Neste trabalho, enzimas álcool-desidrogenases provenientes de fungos marinhos e a lipase imobilizada de Candida antarctica foram utilizadas para produção de compostos de interesse sintético e biológico. No capítulo 1, enzimas álcool-desidrogenases de fungos isolados da alga marinha Bostrychia radicans foram empregadas em reações de redução de cetonas fluoradas 1-5. Os fungos identificados como Botryosphaeria sp. CBMAI 1197, Eutypella sp. CBMAI 1196, Hidropisphaera sp. CBMAI 1194 e Xylaria sp. CBMAI 119 atuaram como biocatalisadores nestas reações levando à produção de álcoois com elevada pureza enantiomérica. O fungo Botryosphaeria sp. CBMAI 1197 destacou-se frente aos demais microrganismos, produzindo os álcoois (S)-2,2,2-trifluoro-1-feniletanol (1a) e (R)-1-(2,4,5-trifluorofenil)etanol (3a) com excelentes conversões (100% e 97%) e excessos enantioméricos (ee >99%). Este fungo também apresentou enzimas álcool-desidrogenases ativas frente a cetonas dicarboniladas 4-5, produzindo os álcoois 4,4,4-trifluoro-1-fenil-1,3-butanodiol (4a) e 4,4,4-trifluoro-1-(2-naftalenil)-1,3-butanodiol (5a) com 100% de conversão em ambos os casos e com purezas enantioméricas respectivas a 99% e 97%. Este foi o primeiro estudo realizado no Brasil com fluorocetonas dicarboniladas e com os fungos isolados da alga marinha Bostrychia radicans. No capítulo 2, a lipase comercial de Candida antarctica foi o biocatalisador empregado em reações de aminólise entre os ésteres linoleato de etila (1) e salicilato de etila (3), a amina graxa N-dodecilamina (2) e os aminoálcoois (4-9). A amina graxa N-dodecilamina (2) também foi utilizada em reações com o linoleato de etila (1), onde a lipase de Candida antarctica produziu a respectiva amida graxa 10 com rendimentos superiores a 95%. Os aminoálcoois foram selecionados para reações com o salicilato de etila (3), onde a lipase exibiu quimiosseletividade pelo grupo amino, produzindo predominantemente amidas fenólicas (12-19) com rendimentos entre 23-68%. A enzima CALB apresentou quimiosseletividade reduzida na reação com o 5-aminopentanol (6) onde os produtos amida 14 e éster 15 foram obtidos com rendimentos de 44 e 33%, respectivamente. O produto 2-hidroxi-N-(2-hidroxipropil)benzamida (19) foi obtido com rendimento superior a 90% a partir da reação catalisada pela lipase de Candida antarctica. Este produto foi selecionado como intermediário para a síntese de uma molécula hidrofóbica 21 que apresenta o éster oleato de etila em sua constituição. O produto 21 foi obtido com 75% de rendimento. As amidas fenólicas 12-21 produzidas neste trabalho são derivadas do ácido linoleico (ômega 6) e do ácido salicílico, os quais apresentam propriedades emolientes e antioxidantes. Estes compostos são interessantes para a formulação de produtos cosméticos de aplicação cutânea. Neste processo biotecnológico as reações foram conduzidas na ausência de solventes orgânicos, evitando o tratamento de solventes voláteis e a formação de subprodutos. Os compostos foram analisados por Cromatografia líquida de alta eficiência e caracterizados por RMN (1H, 13C), EMAR e IV. A aplicação de reações de biocatálise seja através de células microbianas ou de enzimas isoladas foram muito promissoras na síntese de compostos orgânicos de interesse como álcoois enantiomericamente puros ou amidas graxas. / In this work, alcohol dehydrogenase (ADHs) enzymes from marine fungi and immobilized lipase from Candida antarctica were employed for the production of compounds of biological and synthetic interest. In chapter 1, ADHs of fungi isolated from the marine alga Bostrychia radicans were used in reduction reactions of fluorinated ketones 1-5. The fungi identified as Botryosphaeria sp. CBMAI 1197, Eutypella sp. CBMAI 1196, Hidropisphaera sp. CBMAI 1194 and Xylaria sp. CBMAI 119 acted as biocatalysts in these reactions leading to production of alcohols with high enantiomeric purity. The fungus Botryosphaeria sp. CBMAI 1197 presented highlighted compared to other microorganisms producing the alcohols (S)-2,2,2-trifluoro-1-phenylethanol (1a) and (R) -1 - (2,4,5-trifluorophenyl) ethanol (3a) with excellent conversions (100% and 97%) and enantiomeric excesses (ee > 99%). This fungus also exhibited ADHs enzymes active with dicarbonylateds ketones, leading to the production of the alcohols 4,4,4-trifluoro-1-phenylbutane-1,3-diol (4a) and 4,4,4-trifluoro-1-(naphthalen-2-yl)butane-1,3-diol -1,3-butanediol (5a) with conversions of 100% in both cases and enantiomeric excess of 99%-97%, respectively. This was the first study conducted with dicarbonilated fluoroketones 4-5 and with fungi isolated from the marine alga Bostrychia radicans in Brazil. In chapter 2, immobilized lipase from Candida antarctica was used as biocatalyst in the aminolysis reaction between esters of ethyl linoleate (1) and ethyl salicylate (3), the fatty amine N-dodecylamine (2) and the aminoalcohols (4-8). Six aminoalcohols were selected for reactions with ethyl salicylate (3), where the lipase exhibited chemoselectivity by the amino groups, producing predominantly phenolic amides in yields of 23-63%. The CALB exhibited um reduction in chemoselectivity in the reaction with 5-aminopentanol (6) where the amide 14 and ester 15 products were obtained with 44% and 33% yields. The product 2-hydroxy-N-(2-hydroxypropyl) benzamide (19) was obtained in yield greater than 90% from the reaction catalyzed by lipase from Candida antarctica. This product was selected as reagente for the synthesis of a hydrophobic molecule 21 presenting ester ethyl oleate in its constitution. The product 21 was obtained in 75% yield. The phenolic amides 12-21 produced in this work are derived from linoleic acid (omega 6) and salicylic acid, which presents emollient and antioxidants properties. These compounds are interesting for the formulation of cosmetic products for skin application. In this biotechnological process, the reactions were carried out under solvent-free conditions and vacum, avoiding the treatment of volatile solvents and by-product formation. The compounds were analyzed by high performance liquid chromatography and characterized by NMR (1H, 13C), IR and HRMS. Applying biocatalysis reactions, either through microbial cells or isolated enzymes were promising for the synthesis of organic compounds such as enantiomerically pure alcohols and fatty phenolic amides.

Made available in DSpace on 2016-12-23T14:04:28Z (GMT). No. of bitstreams: 1 Jairo Pinto de Oliveira.pdf: 2727767 bytes, checksum: 3b1352014d87848112176e085bb84c8d (MD5) Previous issue date: 2012-12-10 / Conselho Nacional de Desenvolvimento Científico e Tecnológico / Effluents are released daily into water bodies without any treatment with high levels of oil and grease (OG) and are a huge environmental problem. These residues are potentially available may be used for energy recovery, such as oil usage for the production of biodiesel. As the biggest barrier to the production of biodiesel involves the cost of raw materials, grease traps of restaurants, industries and wastewater treatment plants can be used as feedstock for biofuel production, since they have large amounts of oil and grease without cost. However, residual oils and greases contain high levels of free fatty acids (FFA) and as the preferred route for the production of biodiesel transesterification is alkaline, may be formed soap as a final product, impairing the separation of glycerol and decreasing the reaction yield. Thus, the acidic and enzymatic transesterification can present as promising alternatives, since it can catalyze the modification of both triglycerides and free fatty acids. The objective of this study was to investigate the possibility of using four types of oily waste sanitation (skimmings of grease from a University Restaurant, a Food Industry, a Station Wastewater Treatment and Sludge pits and septic tanks); characterize the physicochemical properties of oils and greases extracted and evaluate processes involving generation of biodiesel acid catalyst (H2SO4) and enzyme (immobilized Candida antarctica). The residues studied showed high levels of oil and grease and physicochemical characterization showed high levels of acidity, saponification and humidity. Were detected and quantified the major saturated and unsaturated fatty acids by High Performance Liquid Chromatography (HPLC). The production of biodiesel from raw materials from grease traps showed high levels of conversion, greater than or equal 90%, which shows that both catalysts (H2SO4 and lipase Candida antarctica) are presented in the efficient esterification of raw waste acidic. The best conversion was found to be 96.5% using the lipid material from the grease trap the University Restaurant UFES catalyzed enzymatically at 50 ° C and molar ratio of 1:9 (oil: alcohol) / Efluentes são lançados diariamente em corpos d água sem nenhum tipo de tratamento com elevados teores de óleos e graxas (OG) e constituem um enorme problema ambiental. Estes resíduos potencialmente disponíveis podem ser utilizados para o aproveitamento energético, como o uso de óleo para a produção de biodiesel. Como a maior barreira para produção de biodiesel envolve o custo de matéria prima, caixas de gordura de restaurantes, indústrias e de estações de tratamento de efluentes podem ser utilizados como matéria prima para produção de biocombustível, pois apresentam grandes quantidades de óleos e graxas sem nenhum custo. No entanto, óleos e graxas residuais contêm altos teores de ácidos graxos livres (AGL), e como a via preferencial para a produção de biodiesel é a transesterificação alcalina, pode ocorrer a formação de sabão como produto final, prejudicando a separação do glicerol e diminuindo o rendimento da reação. Desta forma, a transesterificação enzimática e ácida podem se apresentar como alternativas promissoras, visto que podem catalisar a modificação tanto de triglicerídeos como de ácidos graxos livres. O objetivo deste trabalho foi verificar a possibilidade de utilização de quatro tipos de resíduos oleosos do saneamento (Escumas de caixas de gordura de um Restaurante Universitário, de uma Indústria de Alimentos, de uma Estação de Tratamento de Efluentes e de Lodos de Fossas e Tanques Sépticos), caracterizar as propriedades físico-químicas dos óleos e graxas extraídos, bem como avaliar processos de geração de biodiesel envolvendo catalisador ácido (H2SO4) e enzimático (Candida antarctica imobilizada). Os resíduos estudados apresentaram altos teores de óleos e graxas e a caracterização físico-química mostrou elevados índices de acidez, saponificação e umidade. Foram detectados e quantificados os principais ácidos graxos saturados e insaturados por Cromatografia Líquida de Alta Eficiência (CLAE). A produção do biodiesel a partir das matérias primas provenientes de caixas de gordura apresentaram altos níveis de conversões, maior ou igual 90%, o que demonstra que ambos os catalisadores (H2SO4 e a lipase Candida antarctica) apresentam-se eficientes na esterificação de matérias primas residuais ácidas. A melhor conversão encontrada foi de 96,5% utilizando o material lipídico proveniente da caixa de gordura do Restaurante Universitário da UFES catalisado enzimaticamente a 50ºC e razão molar 1:9 (óleo:álcool)

Glacial isostatic adjustment (GIA) is the process by which the solid Earth responds to past and present-day changes in glaciers, ice caps, and ice sheets. This thesis focuses on vertical crustal motion of the Earth caused by GIA, which is influenced by several factors including lithosphere thickness, mantle viscosity profile, and changes to the thickness and extent of surface ice. The viscosity of the mantle beneath Antarctica is a poorly constrained quantity due to the rarity of relative sea-level and heat flow observations. Other methods for obtaining a better-constrained mantle viscosity model must be investigated to obtain more accurate GIA model predictions. The first section of this study uses seismic wave tomography to determine mantle viscosity. By calculating the deviation of the P- and S-wave velocities relative to a reference Earth model (PREM), the viscosity can be determined. For Antarctica mantle viscosities obtained from S20A (Ekstrom and Dziewonski, 1998) seismic tomography in the asthenosphere range from 1016 Pa∙s to 1023 Pa∙s, with smaller viscosities beneath West Antarctica and higher viscosities beneath East Antarctica. This agrees with viscosity expectations based on findings from the Basin and Range area of North America, which is an analogue to the West Antarctic Rift System. Section two compares bedrock elevations in Antarctica to crustal thicknesses, to infer mantle temperatures and draw conclusions about mantle viscosity. Data from CRUST 2.0 (Bassin et al., 2000), BEDMAP (Lythe and Vaughan, 2001) and specific studies of crustal thickness in Antarctica were examined. It was found that the regions of Antarctica that are expected to have low viscosities agree with the hot mantle trend found by Hyndman (2010) while the regions expected to have high viscosity are in better agreement with the trend for cold mantle. Bevis et al. (2009) described new GPS observations of crustal uplift in Antarctica and compared the results to GIA model predictions, including IJ05 (Ivins and James, 2005). Here, we have generated IJ05 predictions for a three layered mantle (viscosities ranging over more than four orders of magnitude) and compared them to the GPS observations using a χ2 measure of goodness-of-fit. The IJ05 predictions that agree best with the Bevis et al. observations have a χ2 of 16, less than the null hypothesis value of 42. These large values for the best-fit model indicate the need for model revisions and/or that uncertainties are too optimistic. Equally important, the mantle viscosities of the best-fit models are much higher than expected for West Antarctica. The smallest χ2 values are found for an asthenosphere viscosity of 1021 Pa•s, transition zone viscosity of 1023 Pa∙s and lower mantle viscosity of 2 x 1023 Pa∙s, whereas the expected viscosity of the asthenosphere beneath West Antarctica is probably less than 1020 Pa∙s. This suggests that revisions to the IJ05 ice sheet history are required. Simulated annealing was performed on the ice sheet history and it was found that changes to the recent ice load history have the strongest effect on GIA predictions. / Graduate

Neste trabalho, enzimas álcool-desidrogenases provenientes de fungos marinhos e a lipase imobilizada de Candida antarctica foram utilizadas para produção de compostos de interesse sintético e biológico. No capítulo 1, enzimas álcool-desidrogenases de fungos isolados da alga marinha Bostrychia radicans foram empregadas em reações de redução de cetonas fluoradas 1-5. Os fungos identificados como Botryosphaeria sp. CBMAI 1197, Eutypella sp. CBMAI 1196, Hidropisphaera sp. CBMAI 1194 e Xylaria sp. CBMAI 119 atuaram como biocatalisadores nestas reações levando à produção de álcoois com elevada pureza enantiomérica. O fungo Botryosphaeria sp. CBMAI 1197 destacou-se frente aos demais microrganismos, produzindo os álcoois (S)-2,2,2-trifluoro-1-feniletanol (1a) e (R)-1-(2,4,5-trifluorofenil)etanol (3a) com excelentes conversões (100% e 97%) e excessos enantioméricos (ee >99%). Este fungo também apresentou enzimas álcool-desidrogenases ativas frente a cetonas dicarboniladas 4-5, produzindo os álcoois 4,4,4-trifluoro-1-fenil-1,3-butanodiol (4a) e 4,4,4-trifluoro-1-(2-naftalenil)-1,3-butanodiol (5a) com 100% de conversão em ambos os casos e com purezas enantioméricas respectivas a 99% e 97%. Este foi o primeiro estudo realizado no Brasil com fluorocetonas dicarboniladas e com os fungos isolados da alga marinha Bostrychia radicans. No capítulo 2, a lipase comercial de Candida antarctica foi o biocatalisador empregado em reações de aminólise entre os ésteres linoleato de etila (1) e salicilato de etila (3), a amina graxa N-dodecilamina (2) e os aminoálcoois (4-9). A amina graxa N-dodecilamina (2) também foi utilizada em reações com o linoleato de etila (1), onde a lipase de Candida antarctica produziu a respectiva amida graxa 10 com rendimentos superiores a 95%. Os aminoálcoois foram selecionados para reações com o salicilato de etila (3), onde a lipase exibiu quimiosseletividade pelo grupo amino, produzindo predominantemente amidas fenólicas (12-19) com rendimentos entre 23-68%. A enzima CALB apresentou quimiosseletividade reduzida na reação com o 5-aminopentanol (6) onde os produtos amida 14 e éster 15 foram obtidos com rendimentos de 44 e 33%, respectivamente. O produto 2-hidroxi-N-(2-hidroxipropil)benzamida (19) foi obtido com rendimento superior a 90% a partir da reação catalisada pela lipase de Candida antarctica. Este produto foi selecionado como intermediário para a síntese de uma molécula hidrofóbica 21 que apresenta o éster oleato de etila em sua constituição. O produto 21 foi obtido com 75% de rendimento. As amidas fenólicas 12-21 produzidas neste trabalho são derivadas do ácido linoleico (ômega 6) e do ácido salicílico, os quais apresentam propriedades emolientes e antioxidantes. Estes compostos são interessantes para a formulação de produtos cosméticos de aplicação cutânea. Neste processo biotecnológico as reações foram conduzidas na ausência de solventes orgânicos, evitando o tratamento de solventes voláteis e a formação de subprodutos. Os compostos foram analisados por Cromatografia líquida de alta eficiência e caracterizados por RMN (1H, 13C), EMAR e IV. A aplicação de reações de biocatálise seja através de células microbianas ou de enzimas isoladas foram muito promissoras na síntese de compostos orgânicos de interesse como álcoois enantiomericamente puros ou amidas graxas. / In this work, alcohol dehydrogenase (ADHs) enzymes from marine fungi and immobilized lipase from Candida antarctica were employed for the production of compounds of biological and synthetic interest. In chapter 1, ADHs of fungi isolated from the marine alga Bostrychia radicans were used in reduction reactions of fluorinated ketones 1-5. The fungi identified as Botryosphaeria sp. CBMAI 1197, Eutypella sp. CBMAI 1196, Hidropisphaera sp. CBMAI 1194 and Xylaria sp. CBMAI 119 acted as biocatalysts in these reactions leading to production of alcohols with high enantiomeric purity. The fungus Botryosphaeria sp. CBMAI 1197 presented highlighted compared to other microorganisms producing the alcohols (S)-2,2,2-trifluoro-1-phenylethanol (1a) and (R) -1 - (2,4,5-trifluorophenyl) ethanol (3a) with excellent conversions (100% and 97%) and enantiomeric excesses (ee > 99%). This fungus also exhibited ADHs enzymes active with dicarbonylateds ketones, leading to the production of the alcohols 4,4,4-trifluoro-1-phenylbutane-1,3-diol (4a) and 4,4,4-trifluoro-1-(naphthalen-2-yl)butane-1,3-diol -1,3-butanediol (5a) with conversions of 100% in both cases and enantiomeric excess of 99%-97%, respectively. This was the first study conducted with dicarbonilated fluoroketones 4-5 and with fungi isolated from the marine alga Bostrychia radicans in Brazil. In chapter 2, immobilized lipase from Candida antarctica was used as biocatalyst in the aminolysis reaction between esters of ethyl linoleate (1) and ethyl salicylate (3), the fatty amine N-dodecylamine (2) and the aminoalcohols (4-8). Six aminoalcohols were selected for reactions with ethyl salicylate (3), where the lipase exhibited chemoselectivity by the amino groups, producing predominantly phenolic amides in yields of 23-63%. The CALB exhibited um reduction in chemoselectivity in the reaction with 5-aminopentanol (6) where the amide 14 and ester 15 products were obtained with 44% and 33% yields. The product 2-hydroxy-N-(2-hydroxypropyl) benzamide (19) was obtained in yield greater than 90% from the reaction catalyzed by lipase from Candida antarctica. This product was selected as reagente for the synthesis of a hydrophobic molecule 21 presenting ester ethyl oleate in its constitution. The product 21 was obtained in 75% yield. The phenolic amides 12-21 produced in this work are derived from linoleic acid (omega 6) and salicylic acid, which presents emollient and antioxidants properties. These compounds are interesting for the formulation of cosmetic products for skin application. In this biotechnological process, the reactions were carried out under solvent-free conditions and vacum, avoiding the treatment of volatile solvents and by-product formation. The compounds were analyzed by high performance liquid chromatography and characterized by NMR (1H, 13C), IR and HRMS. Applying biocatalysis reactions, either through microbial cells or isolated enzymes were promising for the synthesis of organic compounds such as enantiomerically pure alcohols and fatty phenolic amides.

L’objectif de cette thèse était de mieux comprendre les paramètres structuraux et environnementaux gouvernant l’énantiosélectivité de la lipase B de Candida antarctica (CALB), lors de la résolution des alcools secondaires linéaires chiraux. Ces composés sont notamment utilisés comme synthons chiraux dans l’industrie pharmaceutique. Dans un premier temps, une étude systématique des orientations du butan-2-ol et du pentan-2-ol au sein du site actif a été réalisée par modélisation moléculaire. Les résultats suggèrent l’existence de modes d’arrimages supplémentaires à ceux mentionnés dans la littérature. La comparaison selon l’énergie potentielle du substrat des structures les plus stables, combinée à la prise en compte de modes de fixation non productifs, nous a permis d’expliquer qualitativement l’énantiopréférence de la CALB pour la forme R. A l’aide du réacteur solide/gaz, nous avons montré que les résidus hydrophobes formant le canal d’accès du substrat au site actif (Ile189, Leu278 et Ala282), jouaient un rôle significatif dans l’énantiosélectivité de la CALB vis-à-vis des alcools secondaires. L’influence de la partie alkoxy du donneur d’acyle sur le ratio énantiomérique a également pu être mise en évidence. Par ailleurs, nous avons montré que des mutations isostériques de la poche stéréosélective conduisaient à des variations des paramètres thermodynamiques d’activation de l’acylation du pentan-2-ol, probablement suite à des modifications du réseau de liaisons hydrogène formé entre les résidus de la poche. Les études d’adsorption de l'eau et des substrats sur l’enzyme immobilisée nous ont permis de relier l'état d'hydratation de la CALB avec les effets particuliers de l'eau sur l’activité et la sélectivité de l’enzyme. / The aim of this thesis was to understand more precisely the structural and environmental parameters governing the enantioselectivity of lipase B from Candida antarctica (CALB), involved in the discrimination of chiral secondary alcohols enantiomers. These compounds are used in particular for the synthesis of enantiomerically pure pharmaceutical molecules. Initially a systematic study of the orientation of butan-2-ol and pentan-2-ol in the active site was performed by molecular modeling. The results suggest the existence of additional binding modes to those mentioned in the literature. The potential energy comparison of the most stable conformations of the substrate, combined with the existence of non productive binding modes, allowed us to explain qualitatively the enantiopreference of CALB for the R form. Using the solid/gas reactor, we have shown that hydrophobic residues forming the access channel of substrate to the active site (Ile189, Leu278 and Ala282), played a significant role in the enantioselectivity of CALB towards secondary alcohols. The influence of the alkoxy part of the acyl donor on the enatiomeric ratio E has also been highlighted. Furthermore, we showed that isosteric mutations of the stereoselective pocket led to changes in pentan-2-ol activation thermodynamic parameters of acylation, probably due to changes in the hydrogen bonds network formed between residues of the pocket. Studies of water and substrates adsorption on the immobilized enzyme allowed us to relate the hydration status of CALB with specific effects of water on the enzyme activity and selectivity.

Dans un contexte du développement durable, de nouvelles architectures macromoléculaires biosourcées ont été synthétisées à partir de synthons (diacides et diols) pouvant être obtenus par voies fermentaires à partir de sources carbonées issues de la biomasse. Dans un premier temps, différents copolyesters aliphatiques ont été synthétisés en masse, à l’aide d’un catalyseur organométallique à base de titane, à partir de diacides (acides succinique et adipique) et de diols (1,3-propanediol, 1,4-butanediol et 2,3-butanediol) courts. Dans un deuxième temps, des architectures macromoléculaires similaires ont été obtenues par catalyse enzymatique en solution à l’aide de la lipase B de Candida antarctica. L’influence de la longueur et de la structure des monomères sur leur réactivité en présence de la lipase a été particulièrement étudiée. Dans un troisième et dernier temps, des architectures macromoléculaires à base d’oligomères hydroxytéléchéliques d’un polyester bactérien : le poly((R)-3-hydroxybutyrate) (PHB)tels que des poly(ester-éther-uréthane)s et des copolyesters ont été obtenues soit par couplage de chaîne à l’aide d’un diisocyanate, ou par transestérification organométallique et enzymatique. Ces études ont permis d’analyser en détail l’effet de l’addition des synthons biosourcés dans les architectures macromoléculaires et notamment sur la structure cristalline, la stabilité thermique et les propriétés thermiques et optiques de ces polymères. De plus, le grand potentiel de la catalyse enzymatique pour la synthèse de polyesters et celui de l’utilisation d’oligomères de PHB pour l’élaboration de nouveaux matériaux performants ont pu être largement démontrés. / In the context of sustainable development, new biobased and aliphatic macromolecular architectures were synthesized from building blocks that can be obtained by fermentation routes using carbon sources from the biomass. First, several aliphatic copolyesters were synthesized in bulk from short dicarboxylic acids (such as succinic and adipic acids) and diols (such as 1,3-propanediol, 1,4-butanediol and 2,3-butanediol) by organometallic catalysis using an effective titanium-based catalyst. In a second time, similar macromolecular architectures were synthesized by an enzymatic process in solution using Candida antarctica lipase B as catalyst. The influence of the alkyl chain length and the structure of monomers on their reactivity toward the lipase were particularly discussed. In the third and last part, new macromolecular architectures based on hydroxytelechelic oligomers of a bacterial polyester: poly((R)-3-hydroxybutyrate) (PHB), such as poly(ester-ether-urethane)s and copolyesters, were obtained by either chain-coupling using a diisocyanate, or organometallic and enzymatic transesterification, respectively.These studies permitted to determine a close relationship between the effect of the building blocks structure integrated in the final macromolecular architectures and the intrinsic properties, such as the crystalline structure, the thermal stability and the thermal and optical properties, of these polymers. In addition, the great potential of the lipase-catalyzed synthesis of polyesters and the use of PHB oligomers for developing new high performance materials has been clearly established.

[ES] Este trabajo tiene como objetivo investigar los métodos de conservación in situ aplicables a los hallazgos arqueológicos de los loberos-balleneros, los cuales están compuestos por material proveniente del archipiélago Shetland del Sur (Antártida Occidental). Los loberos-balleneros fueron marineros llevados al territorio por compañías de caza de mamíferos marinos en los siglos XVIII y XIX. Esos cazadores habitaban temporalmente en refugios construidos en la Antártida. Las huellas que dejaron se caracterizan por la presencia de materiales muy frágiles, que se conservan debido a las condiciones ambientales particulares del continente antártico. Desde la primera expedición de excavación hecha por el Laboratorio de Estudios Antárticos en Ciencias Humanas de la Universidad Federal de Minas Gerais (Leach), en 2010, un eje de investigación ha estado articulando la metodología de excavación a la conservación in situ. Este eje ha dado paso a este proyecto de investigación doctoral desarrollado en la Universitat Politècnica de València. / [CA] Aquest treball té com a objectiu investigar els mètodes de conservació in situ aplicables a lestroballes arqueològiques dels loberos-balleners, els quals estan compostos per material provinent de l'arxipèlag Shetland de Sud (Antàrtica Occidental). Els loberos-balleners van ser mariners duts al territori per companyies de caça de mamífers marins en els segles XVIII i XIX. Aquests caçadors habitaven temporalment en refugis construïts a l'Antàrtica. Les petjades que van deixar es caracteritzen per la presència de materials molt fràgils, que només es conserven a causa de les condicions ambientals particulars del continent antàrtic. Des de la primera expedició d'excavació feta pel Laboratori d'Estudis Antàrtics en Ciències Humanes de la Universitat Federal de Mines Gerais (Leach), el 2010, un eix d'investigació ha estat articulant la metodologia d'excavació a la conservació in situ. Aquest eix ha donat pas a aquest projecte de recerca doctoral desenvolupat a la Universitat Politècnica de València. / [EN] The proposal aims investigate the methods of the in situ preservation of the whalers' archaeological remains, concerning to the South Shetland Archipelago (Occidental Antarctica). The whalers were sailors taken to the territory by companies hunting of marine mammals of the 18th and 19th centuries. These hunters lived temporarily in shelters made in Antarctica. These traces are characterized by the presence of very fragile materials, that only preserved by the specific environmental conditions provided by the Antarctic context. Since the first excavation expedition made by of the Antarctic Studies Laboratory in Human Sciences of the Federal University of Minas Gerais (Leach) in 2010, an axis of investigation is articulating the methodology excavation with the in situ conservation, which has become this PhD research project, developed together with the Universitat Politècnica de València. / La investigación ha recibido apoyo de la FAPEMIG, Fundação de Amparo à Pesquisa do Estado de Minas Gerais (Proyecto APQ 01366-17), del PROANTAR, Programa Antártico Brasileiro, y se ha llevado a cabo gracias al Programa de Doutorado Pleno no Exterior da Coordenação de Aperfeiçoamento de Pessoal de Nível Superior‒CAPES (Brasil), por medio del Programa de Doutorado Pleno no Exterior de 2015. / De Alkmim Radicchi, G. (2022). Conservación in situ en el Proyecto Arqueología Antártica. Desafíos bajo el paralelo 60°S [Tesis doctoral]. Universitat Politècnica de València. https://doi.org/10.4995/Thesis/10251/182647 / TESIS

<p> </p><p>A chemoselective catalyst is preferred in a chemical reaction where protecting groups otherwise are needed. The two lipases <em>Candida antarctica </em>lipase B and <em>Rhizomucor miehei</em> lipase showed large chemoselectivity ratios, defined as (<em>k_cat</em>/<em>K</em>_M)_OH/ (<em>k_cat</em>/<em>K</em>_M)_SH, in a transacylation reaction with ethyl octanoate as acyl donor and hexanol or hexanethiol as acyl acceptor (<strong>paper I</strong>). The chemoselectivity ratio of the uncatalyzed reaction was 120 in favour of the alcohol. Compared to the uncatalyzed reaction, the chemoselectivity was 730 times higher for <em>Candida antarctica </em>lipase B and ten times higher for <em>Rhizomucor miehei</em> lipase. The <em>K</em>_M towards the thiol was more than two orders of magnitude higher than the <em>K</em>_M towards the corresponding alcohol. This was the dominating contribution to the high chemoselectivity displayed by the two lipases. In a novel approach, <em>Candida antarctica </em>lipase B was used as catalyst for enzymatic synthesis of thiol-functionalized polyesters in a one-pot reaction without using protecting groups (<strong>paper II</strong>). Poly(e-caprolactone) with a free thiol at one of the ends was synthesized in an enzymatic ring-opening polymerization initiated with mercaptoethanol or terminated with either 3-mercaptopropionic acid or g-thiobutyrolactone.</p><p> </p>

Decentralisation for local community development has become the new paradigm of development discourse in Ghana in the present times. There is currently an elaborate legal framework in Ghana on decentralisation as a means for addressing local community development. The role of law in development is therefore implicated in the discourse. This study raises provocative, startling and challenging questions not only on the decentralisation programme, but the appropriate theoretical framework for reading the role of law in development. The study argues that decentralisation in Ghana is a spatial strategy of the state for addressing the crisis of its political economy and not one necessarily for local community development. Taking its starting point in land administration in the Upper West Region of Ghana (predominantly agrarian communities), the study explores how the objectives of decentralisation in Ghana address the subjectivity of development needs of local communities in Ghana. The study's contention is that the legal regime of the decentralisation programme and its praxis fail to address a pertinent development concern (land) of the Upper West communities. The study argues that if local community development were the object of the programme, it would perforce address the problematic of land administration that is an important concern for predominantly subsistence farming communities. The study also demonstrates how a spatial reading of social phenomenon provides critical insights to an understanding of the role of law in development. The study is based on a field study conducted in Ghana and among the communities of the Upper West Region, through interviews with officials of institutions, traditional authorities and civil society organisations. The interviews were complemented by written primary and secondary sources. Primary sources include documents from the National Archives in Ghana and from decentralised institutions in the Upper West Region. Secondary sources include unpublished essays and theses, books, articles, reported cases in the Ghana Law Reports, unreported and/or pending cases in the Ghanaian courts.

The thesis examines the role of Islam and Shariah (Islamic law) in the economic development of Malaysia and it rejects the assumption that Islam and Shariah inhibit economic development. In contemporary Malaysia, there are two 'policies' adopted by the Government. Firstly, 'Islamisation' which is for the advancement of Islamic law and institution building. Secondly, 'Malaynisation' which promotes the socio-economic development of the Malay ethnic group. The study adopts a holistic approach which covers the political economy of law in Malaysia. The thesis explores the relationship between the two policies considering in particular whether they are essentially the same. The study covers the pre-colonial, colonial and post-colonial periods although the focus is on the post-1969 period which involved the application of the New Economic Policy (NEP). The NEP was a pro-Malay Policy to rectif,' the economic imbalance of the Malays vis-à-vis other communities. Therefore, the focus of this thesis is on the Malay- Muslim population of Peninsular Malaysia who form the bulk of the Bumiputera (indigenous people). Two Bum iputera and Islamic organisations, Bank Islam (BIIMB) and Tabung Haji (TH) as well as the Bumiputera unit trust scheme, Amanah Saham Nasional (ASN) are used as the case studies. Their establishment, structure and organisation are examined. There is a specific focus on the extent to which they are examples of Islamisation or Malaynisation. It is clear that in contemporary Malaysia, Islam and Shariah are being used by the Government to promote economic development. Islamic values have been used to further Malay economic participation in the commercial sector. As a consequence, the economic position of many Malay-Muslims has greatly improved. However, the Government position is questioned by the Islamic opposition who say that the Islamisation policy in many respects is either contrary to Islam or merely cosmetic, and want a 'pure' Islamic approach. The thesis therefore involves a critical examination of the perspectives of both the Government and the Islamic opposition.