Orientadores: Maria Regina Wolf Maciel, Cibelem Iribarrem Benites / Dissertação (mestrado) - Universidade Estadual de Campinas, Faculdade de Engenharia Química / Made available in DSpace on 2018-08-18T15:37:18Z (GMT). No. of bitstreams: 1 Galucio_CleysondeSouza_M.pdf: 2671846 bytes, checksum: 073b9a1a95f494699d09f6ea38120b15 (MD5) Previous issue date: 2011 / Resumo: Monoacilgliceróis (MAG) são emulsificantes utilizados em produtos alimentícios, farmacêuticos e cosméticos. A obtenção de MAG a partir de óleos vegetais vem se destacando frente aos processos industriais devido aos benefícios que compostos naturais trazem à saúde humana. Industrialmente, são produzidos através da glicerólise química de triacilgliceróis (TAG), gerando cerca de 40 a 50% de MAG. Para algumas aplicações, é necessário concentrá-lo, sendo o processo de destilação molecular uma alternativa vantajosa, porque possibilita a concentração de compostos termicamente sensíveis e não utiliza solventes. Neste trabalho, foi realizado o estudo da glicerólise química do óleo de girassol (Helianthus annus), que se destaca por ser rico em ácido linoléico, pertencente à família ?-6. Após a reação, os MAG obtidos foram concentrados por destilação molecular. Foram utilizados dois destiladores moleculares de filme descendente agitado das marcas POPE e UIC-GmbH, salientando-se este último por apresentar as melhores condições de operação para o estudo de concentração de MAG. A técnica de planejamento de experimentos foi utilizada para o estudo dos fatores envolvidos na obtenção e concentração de MAG. Assim, nas condições otimizadas de glicerólise química, obteve-se 48,3% de MAG, 42,3% de diacilgliceróis (DAG), 6,9% de TAG e 2,8% de glicerol (GL). No processo destilação molecular foi realizada, primeiramente, a remoção de GL na corrente de destilado; a corrente de resíduo (rica em acilgliceróis) foi submetida a outra destilação molecular, visando aumentar a concentração de MAG. Na primeira destilação, sob temperatura do evaporador (TEV) de 90ºC, retirou-se 99,5% de GL. Na segunda destilação molecular concentraram-se os MAG em 82,6% na corrente de destilado, sob TEV de 170°C. Tanto o óleo vegetal quanto a mistura de acilgliceróis (oriunda da glicerólise) e o concentrado de MAG foram caracterizados por métodos físico-químicos, tomando como referência as características do óleo de girassol. Seguindo essas características de identidade e qualidade, os resultados obtidos apresentaram-se dentro dos padrões de legislação (ANVISA e CODEX). Ressalta-se que o conteúdo de ácidos graxos insaturados não foi alterado durante o processo de obtenção e concentração de MAG que apresentou características de qualidade aceitável para aplicação como emulsificante. A destilação molecular de filme descendente agitado (UIC-GmbH) mostrou-se uma ótima alternativa para concentração de MAG termicamente degradáveis. Portanto, nas condições estudadas, a glicerólise química e a destilação molecular mostraram-se processos viáveis para a obtenção de emulsificantes naturais concentrados / Abstract: Monoacylglycerols (MAG) are emulsifiers used in food, pharmaceutical and cosmetic products. MAG obtained from vegetable oils has been emphasizing to industrial processes due to the benefits that these natural compounds bring to human health. Industrially, these are produced by chemical glycerolysis of triacylglycerols (TAG), generating about 40 to 50% of MAG. For some applications, it is necessary to concentrate it and the process of molecular distillation is attractive because it enables the concentration of thermally sensitive compounds and does not use solvents. This work was carried out to study the chemical glycerolysis of sunflower (Helianthus annus), which is notable for being rich in linoleic acid (?-6 family). After reaction, the MAG obtained was concentrated by molecular distillation. Two falling film molecular distillers were used (POPE and UIC-GmbH), emphasizing this last one by better operating conditions for the study of concentration of MAG. The technique of experimental design was used to study the factors involved in MAG production and concentration. Thus, under optimized conditions, the chemistry glycerolysis obtain 48.3% of MAG, 42.3% diacylglycerols (DAG), 6.9% of TAG and 2.8% of glycerol (GL). Firstly, the molecular distillation process was conducted to remove the GL in the distillate stream, the residue stream (rich in acylglycerols) was feed to a second molecular distillation, to increase the MAG concentration. In the first distillation, at 90°C of evaporator temperature (TEV), 99.5% from GL was removed. In the second molecular distillation, MAG was concentrated at 82.6% in the distillate stream, under 170 °C of TEV. Both, the vegetable oil and the mixture of acylglycerols (from glycerolysis) and the MAG concentrate were characterized by physicochemical methods, with sunflower oil as reference. Following these characteristics of identity and quality, the results were inside the standards (ANVISA and CODEX). It is important to stand out that the unsaturated fatty acids were not changed during the process of obtaining and concentration of MAG showing acceptable quality characteristics for use it as an emulsifier. The agitated falling film molecular distillation (UIC-GmbH) was a great alternative to the concentration of thermally degradable MAG. Therefore, under these studied conditions, the chemical glycerolysis and the molecular distillation proved itself as a viable process for obtaining concentrated natural emulsifiers / Mestrado / Desenvolvimento de Processos Químicos / Mestre em Engenharia Química

La composition en huiles essentielles et en lipides de réserve des graines et fruits saisonniers de quatre espèces végétales d’origine congolaise (Aframomum stipulatum (Gagnep) K. Schum, Aframomum giganteum (Oliv. and Hand) K. Schum, Spondias mombin L. et Nephelium lappaceum L.), a été déterminée par l’utilisation du couplage chromatographie en phase gazeuse/spectrométrie de masse. Les résultats obtenus ont permis de comprendre la bioaccumulation des huiles essentielles et des lipides de réserve dans les organes des différentes espèces. Dans le cas des espèces du genre Aframomum, les graines et les coques de fruits sont sources à la fois des huiles essentielles et des lipides de réserve. Les huiles essentielles des graines des deux espèces du genre Aframomun sont riches en composés monoterpéniques hydrocarbonés et oxygénés (β-pinène, 1,8-cinéole, phellandrène) avec des taux non négligeables de sesquiterpènes (α-sélinène et β-caryophyllène). Les huiles essentielles des coques des deux mêmes espèces se révèlent plus riches en monoterpénes oxygénés que celles des graines avec des composés très caractéristiques (β-pinène, 1,8-cineole, linalool pour A. giganteum et β-pinène, terpinéol, 1,8-cinéole pour A. stipulatum). On note dans les deux espèces, en dépit des procédés unitaires différents utilisés, la présence de lipides de réserve avec un profil acides gras du type palmitique-linoléique. Seuls les lipides de réserve ont été caractérisés dans Spondias mombin L. et Nephelium lappaceum L.. Les différentes parties du fruit de Spondias mombin sont dominées, comme dans le cas des Aframomum, par la présence des acides palmitique-linoléique avec une présence marquée de l’hentriacontane dans l’huile de peaux de fruits. L’huile d’amande de Nephelium lappaceum se distingue par sa richesse en acide arachidique C20:0 et acide 11- eicosénoïque C20:1. Les quatre espèces présentent un apport en phytostérols et en tocophérols. Des essais prometteurs de formulation de phytoproduits ont été réalisés avec des mélanges de tensioactifs, des a-monoglycérides et des huiles essentielles de graines de A. giganteum. Les activités antimicrobienne, anticancéreuse, antipaludique et anti-radicalaire ont été évaluées sur les extraits d’huiles essentielles et sur les lipides de réserve ainsi que sur les analogues synthétiques de lipides pris seuls ou en combinaison. Les résultats obtenus sont prometteurs / The composition of essential oils and fat of seasonal fruits and seeds of four plant species from the Congo (Aframomum stipulatum (Gagnep) K. Schum, Aframomum giganteum (Oliv. and Hand) K. Schum, Spondias mombin L. and Nephelium lappaceum L.), was determined by the combined use of mass spectrometry and gas chromatography. The results were used for understanding the bio-accumulation of essential oils and the storage of lipids in the organs of different species. In the case of the genus Aframomum, seeds and fruit shells are both sources of essential oils and fat. Seeds essential oils of the two species of Aframomun were rich in hydrocarbon and oxygenated monoterpene compounds such as β-pinene, 1,8-cineole, phellandrene, with significant levels of sesquiterpenes (α-selinene and β-caryophyllene). The shells essential oils of the same two species appear to be more rich in oxygenated monoterpenes than seeds, with a large structural features (β-pinene, 1,8-cineole, linalool for A. giganteum and b-pinene, terpineol, 1.8 -cineole for A. stipulatum). It is notified in both species that despite the different unit processes used, the presence of lipid with a fatty acid profile of the type palmitic-linoleic. Only lipids have been characterized from Spondias mombin L. and Nephelium lappaceum L.. The different parts of the fruit of Spondias mombin are dominated, like Aframomum, by the presence of palmitic-linoleic with a large presence of hentriacontane in the oil fruit skins. The kernel oil Nephelium lappaceum is distinguished by its wealth of arachidic acid C20:0 and 11-eicosénoïc acid C20:1. The four species contained in phytosterols and tocopherols. Testing promising formulation of herbal products were made with mixtures of surfactants, α-monoglycerides and essential oils from seeds of A. giganteum. Antimicrobial, anticancer, antimalarial and anti-radical activities were evaluated on the essential oils on the lipid as well as on the synthetic analogs of lipid alone or in combination. The results are promising

In the last decade, there has been a growing interest in the use of differential sensing for molecular recognition. Inspired by the mammalian olfactory system, differential sensing employs an array of non-selective receptors, which through cross-reactive interactions, create a distinct pattern for each analyte tested. The unique fingerprints obtained for each analyte with differential sensing are studied with statistical analysis techniques, such as principal component analysis and linear discriminant analysis. It was postulated that serum albumin proteins would be applicable to differential sensing schemes due to significant differences in sequence identity between different serum albumin species, and due to the wide range of hydrophobic molecules which are known to bind to these proteins. Consequently, cross-reactive serum albumin arrays were developed, utilizing hydrophobic fluorescent indicators to detect hydrophobic molecules. As such, serum albumin cross-reactive arrays were employed to discriminate subtly different hydrophobic analytes, and mixtures of these analytes, in the form of terpenes and perfumes, plasticizers and plastic explosive mixtures, and glycerides and adipocyte extracts. In this doctoral work, a detailed review of the field of differential sensing, and a thorough study of principal component analysis and linear discriminant analysis in various differential sensing scenarios, are given. These introductory chapters aid in better understanding the methods and techniques applied in later experimental chapters. In chapter 3, serum albumins, a PRODAN indicator, and an additive are shown to discriminate five terpene analytes and terpene doped perfumes. Chapter 4 describes an array with serum albumins, two dansyl fluorophores, and an additive which successfully differentiate the plasticizers found within the plastic explosives C4 and Semtex and simulated C4 and Semtex mixtures. Discrimination of these simulated mixtures was also achieved with this array in the presence of soil contaminants, demonstrating the potential real-world applicability of this sensing ensemble. Finally, chapter 5 details an array consisting of serum albumins, several fluorescent indicators, and a Grubb's olefin metathesis reaction, to differentiate saturated and unsaturated triglycerides, diglycerides, and monoglycerides. Mixtures of glycerides in adipocyte extracts taken from rats with different health states were then successfully discriminated, showing promise for clinical applications in differentiating adipoctyes from pre-diabetic, type 2 diabetic, and non-diabetic individuals. / text

Le travail de thèse porte sur la synthèse de nouveaux monomères photopolymérisables issus de la biomasse, l’étude de leur photopolymérisation et la caractérisation des matériaux qui en résultent. Les monomères formulés ont été testés dans un procédé d’impression de caractères Braille.Les monomères ont été élaborés en deux étapes en utilisant un chemin réactionnel simple, économique et respectueux de l’environnement. La première étape a consisté à faire réagir des dérivés du glycérol (carbonate de glycérol ou glycidol) avec des acides gras. Dans un deuxième temps, les [alpha]-monoglycérides obtenus ont été fonctionnalisés en vue de les rendre photopolymérisables. Les différents monomères obtenus porteurs de fonctions (méth)acrylate et/ou époxy ont été photopolymérisés en quelques secondes en présence d’un photoamorceur. Les cinétiques de photopolymérisation ont été suivies par spectrométrie IR-TF en mode ATR et différents paramètres tels que la quantité et la nature du photoamorceur, l’intensité d’irradiation et la température ont été optimisés. Les différents matériaux obtenus après photoréticulation ont été caractérisés afin de mettre en évidence leurs principales physico-chimiques. Des relations structure – propriétés ont ainsi été établies.Enfin, une formulation photopolymérisable présentant une viscosité compatible avec le procédé d’impression Braille a été élaborée par ajout de silice nanométrique. Les points Braille obtenus présentent des caractéristiques proches de ceux réalisés par le partenaire industriel. / The work of the PhD deals with the synthesis of polymerizable monomers derived from biomass, the study of their photopolymerization and the characterization of the resulting materials. The formulated monomers were tested in a printing method of Braille characters.The monomers were prepared in a two-steps reaction that is simple, economic and environmentally friendly. The first step comprised a reaction between glycerol derivatives (glycerol carbonate or glycidol) and fatty acids. In the second step, the obtained [alpha]-monoglycerides were functionalized to obtain photopolymerizable monomers. The different obtained monomers that bear (meth)acrylate and/or epoxy groups were photopolymerized in a few seconds in the presence of photoinitiator.The photopolymerization kinetics were followed by FT-IR spectroscopy in ATR mode, and various parameters such as the amount and the nature of the photoinitiator, the irradiation intensity and the temperature were optimized. The different photocured materials were characterized to highlight their main physicochemical properties. Structure-properties relations were then established.Finally, a photopolymerizable formulation having a viscosity compatible with the printing process of Braille characters was developed by adding nanometric silice. The obtained Braille characters exhibited features close those carried out by the industrial partner.