No / The surface energy of a-lactose monohydrate measured by inverse gas chromatography (IGC) is reported along with a dynamic molecular modelling study of the interaction of the various molecular probes with different surfaces of a-lactose monohydrate. The IGC results show that a-lactose monohydrate is acidic in nature. Using quantitative calculations of the energy of adsorption, the acidic nature of the surface is confirmed and the calculated values agree closely with the experimentally measured values. Along with the acidic nature, dynamic molecular modelling also reveals that the presence of a channel and water molecules on a surface affects the surface energetics of that face. The presence of water on the surface can decrease or increase the surface energy by either blocking or attracting a probe molecule, respectively. This property of water depends on its position and association with other functional groups present on the surface. The effect of a channel or cavity on the surface energy is shown to depend on its size, which determines whether the functional groups in the channel are assessable by probe molecules or not. Overall molecular modelling explains, at the molecular level, the effect of different factors affecting the surface energy of individual faces of the crystal.

No / A buried or dumped body may be accompanied by a range of materials, including clothing and other textiles, metals such as tools and weapons, as well as plastics and paper products. This chapter concentrates on clothing and metal fastenings associated with clothing. Bodies that have been subject to clandestine disposal may be clothed, semiclothed, or naked. Reconstructing the nature and position of this clothing is critical to understanding the circumstance of disposal as well as perhaps to assisting in establishing motive and offender behavior. In addition, clothing and personal effects may provide assistance in establishing identity, although this will need confirmation by dental records or DNA. Modern clothing, footwear, and accessories are made from a range of materials: natural and synthetic textiles, leather, plastic, and metal. Along with the body they may be subject to a range of depositional environment, including surface disposal and burial in a range of soil types and microclimates. These materials will respond and degrade at different rates often leading to differential preservation.

Yes / Properties of a matter are intrinsically dependent upon the internal arrangement of molecules in the solid state. Therefore, knowledge of 3-dimensional structure of the matter is prerequisite for structure-property correlations and design of functional materials. Over the past century, X-ray crystallography has evolved as a method of choice for accurate determination of molecular structure at atomic resolution. The structural information obtained from crystallographic analysis paved the way for rapid development in electronic devices, mineralogy, geosciences, materials science, pharmaceuticals, etc. Knowledge of the structural information of active pharmaceutical ingredients (APIs) is prerequisite for rational drug design and synthesis of new chemical entities for development as new medicines. Over the past two decades, X-ray crystallography has played a key role in the design of pharmaceutical cocrystals-crystalline solids containing an API and one or more of pharmaceutically acceptable coformers. These materials have proved promising for fine-tuning several important properties of APIs. This short review highlights the history of crystallography, early breakthroughs, and the role of crystallography in understanding physicochemical properties of pharmaceutical cocrystals. / S. Aitipamula gratefully acknowledges the financial support from the Institute of Chemical and Engineering Sciences of A*STAR (Agency for Science, Technology and Research), Singapore. V. R. Vangala thanks Royal Society of Chemistry for Researcher Mobility Grant (2015/17).

As características físicas e físico-químicas dos híbridos de milho verde para a produção de pamonha e ainda o efeito do armazenamento da matéria-prima sobre as características de qualidade do produto final são ainda pouco conhecidas, mas de grande importância para se implantar agroindústrias melhor estruturadas. Os objetivos do presente trabalho foram avaliar híbridos de milho para a produção de pamonhas e também avaliar o efeito do armazenamento (condições ambientes e de refrigeração) desses híbridos sobre as características físicas, físico-químicas e sensoriais das pamonhas produzidas. Os híbridos avaliados foram o AG1051, BM3061 e DOW8003. Para a caracterização dos mesmos foram utilizadas espigas recém-colhidas, que foram avaliadas (análises físicas, físico-químicas, porcentagem de massa) e processadas em pamonhas que foram avaliadas mediante análises físicas, físico-químicas e análise sensorial (ADQ). Os grãos dos três híbridos avaliados apresentaram semelhanças quanto à composição (teor de umidade de 67,4% e de fibras solúveis de 0,3%), cor (luminosidade 72, croma a* -0,8 e croma b* de 33). Nas demais características, os híbridos apresentaram diferenças estatísticas (p<0,05) entre si, com teores de amido (11,4 a 12,8%), carboidratos solúveis (0,8 a 1,6%) e fibras insolúveis (2,2 a 2,8%). Nas propriedades de pasta (RVA) apresentaram valores mais amplos, variando a viscosidade máxima entre 202 e 314RVU e tendência à retrogradação entre 94 e 164RVU. As pamonhas elaboradas com estes híbridos apresentaram composição mais variável, com pH entre 7,1 e 7,5, umidade (63,6 a 65,9%), amido (5,0 a 5,4%), carboidratos solúveis totais (18,9 a 21,8%), fibras solúveis (0,3 a 1,0%), fibras insolúveis (1,1 a 1,5%). Os parâmetros de cor foram luminosidade (54,8 a 59,8%), croma a* (-4,6 a -5,1) e croma b* (20,5 a 29,6). A firmeza em texturômetro entre 804 e 1584N. Na avaliação sensorial as notas variaram para cor amarela de 5,7 a 6,3, textura cremosa (4,2 a 5,8), fibrosa (5,4 a 6,1), firme (6,0 a 7,1) e impressão global (6,4 a 7,5). O efeito do armazenamento dos híbridos na palha em condições ambientes (25ºC e 80%UR) e sob refrigeração (7&#176;C e 98%UR) sobre a qualidade dos grãos e das pamonhas foi avaliado aos zero, 3 e 6 dias após a colheita. É recomendado o armazenamento na condição de refrigeração (7&#176;C) das espigas de milho verde para elaboração de pamonha, pois foi mais eficiente em manter as características físicas e físicoquímicas do milho e alterar menos as características das pamonhas. Os produtos dos três híbridos armazenados ao ambiente e sob refrigeração receberam, no geral, boas notas pelos provadores, porém, observa-se tendência das pamonhas obtidas com matérias-primas armazenadas por 6 dias, de apresentarem-se mais firmes e fibrosas, menos cremosas e com sabor de fermentado. Pode-se concluir que, além das variações decorrentes do armazenamento, ocorre também variabilidade dentro dos híbridos e deve haver interferência do processamento nas características destes produtos, principalmente nas etapas de formulação e cocção em água, além do tipo de embalagem requisitada. / The physicochemical characteristics of the hybrids of green corn for the production of pamonha and the effect of the raw materials storage on the quality of the final product are still not well known, but of great importance to the development of the agro-industry. The objectives of the present study were to evaluate hybrids of corn for the production of pamonha and the effects of the storage (ambient conditions and refrigeration) of these hybrids on the physical, physicochemical and sensory characteristics of pamonha. The hybrids evaluated were the AG1051, BM3061 and DOW8003. Newly harvested corn-cobs have been used to characterize the hybrids. They were evaluated with regard to physical and physicochemical characteristics and mass percentage. The processed pamonhas were also analysed regarding their physical, physicochemical and sensory characteristics (DQA). The grains of the three hybrids presented similarities with regard to composition (moisture content of 67.4% and soluble fibers of 0.3%) and color (luminosity 72, chroma a* -0.8 and chroma b* 33). The hybrids were statistically different (p<0.05) with regard to starch content (11.4 a 12.8%), soluble carbohydrates (0.8 a 1.6%) and insoluble fibers (2.2 a 2.8%). With regard to the pasting properties (RVA), the results presented wider differences: the peak viscosity varied between 202 and 314RVU and the setback, between 94 and 164RVU. The pamonhas prepared with the hybrids presented more variable composition, with pH between 7.1 and 7.5, moisture content between 63.6 and 65.9%, starch content between 5.0 and 5.4%, total soluble carbohydrates between 18.9 and 21.8%, soluble fibers between 0.3 and 1.0%, and insoluble fibers between 1.1 and 1.5%. The parameters of color were Luminosity (54.8 to 59.8%), chroma a* (-4.6 to -5.1) e chroma b* (20.5 to 29.6). The hardness (texture analyzer) varied between 804 and 1584N. In the sensory analysis, the grades varied from 5.7 to 6.3 for the yellow color, 4.2 to 5.8 for the creamy texture, 5.4 to 6.1 for the fibrous texture, 6.0 to 7.1 for the firmness and the general impression varied from 6.4 to 7.5. The effects of the storage of the hybrids with husks, at room temperature (25&#176; C and 80% UR) and under refrigeration (7&#176; and 98% UR), on the quality of the grains and pamonhas were assessed at 0, 3 and 6 days after the harvest. It is recommended the storage of the corn cobs for the production of pamonha under refrigeration (7oC) because this condition results in better maintenance of the physical and physicochemical characteristics of the corn and pamonhas. The products of the three hybrids stored at room temperature and under refrigeration received, in general, good grades by the provers, however, it was observed that the pamonhas produced with raw materials stored for 6 days were firmer and more fibrous, less creamy and with some yeasty flavour. It can be concluded that, apart from the variations due to the storage, there is variability within the hybrids and there must be interference of the processing in the characteristics of the products, mainly in the steps of formulation and boiling into water, besides of the type of packaging required.

As características físicas e físico-químicas dos híbridos de milho verde para a produção de pamonha e ainda o efeito do armazenamento da matéria-prima sobre as características de qualidade do produto final são ainda pouco conhecidas, mas de grande importância para se implantar agroindústrias melhor estruturadas. Os objetivos do presente trabalho foram avaliar híbridos de milho para a produção de pamonhas e também avaliar o efeito do armazenamento (condições ambientes e de refrigeração) desses híbridos sobre as características físicas, físico-químicas e sensoriais das pamonhas produzidas. Os híbridos avaliados foram o AG1051, BM3061 e DOW8003. Para a caracterização dos mesmos foram utilizadas espigas recém-colhidas, que foram avaliadas (análises físicas, físico-químicas, porcentagem de massa) e processadas em pamonhas que foram avaliadas mediante análises físicas, físico-químicas e análise sensorial (ADQ). Os grãos dos três híbridos avaliados apresentaram semelhanças quanto à composição (teor de umidade de 67,4% e de fibras solúveis de 0,3%), cor (luminosidade 72, croma a* -0,8 e croma b* de 33). Nas demais características, os híbridos apresentaram diferenças estatísticas (p<0,05) entre si, com teores de amido (11,4 a 12,8%), carboidratos solúveis (0,8 a 1,6%) e fibras insolúveis (2,2 a 2,8%). Nas propriedades de pasta (RVA) apresentaram valores mais amplos, variando a viscosidade máxima entre 202 e 314RVU e tendência à retrogradação entre 94 e 164RVU. As pamonhas elaboradas com estes híbridos apresentaram composição mais variável, com pH entre 7,1 e 7,5, umidade (63,6 a 65,9%), amido (5,0 a 5,4%), carboidratos solúveis totais (18,9 a 21,8%), fibras solúveis (0,3 a 1,0%), fibras insolúveis (1,1 a 1,5%). Os parâmetros de cor foram luminosidade (54,8 a 59,8%), croma a* (-4,6 a -5,1) e croma b* (20,5 a 29,6). A firmeza em texturômetro entre 804 e 1584N. Na avaliação sensorial as notas variaram para cor amarela de 5,7 a 6,3, textura cremosa (4,2 a 5,8), fibrosa (5,4 a 6,1), firme (6,0 a 7,1) e impressão global (6,4 a 7,5). O efeito do armazenamento dos híbridos na palha em condições ambientes (25ºC e 80%UR) e sob refrigeração (7&#176;C e 98%UR) sobre a qualidade dos grãos e das pamonhas foi avaliado aos zero, 3 e 6 dias após a colheita. É recomendado o armazenamento na condição de refrigeração (7&#176;C) das espigas de milho verde para elaboração de pamonha, pois foi mais eficiente em manter as características físicas e físicoquímicas do milho e alterar menos as características das pamonhas. Os produtos dos três híbridos armazenados ao ambiente e sob refrigeração receberam, no geral, boas notas pelos provadores, porém, observa-se tendência das pamonhas obtidas com matérias-primas armazenadas por 6 dias, de apresentarem-se mais firmes e fibrosas, menos cremosas e com sabor de fermentado. Pode-se concluir que, além das variações decorrentes do armazenamento, ocorre também variabilidade dentro dos híbridos e deve haver interferência do processamento nas características destes produtos, principalmente nas etapas de formulação e cocção em água, além do tipo de embalagem requisitada. / The physicochemical characteristics of the hybrids of green corn for the production of pamonha and the effect of the raw materials storage on the quality of the final product are still not well known, but of great importance to the development of the agro-industry. The objectives of the present study were to evaluate hybrids of corn for the production of pamonha and the effects of the storage (ambient conditions and refrigeration) of these hybrids on the physical, physicochemical and sensory characteristics of pamonha. The hybrids evaluated were the AG1051, BM3061 and DOW8003. Newly harvested corn-cobs have been used to characterize the hybrids. They were evaluated with regard to physical and physicochemical characteristics and mass percentage. The processed pamonhas were also analysed regarding their physical, physicochemical and sensory characteristics (DQA). The grains of the three hybrids presented similarities with regard to composition (moisture content of 67.4% and soluble fibers of 0.3%) and color (luminosity 72, chroma a* -0.8 and chroma b* 33). The hybrids were statistically different (p<0.05) with regard to starch content (11.4 a 12.8%), soluble carbohydrates (0.8 a 1.6%) and insoluble fibers (2.2 a 2.8%). With regard to the pasting properties (RVA), the results presented wider differences: the peak viscosity varied between 202 and 314RVU and the setback, between 94 and 164RVU. The pamonhas prepared with the hybrids presented more variable composition, with pH between 7.1 and 7.5, moisture content between 63.6 and 65.9%, starch content between 5.0 and 5.4%, total soluble carbohydrates between 18.9 and 21.8%, soluble fibers between 0.3 and 1.0%, and insoluble fibers between 1.1 and 1.5%. The parameters of color were Luminosity (54.8 to 59.8%), chroma a* (-4.6 to -5.1) e chroma b* (20.5 to 29.6). The hardness (texture analyzer) varied between 804 and 1584N. In the sensory analysis, the grades varied from 5.7 to 6.3 for the yellow color, 4.2 to 5.8 for the creamy texture, 5.4 to 6.1 for the fibrous texture, 6.0 to 7.1 for the firmness and the general impression varied from 6.4 to 7.5. The effects of the storage of the hybrids with husks, at room temperature (25&#176; C and 80% UR) and under refrigeration (7&#176; and 98% UR), on the quality of the grains and pamonhas were assessed at 0, 3 and 6 days after the harvest. It is recommended the storage of the corn cobs for the production of pamonha under refrigeration (7oC) because this condition results in better maintenance of the physical and physicochemical characteristics of the corn and pamonhas. The products of the three hybrids stored at room temperature and under refrigeration received, in general, good grades by the provers, however, it was observed that the pamonhas produced with raw materials stored for 6 days were firmer and more fibrous, less creamy and with some yeasty flavour. It can be concluded that, apart from the variations due to the storage, there is variability within the hybrids and there must be interference of the processing in the characteristics of the products, mainly in the steps of formulation and boiling into water, besides of the type of packaging required.

Surface engineering of tailored materials with adjustable characteristics in relation to biological environment, is one of the main prerequisites for biotechnological applications. In recent years, advanced surface coatings in the nanometer range have drawn big attention. A special category of this group are stimuli responsive polymers tethered by one functional end to the surface. When the surface grafting density is big enough, the polymer chains are forced to stretch away from the interface due to excluded volume effects, creating a so called polymer brush. Nano-scaled polymer brushes are advantageous due to their nanostructure, which can be comparable to biological species, and their collaborative response to external stimuli. Moreover, the material design parameters such as chemistry, surface topography, charge, and surface wettability can be adjusted by using the appropriate polymer, or a combination of polymers with respect to the desired material performance. In case of binary polymer brushes, the materials' properties are switched between the properties of two constituent polymers. Besides, upon switching of external stimuli, biomodified binary polymer brushes can hide or expose biofunctionalities, on demand. Hence, they are classified as smart biomaterials' surface coatings.

Rheumatoid arthritis (RA) is a chronic inflammatory joint disease associated with high levels of tumour necrosis factor-alpha (TNF-a) in synovial fluid and synovial tissue (Saxne et al., 1989). Thalidomide is a proven inhibitor of the biological synthesis of TNF-a (Sampaio et al., 1991) and is believed to rely on this action for its suppression of the wasting of tissue which accompanies RA. Oral administration of thalidomide has proven to be effective in RA, but unacceptable side effects are easily provoked (Gutierrez-Rodriguez, 1984). Administration of thalidomide via the dermal route can down-regulate TNF-a production in and around the affected joint, and this without raising the systemic blood level to a problematical level. Based on thalidomide's physicochemical properties, it is unlikely that it can be delivered percutaneously at a dose required for RA. Therefore, we have embraced the idea of using N-alkyl analogues of thalidomide. The most important feature that an analogue of this compound might contribute is decreased crystallinity and increased lipophilicity. Ordinarily both these parameters should favour percutaneous delivery. The current study was primarily aimed at exploring the feasibility of percutaneous delivery of thalidomide and subsequently, three of its odd chain IV-alkyl analogues (methyl, propyl and pentyl) via physicochemical characterization and assessment of their innate abilities to diffuse through skin as an initial step towards developing a topical dosage form for the best compound. The biological activities, more specifically their potential to inhibit the production of TNF-a was determined for thalidomide and its N-alkyl analogues. In order to achieve the objectives, the study was undertaken by synthesizing and determining the physicochemical parameters of thalidomide and its N-alkyl analogues. A high level of crystallinity is expressed in the form of a high melting point and heat of fusion. This limits solubility itself, and thus also sets a limit on mass transfer across the skin. Generally, the greater a drug's innate tendency to dissolve, the more likely it is that the drug can be delivered at an appropriate rate across the skin (Ostrenga et al., 1971). Therefore, the melting points and heats of fusion were determined by differential scanning calorimetry. Aqueous solubility and the partition coefficient (relative solubility) are major determinants of a drug's dissolution, distribution and availability. N-octanollwater partition coefficients were determined at pH 6.4. Solubilities in water, a series of n-alcohols and mixed solvents were obtained, as well as the solubility parameters of the compounds in study. Secondly, in vitro permeation studies were performed from these solvents and vehicles using vertical Franz diffusion cells with human epidermal membranes. Thirdly, tumour necrosis factor-alpha (TNF-a) inhibition activities were assessed for thalidomide and its N-alkyl analogues. By adding a methyl group to the thalidomide structure, the melting point drops by over 100°C and, in this particular instance upon increasing the alkyl chain length to five -CH2- units the melting points decrease linearly. Heats of fusion decreased dramatically upon thalidomide's alkylation as well. Methylation of the thalidomide molecule enhanced the aqueous solubility 6-fold, but as the alkyl chain length is further extended from methyl to pentyl, the aqueous solubility decreased exponentially. The destabilization of the crystalline structure with increasing alkyl chain length led to an increase in lipophilicity and consequently an increase in solubility in nonpolar media. Log partition coefficients increased linearly with increasing alkyl chain length. Solubilities in a series of n-alcohols, methanol through dodecanol, were found to be in the order of pentyl > propyl > methyl > thalidomide. The N-alkyl analogues have more favourable physicochemical properties than thalidomide to be delivered percutaneously. The in vitro skin permeation data proved that the analogues can be delivered far easier than thalidomide itself. N-methyl thalidomide showed the highest steady-state flux through human skin from water, n-alcohols and combination vehicles. Thalidomide and its N-alkyl analogues were all active as TNF-a inhibitors. Finally, active as a TNF-a inhibitor, N-methyl thalidomide is the most promising candidate to be delivered percutaneously for treatment of rheumatoid arthritis, of those studied. / Thesis (PhD (Pharmaceutics))--PU for CHE, 1999.

Une exposition aux nanoparticules (NP) de dioxyde de titane (TiO2) peut entraîner un remodelage matriciel, dans lequel la Matrix Metalloprotéase-1 (MMP-1) notamment pourrait jouer un rôle important. Pour vérifier cette hypothèse, nous avons 1/ mesuré l' expression de la MMP-1 sur des fibroblastes pulmonaires humains après exposition à des particules de TiO2 de différentes tailles, formes et variétés cristallines, ainsi qu' une NP de noir de carbone (NC), et 2/ administré des NP de TiO2 et de NC sur un modèle d‟emphysème pulmonaire induit par l' élastase chez le rat. Sur les fibroblastes pulmonaires humains, certaines NP de TiO2 induisent l' expression de la MMP-1 via l' interleukine-1β (IL-1β) et augmentent son activité. Les particules de TiO2 micrométriques induisent l' expression de la MMP-1 sans lien avec l' IL-1β et les NP de NC ne modulent pas l' expression de la MMP-1. L' exposition des rats aux NP de TiO2 n' entraîne pas d' effet ; l' exposition aux NP de NC entraîne une inflammation et une induction de l' expression de la MMP-12. Cette exposition aggrave, de plus, l' inflammation provoquée par l' élastase, ce qui n' est pas observé avec les NP de TiO2. Au total, notre travail montre bien un rôle pour les NP de TiO2 dans le remodelage matriciel, via l' induction et l' activation de la MMP-1 in vitro. In vivo, les NP de NCpeuvent aggraver ceertaines réponses à l' élastse. La composition chimique et la taille des particules semblent être des déterminants importants de leurs effets. / Exposure to titanium dioxide (TiO2) nanoparticles (NP) can lead to matrix remodeling, a phenomenon in which Matrix metalloprotease-1 (MMP-1) notably could play an important role. To validate this hypothesis, we 1/ studied MMP-1 expression in human pulmonary fibroblasts after exposure to TiO2 particles of different sizes, shapes and crystal phases and one Carbon Black (CB) NP, and 2/ measured the effect of TiO2 CB NP on an elastase-induced emphysema model in rats.On human lung fibroblasts, some TiO2 NP induced MMP-1 through an interleukin-1β (IL-1β) dependent mechanism, and increased MMP-1 activity. TiO2 micrometric particles induced MMP-1 without IL-1β implication, and CB NP did not induce MMP-1. Rat exposure to TiO2 NP had no effect but exposure to NC NP induced inflammation and MMP-12 expression. TiO2 NP did not modulate elastase effects. NC NP aggravated elastase-induced inflammation.In total, our work shows a role for TiO2 NP in matrix remodeling, via MMP-1 induction and activation in vitro. In vivo, CB NP can aggravate some elastase-induced effects. Particles composition and size seem to be important determinants of their effect.

Le poly(butylène succinate) (PBS) est un polyester aliphatique biodégradable dont les propriétés en font un bon candidat pour le remplacement des polyoléfines. De plus, ses deux monomères, l'acide succinique et le butane-1,4-diol, peuvent être issus de la biomasse via un procédé de fermentation de sucres. L'étude réalisée ici a été séparée en deux grandes parties : le PBS linéaire d'une part et le PBS branché d'autre part. La première partie montre que la cinétique de synthèse du PBS suit bien le modèle d'estérification établi par Flory. Par la suite, l'étude des propriétés physico-chimiques du PBS a permis de remonter à des paramètres comme la masse molaire critique d'enchevêtrement, le module du plateau caoutchoutique, l'énergie d'activation du PBS fondu ou encore les paramètres de l'équation Mark-Houwink-Sakurada. Une étude sur ses propriétés thermiques a permis de décrire l'évolution de son comportement en fonction de sa masse molaire. Enfin, le profil d'énergie potentielle de l'estérification entre l'acide succinique et le butane-1,4-diol a été tracé en utilisant un outil de chimie quantique. La seconde partie traite de l'étude de PBS branchés obtenus en employant des agents de branchement (polyols) pouvant être issus de la biomasse comme l'huile de ricin, le glycérol et le polyglycérol. La stratégie adoptée a été le couplage entre un oligomère PBS fonctionnalisé acide carboxylique et les agents de branchement. L'étude en présence d'huile de ricin a mis en avant les relations entre la structure, déterminée en SEC-Triple Détection, et les propriétés physico-chimiques du PBS branché. L'optimisation de la synthèse en présence de glycérol ou de polyglycérol a été abordée à partir de la méthode des plans d'expériences. Comparé à la méthode « un facteur à la fois », des résultats prometteurs et semblables à ce qui est rapporté dans la littérature ont été obtenus pour l'étude du PBS branché en présence de glycérol. / Poly(butylene succinate) (PBS) is a biodegradable aliphatic polyester whose properties make it a promising polymer for the replacement of polyolefins. Moreover, its two monomers, succinic acid and 1,4-butanediol, can be produced via a fermentation process of sugars. This study has been separated into two great parts: linear PBS on the one hand and branched PBS on the other hand. In the first part, kinetics of the PBS synthesis showed a good agreement with the esterification model of Flory. We determined some fundamental parameters of PBS like critical molecular weight of entanglement, the rubbery plateau modulus, the energy of activation of melt PBS and parameters of the Mark-Houwink-Sakurada relationship. We have also realized a study on the influence of the molecular weight on the thermal properties of PBS. Finally, we constructed the potential energy profile of the esterification between succinic acid and 1,4-butanediol through a quantum chemistry study. The second part dealt with the study of branched PBS in the presence of biosourced polyols like castor oil, glycerol and polyglycerol. These syntheses were realized between an acid-functionalized PBS oligomer and the branching agents. We put forward the relationships between the structure, determined by SEC-Triple Detection, and the physicochemical properties of branched PBS in presence of castor oil. Syntheses of branched PBS in presence of glycerol or polyglycerol were optimized with design of experiments technique. Promising and similar results from the literature were obtained in the case of branched PBS in presence of glycerol compared to the method of “one parameter at a time”.

Foram sintetizadas duas séries de tensoativos catiônicos de estruturas gerais RCONH(CH2)2-N+(CH3)3 Cl- e RCONH(CH2)2-N+(CH3)2-CH2-C6H5 Cl-, sendo RCO uma cadeia acílica contendo 10, 12, 14 e 16 átomos de carbono. Estes tensoativos foram sintetizados pela reação do ácido carboxílico puro com N,N-dimetiletilenodiamina resultando na amidoamina correspondente. A quaternização desta última foi feita pela reação com cloreto de benzila ou com iodeto de metila. Os iodetos foram convertidos nos correspondentes cloretos por troca-iônica. A localização média da interface micelar e a conformação do grupo hidrofílico na micela foram investigadas por IV e RMN. A adsorção na interface solução-ar e a micelização foram estudadas por diversas técnicas: calorimetria, condutância, FEM (força eletromotriz), IV de FT, RMN e tensão superficial. Os resultados foram comparados com os de tensoativos catiônicos comuns, como R\'N+(CH3)3R\" Cl-, sendo R\' = grupo alquílico contendo de 10 a 16 carbonos e R\" = um grupo metila ou benzila. A adsorção e a micelização dos tensoativos contendo o \"espaçador\" (CONH-CH2-CH2) são mais favoráveis. Os valores de &#916;G&#186;ads e &#916;G&#186;mic mais negativos para estes tensoativos, refletem principalmente a transferência mais favorável do grupo polar da solução aquosa para a interface solução/ar e/ou para a micela. Isto ocorre devido à formação de ligações de H, diretas e/ou via água, entre os grupos amida dos monômeros de tensoativo na interface e micela. As diferenças nos valores de &#916;G&#186;cabeça+CH3 dos tensoativos com e sem o grupo amida na adsorção (&#916;&#916;G&#186; ads cabeça+CH3 = -17.2 kJ mol-1) e micelização (&#916;&#916;G&#186; ads cabeça+CH3 = -5 a -7 kJ mol-1) estão de acordo com a energia de ligações de H fracas. Os resultados de IV de FT e RMN de 1H comprovaram a formação destas ligações de H e indicaram que a carbonila está presente na interface e o grupo benzila está voltado para o interior da micela. / Two series of cationic surfactants have been synthesized: benzyl-(2acylaminoetil) dimethylammonium chlorides, RCONH(CH2)2-N+(CH3)3 Cl-, and (2-acylaminoethyl)dimethylammonium chlorides, RCONH(CH2)2-N+(CH3)2-CH2-C6H5 Cl-, where RCO refers to an acyl group with 10, 12, 14 and 16 carbon atoms. These surfactants were obtained by reacting chromatographically pure carboxylic acids with N,N-dimethylethylenediamine to give an intermediate amidoamine. The latter was quaternized with benzyl chloride or methyl iodide. Surfactants with iodide counter-ion were transformed into the corresponding chlorides by ion exchange on a macro-porous resin. The average position of micellar interface and conformation of the headgroup were studied by FTIR and NMR. A multi-technique approach has been employed in order to study the effects of the presence of the \"spacer\" group (-CONH- CH2-CH2) on the adsorption and aggregation of these surfactants. The techniques employed were: calorimetry, conductance and EMF measurements, FTIR, NMR, surface tension, and Iight scattering. Surfactants with the spacer group (CONH-CH2-CH2) have more favorable Gibbs free energies of adsorption and/or micellization due to the more favorable transfer of the head-group from bulk phase to the interface and/or the micelle. This is attributed to the formation of direct, and/or water-mediated H-bonding between the surfactant amide groups. Differences in values of &#916;G&#186;Head-group+CH3 of surfactants with and without spacer group (&#916;&#916;G&#186; ads Head-group+CH3 = -17.2 kJ mol-1 and &#916;&#916;G&#186; ads Head-group+CH3 = -5 a -7 kJ mol-1 for adsorption and/or micellization, respectively) are in agreement with weak hydrogen bonding. Additional evidence for H-bond formation and for the (average) conformation of the benzyl head-group in the micelle was provided by FTIR and NMR data. The former showed that the amide group is highly hydrated, whereas the latter showed shielding/deshielding of the methylene groups of the surfactant hydrophobic tail, in agreement with a conformation in which the benzyl group is \"bent\" toward the micellar interior.