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O ultra-som terapêutico é um recurso físico muito empregado como coadjuvante na promoção do reparo tecidual. Neste trabalho, foi estudada a influência do ultra-som terapêutico na integração dos enxertos de pele total num modelo experimental em coelhos. Foram utilizados 20 coelhos adultos, fêmeas, nos quais foram realizadas cirurgias de enxerto autógeno de pele total nas regiões escapulares, pela ressecção de dois retalhos quadrados de pele de 2 cm de lado, invertendo sua posição, o enxerto retirado do lado direito sendo colocado na área receptora esquerda e vice-versa. O enxerto do lado direito era submetido ao tratamento efetivo com o ultra-som (3 MHz, 0,5 W/cm2, 5 minutos) e o enxerto do lado esquerdo, a tratamento placebo, iniciado no 3o dia pós-operatório e aplicado diariamente por sete dias. Os animais eram sacrificados no 11o dia pós-operatório e os enxertos, ressecados com uma margem de segurança, para análise histopatológica, com cortes de 5 µm. Foram obtidos cortes histológicos corados com técnicas específicas (Tricrômico de Gomori, PCNA e Picrosirius) e analisados ao microscópio de luz, sendo realizada a contagem das células em proliferação e dos vasos neoformados e a morfometria das áreas da epiderme e derme. Os resultados mostraram um significativo aumento no número de células em proliferação na epiderme e vasos neoformados na camada reticular da derme, mas isto não implicou em uma diferença entre as áreas da epiderme e derme, nos enxertos irradiados e não irradiados. Concluímos que o ultra-som terapêutico induz alterações morfológicas nos processos biológicos, como proliferação celular da camada germinativa da epiderme e neoangiogênese, envolvidos na integração de enxertos de pele total, com um potencial de aplicação clínica em humanos. / Therapeutic ultrasound is a widely used co-adjuvant physical mean to promote tissue repair. In the present investigation, the influence of therapeutic ultrasound on the integration of full-thickness skin graft was studied in rabbits. Twenty female adult rabbits were used, two 2x2 cm square-shaped full-thickness skin grafts being obtained from both scapular regions and swapped, the one cut out on the right being placed on the left and vice-versa. The graft on the right was effectively irradiated with the therapeutic ultrasound (3 MHz, 0,5 W/cm2, 5 minutes) for seven days beginning on the third postoperative day. The graft on the left was submitted to a sham irradiation. The animals were killed on the 11th day and the grafted areas were resected (graft + safety margin) for histologic examination by means of 5 µm-thick sections alternatively stained with Gomori's trichrome, PCNA and Picrosirius and examined on the light microscope. Eider proliferating cells and new blood vessels were counted, as well as the epidermic and dermic areas were measured. The results showed a significant increase in the number of epidermic proliferating cells and new blood vessels, but this did not imply any difference between the epidermic and dermic areas between irradiated and non-irradiated grafts. We conclude that the therapeutic ultrasound induces morphologic alterations in the biologic processes, as epidermic germinative layer cell proliferation and neo-angiogenesis, involved in the integration of full-thickness skin grafts and this has a potential for clinical use in humans.

O ultra-som terapêutico é um recurso físico muito empregado como coadjuvante na promoção do reparo tecidual. Neste trabalho, foi estudada a influência do ultra-som terapêutico na integração dos enxertos de pele total num modelo experimental em coelhos. Foram utilizados 20 coelhos adultos, fêmeas, nos quais foram realizadas cirurgias de enxerto autógeno de pele total nas regiões escapulares, pela ressecção de dois retalhos quadrados de pele de 2 cm de lado, invertendo sua posição, o enxerto retirado do lado direito sendo colocado na área receptora esquerda e vice-versa. O enxerto do lado direito era submetido ao tratamento efetivo com o ultra-som (3 MHz, 0,5 W/cm2, 5 minutos) e o enxerto do lado esquerdo, a tratamento placebo, iniciado no 3o dia pós-operatório e aplicado diariamente por sete dias. Os animais eram sacrificados no 11o dia pós-operatório e os enxertos, ressecados com uma margem de segurança, para análise histopatológica, com cortes de 5 µm. Foram obtidos cortes histológicos corados com técnicas específicas (Tricrômico de Gomori, PCNA e Picrosirius) e analisados ao microscópio de luz, sendo realizada a contagem das células em proliferação e dos vasos neoformados e a morfometria das áreas da epiderme e derme. Os resultados mostraram um significativo aumento no número de células em proliferação na epiderme e vasos neoformados na camada reticular da derme, mas isto não implicou em uma diferença entre as áreas da epiderme e derme, nos enxertos irradiados e não irradiados. Concluímos que o ultra-som terapêutico induz alterações morfológicas nos processos biológicos, como proliferação celular da camada germinativa da epiderme e neoangiogênese, envolvidos na integração de enxertos de pele total, com um potencial de aplicação clínica em humanos. / Therapeutic ultrasound is a widely used co-adjuvant physical mean to promote tissue repair. In the present investigation, the influence of therapeutic ultrasound on the integration of full-thickness skin graft was studied in rabbits. Twenty female adult rabbits were used, two 2x2 cm square-shaped full-thickness skin grafts being obtained from both scapular regions and swapped, the one cut out on the right being placed on the left and vice-versa. The graft on the right was effectively irradiated with the therapeutic ultrasound (3 MHz, 0,5 W/cm2, 5 minutes) for seven days beginning on the third postoperative day. The graft on the left was submitted to a sham irradiation. The animals were killed on the 11th day and the grafted areas were resected (graft + safety margin) for histologic examination by means of 5 µm-thick sections alternatively stained with Gomori's trichrome, PCNA and Picrosirius and examined on the light microscope. Eider proliferating cells and new blood vessels were counted, as well as the epidermic and dermic areas were measured. The results showed a significant increase in the number of epidermic proliferating cells and new blood vessels, but this did not imply any difference between the epidermic and dermic areas between irradiated and non-irradiated grafts. We conclude that the therapeutic ultrasound induces morphologic alterations in the biologic processes, as epidermic germinative layer cell proliferation and neo-angiogenesis, involved in the integration of full-thickness skin grafts and this has a potential for clinical use in humans.

Parmi les procédés avancés d'oxydation (AOPs), les procédés de type Fenton (réactif de Fenton: Fe2+/H2O2) et les procédés d'oxydation par le persulfate, sont décrits comme des procédés très performants. Le procédé Fenton est une voie prometteuse et attractive pour le traitement d'une large variété de composés organiques polluants, difficiles à traiter par les voies classiques de dépollution. Au cours du procédé Fenton, des radicaux hydroxyles, molécules à fort pouvoir oxydant capable de réagir avec pratiquement tous types de composés organiques et inorganiques, sont générés. De même, du fait de la structure similaire entre H2O2 et les ions peroxydisulfate, ces derniers peuvent se décomposer en radicaux sulfates (SO4-•), un autre type d'oxydant hautement réactif pouvant réagir avec les composés organiques. Cependant, les procédés Fenton et d'activation du peroxydisulfate classiques présentent plusieurs inconvénients. En effet, la solution doit être acidifiée avant la réaction, et des procédés complexes de purification / séparation sont nécessaires après réaction. Afin de contourner ces inconvénients, le développement de procédés de traitement hétérogènes est proposé pour le traitement de l'eau. Dans cette optique de développement de procédés économes, les oxydes de fer comme la magnétite sont proposés comme remplaçants des sels solubles de fer. Une utilisation de tels matériaux, à l'état solide, présente des avantages indéniables, dont la séparation aisée de l'espèce active après réaction par sédimentation ou filtration. Dans le cadre de ce travail de doctorat, différents types d'oxydes de fer, hématite ou magnétite, ont été synthétisés en milieu liquide ionique. La morphologie, les propriétés structurales, les rapports de surface FeII/FeIII, les surfaces spécifiques, les tailles de domaine cristallin, etc. ont été évaluées. Deux molécules différentes, la tétracycline (TC) et le phenol, couramment utilisées dans l'industrie chimique, ont été sélectionnées comme polluants modèles afin d'évaluer les performances des matériaux préparés pour leur élimination. Une partie importante du travail de doctorat a donc été l'étude des propriétés des matériaux pour l'élimination de polluants organiques par le procédé Fenton hétérogène. Les résultats montrent clairement que les principaux facteurs affectant les performances du procédé sont reliés aux propriétés de la phase active, du fait du caractère surfacique des réactions. La stabilité des systèmes catalytiques préparés est néanmoins une propriété cruciale également étudiée. Le manuscrit de doctorat met donc l'accent sur la conception de matériaux originaux destinés à une utilisation dans les procédés avancés d'oxydation dans l'eau. / Fenton reaction (Fenton reagent: (Fe2+/H2O2)) and persulfate oxidation process, as advanced oxidation processes, are powerful oxidations used world around. Fenton reaction has been evidenced to be a promising and attractive treatment method for the degradation of a wide variety of hazardous organic pollutants, which are difficult to be treated using traditional soft treatment technologies. During Fenton process, free hydroxyl radicals (HO•), strong oxidant molecules capable of reacting with practically all types of organic and inorganic compounds, are generated. In the meanwhile, due to the similar structure between H2O2 and peroxydisulfate ions, peroxydisulfate ions can be decomposed to sulfate radicals (SO4-•), another kind of highly active oxidant that can react with organic compounds. However, the classical Fenton or peroxydisulfate activation processes present some disadvantages. Indeed, the solution needed acidification before carrying out the reaction and complex separation processes have to be applied after reaction. To overcome these drawbacks, heterogeneous catalytic oxidation processes were introduced for wastewater treatment. In this line, magnetite was evidenced as potential substituent to soluble iron ions, and it offers significant advantages such as an easy separation after reaction since the active material can be easily recovered by sedimentation or filtration for further used. In this PhD work, iron oxides, hematite and magnetite, were synthesized using an ionic liquid mediated process. The morphology, structural properties, FeII/FeIII surface ratios, specific surface areas (SSA), mean particle diameters, site densities, etc. were evaluated. Two different model pollutants (tetracycline (TC) and phenol), which are widely used chemicals all over the world, were selected to evaluate the performance of the prepared active materials. A significant part of the PhD study was then on the study of heterogeneous Fenton-like reaction for phenol and TC degradation. Experiments showed that the main factors affecting the heterogeneous Fenton-like system are related to the heterogeneous active phase properties, due to the surface reaction nature occurring over iron oxide surface. However, stability of this active phase, with progressive dissolution under reaction, is also a real challenge. This PhD manuscript, focusing on the design of highly active materials for advanced oxidation processes (AOPs), is constituted of five experiment result parts.

Made available in DSpace on 2017-07-10T18:08:17Z (GMT). No. of bitstreams: 1 Jamal Abd Awadallak.pdf: 7067148 bytes, checksum: 8e321c5aa3d2b9b3eeaafb2fd17b9d47 (MD5) Previous issue date: 2012-02-15 / Coordenação de Aperfeiçoamento de Pessoal de Nível Superior / Diacylglycerol rich oils have its organoleptic characteristics very similar to those of conventional edible oils, but these oils do not tend to accumulate in the body, even when consumed in high quantities, making them a great resource in the fight against obesity. Palm oil ranks first the world production of edible oils mainly due to its low cost. This work aimed to propose a new technology for enzyme production using diacylglycerol lipase Lipozyme RM IM and ultrasound to promote water in oil emulsions, which increases the interfacial area of the system leading to higher reaction rates compared to conventional enzymatic processes. . The reactions were carried out at 55 °C with two different methods. First, the reaction system was exposed to ultrasonic waves for the whole reaction time, which led to enzymatic inactivation and water evaporation. Ultrasound was then used to promote emulsification of the water/oil system before the hydrolysis reaction, avoiding contact between the probe and the enzymes. Achieved conversions were superior to the conventional method further hydrolysis rate when the ultrasound is employed for emulsion formation was significantly greater. For 12 hours of reaction the conversion was 85% higher than the conventional method and 15% higher for a period of 24 hours of reaction. . An experimental design was used to optimize the ultrasound-related parameters and maximize the hydrolysis rate, and in these conditions, with a change in equilibrium, DAG production was evaluated.Better reaction conditions were achieved for the second method: 11.20 wt% (water+oil mass) water content, 1.36 wt% (water+oil mass) enzyme load, 12 h of reaction time, 1.2 min and 200 W of exposure to ultrasound. In these conditions diacylglycerol yield was 37.69 wt%. / Óleos enriquecidos com diacilglicerol possuem características organolépticas muito semelhantes às dos óleos comestíveis convencionais, porém, estes óleos não tendem a se acumular no organismo, mesmo quando consumidos em altas quantidades, tornando-os um grande recurso no combate à obesidade. O óleo de palma está no topo da produção mundial de óleos comestíveis principalmente devido ao seu baixo custo. Este trabalho teve como objetivo propor uma nova tecnologia para a produção enzimática de diacilglicerol empregando a lipase Lipozyme RM IM e utilizando ultrassom como gerador de emulsões de água em óleo, o que aumenta a área interfacial do sistema conduzindo a maiores taxas de reação em relação aos processos enzimáticos convencionais. A hidrólise parcial do óleo de palma foi realizada em meio livre de solventes a 55 °C em duas etapas distintas e comparadas com reações em condições semelhantes sem o uso do ultrassom. Primeiramente o sistema reacional foi exposto às ondas ultrassônicas, o que levou a taxas iniciais de reação elevadas, porém, as conversões obtidas foram baixas, em função da desativação enzimática e da evaporação de água, pelo longo período de exposição ao ultrassom. Posteriormente, utilizou-se o ultrassom para gerar emulsões antes a etapa reacional, não permitindo seu contato com o sistema contendo a enzima. As conversões obtidas foram superiores ao método convencional, além disso, taxa de hidrólise quando se empregou o ultrassom para a formação de emulsões foi significativamente maior. Para 12 horas de reação a conversão foi 85% superior ao método convencional e de 15% superior para um período de 24 horas de reação. Foi desenvolvido um planejamento fatorial, o delineamento central composto rotacional para avaliar os efeitos das variáveis tempo de exposição ao ultrassom, potência do ultrassom e razão água/óleo na conversão em ácidos graxos livres da reação, sendo que a razão água/óleo e o produto tempo x potência apresentaram os maiores efeitos. Nas melhores condições, foi produzido um óleo concentrado com 37,69% de DAG em de 12h de reação, exposto ao ultrassom por 1,2min à 200W.

Abstract The rapid increase of energy demand for transportation generates a rise of environmental pollution, stimulating the development of alternative sources of energy. Biomass is considered as the main organic carbon source of energy to substitute petroleum permitting sustainable production of chemicals and transportation fuels. Biowastes, residues and non-edible feedstock possess high potential resources avoiding food competition. This research aims to convert starch-based industrial waste, potato peels, into reducing sugars and platform molecules, such as glucose. These high added-value chemicals can further be transformed into chemicals and fuels. Catalytic conversion of starch, the main constituent of potato peels, was activated with non-conventional technologies to enhance the depolymerisation rate and to reduce energy consumption according to the principles of green chemistry. Depolymerisation of starch was first performed in acidic water as reaction medium assisted with ultrasonic and/or microwave irradiation. Ultrasonic irradiation enhanced mass transfer of heterogeneous system, whereas the use of microwaves improved heat transfer in the reaction medium. The frequency applied leads to different effects on heterogeneous systems: low frequencies irradiation (below 100 kHz) generates turbulences resulting in enhanced transport properties, whereas higher frequencies produce chemical effects. Catalytic conversion of starch into reducing sugars required more energy than individual irradiation could provide. Simultaneous irradiation, combining ultrasound and microwave or several ultrasonic frequencies, on potato peels led to 50% yield of sugars without former separation processes, at moderate temperature. A weak synergetic effect was only observed with potato peels. The second part of this research is dedicated to study the effect of catalytic reaction medium (acids, ionic liquids). More appropriate systems possess the ability to dissolve and hydrolyse carbohydrates: specific ionic liquids. A room-temperature ionic liquid and a task-specific ionic liquid were selected for their solvability properties to dissolve and depolymerise starch present in potato peels. The depolymerisation of starch in the task-specific ionic liquid generated a yield of 43% of sugars, without former separation process. / Tiivistelmä Liikenteen energiantarpeen nopea kasvu on johtanut päästöjen sekä ympäristösaasteiden lisääntymiseen. Biomassa on merkittävä raaka-ainevaihtoehto fossiiliselle hiilelle energian, kemikaalien ja liikenteen polttonesteiden tuotannossa. Erityisesti jätebiomassoilla on suuri merkitys biomassaraaka-aineena, koska ne eivät kilpaile ruoantuotannon kanssa. Väitöskirjatutkimuksen tavoitteena on tärkkelyspohjaisen teollisen jätteen, perunan kuorilietteen, katalyyttinen muuttaminen pelkistäviksi sokereiksi ja ns. platform-kemikaaleiksi, kuten glukoosiksi. Näistä korkean lisäarvon omaavista välituotteista voidaan edelleen valmistaa uusia biomassapohjaisia kemikaaleja ja polttoaineita. Tärkkelyksen, perunankuoren keskeisimmän aineosan, muuttaminen tehtiin tässä työssä mm. ultraääni- ja mikroaaltoavusteisella hajotuksella. Tavoitteena oli parantaa perunan kuorilietteen liukenemis- ja hajoamisnopeutta, lisätä saantoa sekä vähentää energian kulutusta vihreän kemian periaatteiden mukaisesti. Tärkkelyksen depolymerointi tehtiin ensin happokatalysoidussa liuoksessa ultraäänen ja/tai mikroaaltojen avulla. Ultraäänihajotus lisäsi aineensiirtoa heterogeenisessä reaktioväliaineessa, kun taas mikroaallot lisäsivät lämmönsiirtoa reaktioseoksessa. Eri ultraäänitaajuuksilla havaittiin olevan erilaisia vaikutuksia reaktioseokseen: alhaisilla taajuuksilla (alle 100 kHz) muodostuneet pyörteiset virtaukset edistivät aineensiirtoa ja korkeammat taajuudet kemiallisia ilmiöitä. Tärkkelyksen katalyyttinen depolymerointi vaatii enemmän energiaa kuin perinteisillä menetelmillä, kuten lämmittämällä, voidaan tuottaa. Yhdistämällä ultraäänen ja mikroaaltojen säteilytystä tai eri taajuuden omaavia ultraääniä, yli 50% perunajätteen tärkkelyksestä saadaan hajotettua pelkistyneiksi sokereiksi alhaisissa lämpötiloissa. Sen sijaan, ainoastaan perunankuorijätteellä havaittiin heikko synenerginen efekti mitä ei havaittu vertailunäytteellä (perunajauho). Toisena tavoitteena oli tutkia katalyyttisen reaktioseoksen (hapot, ioniset liuottimet) vaikutusta perunan kuorijätteen ja sen sisältämän tärkkelyksen liuottamiseen ja hajottamiseen. Erityisesti keskityttiin uusiin, spesifisiin ionisiin liuottimiin, jotka kykenevät samanaikaisesti sekä liuottamaan että hydrolysoimaan hiilihydraatteja. Huoneenlämpötilassa toimiva spesifinen ioninen liuotin valittiin sen katalyyttisten ominaisuuksien vuoksi. Tässä liuottimessa kuorilietteen sisältämästä tärkkelyksestä pelkistyneiden sokerien saanto oli 43%. / Résumé La forte demande en énergie, la conscience sociale sur les changements climatiques mondiaux et l'épuisement à moyen terme des réserves d’énergies fossiles stimulent le développement de ressources alternatives. Considérée comme la principale source de carbone organique renouvelable, la biomasse peut être utilisée pour remplacer les carburants d’origine fossile tout en étant plus respectueuse de l’environnement. Des déchets biosourcés ainsi que des végétaux d’origine agricole ou forestière, appelés biomasse végétale, possèdent de fort potentiels évitant la concurrence alimentaire. Cette recherche a pour objectif de convertir un déchet industriel amidonné, des pelures de pommes de terre, en sucres réducteurs et molécules plateformes, tels que le glucose, qui par la suite peuvent être transformées en carburants de transport. L’utilisation des ultrasons ainsi que des micro-ondes, méthodes non-conventionnelles, en milieu acide ont permis d’améliorer le rendement ainsi que de réduire la consommation énergétique en accord avec les principes de la chimie verte. L’irradiation ultrasonore améliore le transfert de masse de systèmes hétérogènes, alors que les micro-ondes renforcent le transfert de chaleur dans le milieu réactionnel. De plus, la fréquence ultrasonore appliquée induit différents effets sur le système : les ultrasons de basse fréquence (en dessous de 100 kHz) génèrent des turbulences améliorant les propriétés de transport de la matière, alors que les ultrasons de plus haute fréquence produisent des effets chimiques, tels que la formation de radicaux libres. L’apport énergétique fourni par les ultrasons et micro-ondes seuls étant insuffisant, l’utilisation d’irradiations simultanées et combinées a conduit à un rendement de 50% de sucres depuis l’amidon, ne nécessitant aucun procédé de séparation pré-réactionnel. Un faible effet synergique a pu être observé sur la dépolymérisation de la pelure de pommes de terre. L’étude d’un milieu réactionnel permettant simultanément la dissolution ainsi que l’hydrolyse des glucides présents dans la matière première est développée dans la seconde partie de ce mémoire. Certains liquides ioniques possèdent les propriétés recherchées. La dépolymérisation de l'amidon dans un liquide ionique à tâches spécifiques a permis d’obtenir un rendement de 43% de sucres, sans aucun procédé de séparation pré-réactionnel.