrolysis of the following two series of phenylbenzoate esters catalyzed by 1-oxi-1,2-benziodoxol-3(1H)-one (o-iodosobenzoate anion, IBA-), was studied in water-in-oil microemulsion (W/O mE) of benzylhexadecyl- dimethylammonium chloride (CBzCl) in benzene. 4-nitrophenyl 4-X-benzoates (X= NO2, CN, Cl and H) and Y-nitrophenyl 4-nitrobenzoates (Y= 4-NO2, 3-NO2, 4-CN, 3-CN, 4-Cl and H). The following results show that IBA- is acting as a nucleophilic catalyst: detection of the intermediate 1-(4-X-benzoyloxi)-1,2-benziodoxol-3(1H)-one (benzoyl-IBA) by FT-IR; absence of catalysis by the leaving group; and inverse kinetic solvent isotopic effect. The reaction proceeds by a two-step mechanism: - nucleophilic attack of IBA- on the ester, resulting in the formation of benzoyl-IBA and liberation of the corresponding phenol; - hydrolysis of this intermediate, giving the final products of the reaction, substituted benzoates and IBA-. Absorbance by the solvent precluded observation of the reaction intermediate, consequently only the first part of the reaction (i.e., micellar attack of IBA- on the ester) was studied in this Dissertation. The nature of the rate determining step, formation of the tetrahedral intermediate (Ester-IBA), was determined from application of the Hammett equation. A comparison between the data in W/O microemulsions and in binary organic solvent-water mixtures showed that the reaction is rather insensitive to medium effects. The catalytic rate constants in W/O microemulsion, in 14% CH3CN/H2O, in 35,1% CH3CN/H2O, and in 56,5% CH3OH/H2O are very similar. The activation enthalpy of the micellar reaction is 3 kcal.mol-1 lower than the value in aqueous media, but this is compensated by a decrease of the same order in the entropic term. The sensitivity of the reaction to substitution in the acyl group increases in going from aqueous media to the W/O microemulsions, while the sensitivity to substitution in the phenyl moiety is almost the same in all media. These effects are apparently caused by a partial desolvation of both IBA- and the transition state in the interfacial region, the former desolvation being more pronounced. The catalysis mechanism by IBA- seems to be the same, with the same rate determining step (nucleophilic attack of IBA- on the ester), for all the studied systems. The differences observed for the reaction in W/O mE (greater sensitivity to substitution in the ester acyl group, lower values of enthalpy and entropy) are a result of the partial desolvation of IBA- in this system.

Neste trabalho, foi avaliada a resolução cinética de ésteres carboxílicos β-borilados, catalisada por lipases, através de hidrólise e transesterificação. Foram sintentizados ésteres contendo diferentes cadeias carbônicas. A hidrólise enantiosseletiva catalisada por CAL-B forneceu o correspondente ácido carboxílico β-borilado com excesso enantiomérico moderado (e.e. 62%), enquanto os ésteres β-borilados metílico e etílico foram recuperados com excelente pureza enantiomérica (e.e.>99%). A reação de transesterificação enantiosseletiva entre ésteres carboxílicos β-borilados e álcoois, catalisada por CAL-B, demonstrou uma alta seletividade somente quando etanol e (β-pinacolilboronato)-butanoato de metila foram usados como substratos, levando a formação de (β-pinacolilboronato)-butanoato de etila enantioenriquecido (e.e.>99%). Entretanto, ésteres contendo longas cadeias carbônicas ligadas à carboxila não sofreram as reações desejadas, mesmo em temperaturas mais elevadas. Adicionalmente, foi investigada a reação de aminação redutiva assimétrica, catalisada por ω-transaminases, de cetonas pró-quirais contendo grupos borônicos (ácido, éster ou trifluoroborato de potássio). Após as sínteses de cetonas aromáticas e alifáticas, os melhores resultados para a biotransformação foram obtidos com ω-transaminases (R)-seletivas de Arthrobacter sp. e Aspergillus terreus e (S)-seletiva de Chromobacterium violaceum. Sob as condições otimizadas, foram obtidas altas conversões (94%) com perfeitas enantiosseletividades (e.e.>99%), proporcionando assim uma nova via de acesso a aminas (R) ou (S) contendo boro em condições reacionais suaves. / In this work, the kinetic resolution of β-borylated carboxylic esters via lipase-catalyzed hydrolysis and transesterification reactions was evaluated. Esteres with different carbon chains were synthesized. The enantioselective hydrolysis catalyzed by CAL-B furnished the corresponding β-borylated carboxylic acid with reasonable enantiomeric excess (ee 62%), while both methyl and ethyl β-borylated carboxylic esters were recovered with excellent enantiomeric purity (ee>99%). The enantioselective transesterification reaction of β-borylated carboxylic esters and several alcohols, catalyzed by CAL-B, only indicated a high selectivity when ethanol and methyl-(β-pinacolylboronate)-butanoate were used as substrates, which gave the enantioenriched ethyl-(β-pinacolylboronate)-butanoate (ee >99%). However, esters with longer carbon chains or steric hindrance at the carboxyl group did not undergo the desired reactions, even at high temperatures. Additionally, the asymmetric reductive amination ω-transaminase catalyzed of boron-containing (acid, ester or potassium trifluoroborate) prochiral ketones was investigated. After the syntheses of aromatic and aliphatic ketones, the best results of biotransformation were obtained with (R)-selective ω-transaminases from Arthrobacter sp. and Aspergillus terreus and (S)-selective one from Chromobacterium violaceum. Under the optimized conditions, high conversions (94%) with perfect enantioselectivities (ee >99%) were found, providing a new access to (R) or (S) boron-containing amines under mild reaction conditions.