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La richesse moléculaire des végétaux constitue une source importante de molécules bioactives d‘origine naturelle. La mise en évidence de ces molécules nécessite de nombreuses étapes souvent longues et couteuses. L‘objectif de cette thèse a donc consisté en l‘innovation et le développement de nouvelles méthodologies d‘extraction, de fractionnement et d‘identification de produits naturels d‘origine végétale. Pour cela nous avons utilisé comme modèle végétal l‘argousier (Hippophaë rhamnoides, Elaeagnaceae) qui est un arbuste épineux du plateau Eurasiatique connu pour sa richesse phytochimique et son potentiel thérapeutique. Ce travail a d‘abord conduit au développement d‘une méthode d‘extraction « verte » sans solvant assistée par micro-ondes, basée sur l‘utilisation combinée de la pression, de la température et des micro-ondes. Il a pu être démontré que cette méthodologie permet d‘extraire rapidement et efficacement des composés phénoliques tout en conservant un potentiel antioxydant important. Dans une seconde partie, une nouvelle approche multidimensionnelle couplant la CPC et l‘HPLC-UV-MS a été développée. Cette technique permet la séparation à l‘échelle semi-préparative et l‘identification en ligne des molécules séparées. Il a ainsi pu être identifié par HPLC-MS/MS 3 acides phénoliques et 20 dérivés de flavonols dans l‘extrait micro-ondes sans solvant de baies d‘argousier. L‘activité antioxydante et la cytotoxicité des fractions a également été étudiée in vitro et in cellulo. Enfin la dernière partie de ce travail a démontré le potentiel antioxydant et antimicrobien de différents organes de l‘argousier, qui a été corrélé à la présence flavonoïdes et de proanthocyanidine. L‘intérêt du couplage CPC-HPLC-UV-MS a également été illustré par le fractionnement de deux molécules d‘un extrait actif de racines d‘argousier. / Plant materials constitute an important source of natural bioactive molecules. Characterisation of these molecules requires often multiple, long and expensive development steps. The aim of this PhD thesis consists of innovation and development of new methods of extraction, fractionation and identification of natural metabolites from plants. We used sea buckthorn as plant model (Hippophaë rhamnoides, Elaeagnaceae) an Eurasian thorny shrub known to possess various phytochemical properties and pharmaceutical effects. In the first part of this work a ―green‖ solvent-free microwave assisted extraction, based on the combined use of pressure, temperature and microwave irradiation has been developed. This approach allows fast and efficient extraction of phenolic compounds while maintaining an important antioxidant capacity. In the second part of this work, a new multidimensional approach coupling CPC and HPLC-UV-MS was developed. This technique allows the separation at semi-preparative scale and the online identification of isolated molecules. Using this approach, 3 phenolic acids and 20 flavonols from the solvent free sea buckthorn berries extract were identified by HPLC-MS/MS. Antioxidant activity and cytotoxicity of fractions were studied in vitro and in cellulo. In the last part of this work, the antioxidant and antimicrobial potentials of different sea buckthorn organs, which were correlated to the presence of flavonoids and proanthocyanidins has been demonstrated. The CPC-HPLC-UV-MS technique was also applied to the fractionation and the partial identification of compounds extracted from sea buckthorn root.

Thesis (M.Sc. (Chemistry)) --University of Limpopo, 2017 / The presence of polycyclic aromatic hydrocarbons (PAHs) in the environment is of major concern since these compounds are highly persistent, toxic and wide spread pollutants. The aim of this study was to evaluate the levels of PAHs in water and sediment samples collected from Blood and Mokolo Rivers in Limpopo Province, South Africa. Liquid-liquid extraction (LLE) was used for the extraction of PAHs from water, whereas PAHs in sediments were extracted using optimised microwaveassisted extraction (MAE). Furthermore, ultrasonication and a combination of ultrasonication and mechanical agitation were used for the extraction of PAHs from sediments samples. The quantification of sixteen (16) PAHs in water and sediment was carried out using gas chromatography-mass spectrometry (GC-MS) in selected ion monitoring (SIM) mode and by GC-flame ionisation detector (GC-FID). Concentrations of PAHs in sediments were higher than in water. The highest concentrations of PAHs were obtained in Mokolo River sediments, with the concentration ranging between 0.044 and 51.9 mg/kg. The levels of PAHs recorded in Blood River sediments were lower than those obtained in Mokolo River with concentrations ranging between 0.014 and 3.10 mg/kg. In water samples, higher levels of PAHs were observed in Mokolo River (between 0.0219 and 1.53 µg/L) while lower concentrations were recorded in Blood River (between 0.0121 and 0.433 µg/L). In water and sediment samples from both Rivers, higher molecular weight (HMW) PAH compounds (4-6 rings) were found at greater concentration levels than lower molecular weight (LMW) PAHs (2-3 rings), and this can be attributed to pyrogenic activities in the study areas. The efficiencies and accuracy of the methods for the extraction of PAHs were determined by assessing the recoveries of samples spiked with known amount of standards (for water samples), while a certified reference material (CRM) was used for sediments. Percentage recoveries ranged from 67.6 to 115% for LLE and 83.8 to 125% for MAE for both sample types. Diagnostic ratio was used for the source identification of PAHs in sediment samples. Several PAHs ratios indicated that both pyrogenic and petrogenic could be the sources of these compounds in both rivers. Toxic equivalency factors (TEFs) and benzo(a)pyrene equivalent (BaPE) were used to quantitatively estimate the PAHs potential human health risk. The assessment of ecotoxicological risk indicated that the v sediment samples collected from Mokolo River are at high toxicity risk while sediments from Blood River are at low sediment toxicity risk. / Water Research Commission (WRC), National Research Foundation (NRF) and Sasol Inzalo Foundation

The current understanding of contaminant migration in fractured sedimentary rock aquifers is inadequate due to the difficulty in describing the geologic and hydrogeologic controls on contaminant fate and transport with appropriate detail. To address contamination at fractured rock sites, multiple methods focusing on different aspects of the hydrologic system are required, and particular emphasis needs to be placed on the rock matrix. This thesis shows the further development and utility of the decade-old rock core VOC method (i.e. CORETM), a rock matrix method, when used in conjunction with multiple high resolution datasets as it applies to a 100 m thick highly productive dolostone aquifer in Guelph, Ontario. The research site and surrounding area, located in the northwestern quadrant of the municipality of Guelph, was a productive zone for water supply until the early 1990s when the two closest municipal supply wells (Sacco, Smallfield) were shut down (1991, 1993 respectively) due to volatile organic compounds (VOCs) in the groundwater. Trichloroethene (TCE), a VOC, was used as a degreaser at the Guelph site and likely entered the groundwater more than 20 years ago. The thin overburden, shallow water table, relatively constant dolostone mineralogy, proximity to the UW analytical laboratory, relatively simple plume composition showing minimal degradation, and local importance make this an excellent study site for TCE fate and migration in fractured sedimentary rocks. This thesis is composed of four chapters. Chapter 1 provides a brief background to the rock core VOC method and gives the conceptual framework for the investigation. Chapter 2 focuses on the further development of the rock core VOC method by providing the field validation of a recently adapted extraction method for VOCs in rock core using microwave assisted extraction (MAE), demonstrating the importance of rapid field preservation of samples, and comparing to the industry standard purge and trap method for VOCs on solid matrices. Results indicate that the microwave assisted extraction (MAE) method typically provides equivalent or higher concentrations when compared with the shake-flask and purge and trap extraction methods, indicating more complete extraction or less loss during transfer and/or storage. The purge and trap method provided false negatives (i.e. non-detects) due to inadequate preservation, incomplete extraction, and the elevated detection limit for TCE. The necessity for field preservation was examined by comparing crushed rock samples preserved in methanol in the field to samples unpreserved in the field with a laboratory addition of methanol less than 12 hours later. Chapter 3 creates high resolution porosity and bulk density logs by using selected geophysical logging tools in combination with core derived physical properties for the purpose of calculating porewater concentrations from total contaminant mass concentrations obtained from the rock core VOC method and sample specific rock properties relevant to the conversion. This is beneficial because total mass estimates obtained from the rock core VOC method are not necessarily indicative of the groundwater concentrations given the presence of solid organic carbon controlled sorption. Chapter 4 is a demonstration of the discrete fracture network approach (Parker 2007) applied to the Guelph field site with emphasis on the insights gained through high resolution contaminant profiles generated from cored holes in or near the source area and along a transect. Together, these four chapters present a framework for investigating VOC contamination in fractured sedimentary rocks and with emphasis on evaluating recent advances in the rock core VOC methodology in a field site context.

The current understanding of contaminant migration in fractured sedimentary rock aquifers is inadequate due to the difficulty in describing the geologic and hydrogeologic controls on contaminant fate and transport with appropriate detail. To address contamination at fractured rock sites, multiple methods focusing on different aspects of the hydrologic system are required, and particular emphasis needs to be placed on the rock matrix. This thesis shows the further development and utility of the decade-old rock core VOC method (i.e. CORETM), a rock matrix method, when used in conjunction with multiple high resolution datasets as it applies to a 100 m thick highly productive dolostone aquifer in Guelph, Ontario. The research site and surrounding area, located in the northwestern quadrant of the municipality of Guelph, was a productive zone for water supply until the early 1990s when the two closest municipal supply wells (Sacco, Smallfield) were shut down (1991, 1993 respectively) due to volatile organic compounds (VOCs) in the groundwater. Trichloroethene (TCE), a VOC, was used as a degreaser at the Guelph site and likely entered the groundwater more than 20 years ago. The thin overburden, shallow water table, relatively constant dolostone mineralogy, proximity to the UW analytical laboratory, relatively simple plume composition showing minimal degradation, and local importance make this an excellent study site for TCE fate and migration in fractured sedimentary rocks. This thesis is composed of four chapters. Chapter 1 provides a brief background to the rock core VOC method and gives the conceptual framework for the investigation. Chapter 2 focuses on the further development of the rock core VOC method by providing the field validation of a recently adapted extraction method for VOCs in rock core using microwave assisted extraction (MAE), demonstrating the importance of rapid field preservation of samples, and comparing to the industry standard purge and trap method for VOCs on solid matrices. Results indicate that the microwave assisted extraction (MAE) method typically provides equivalent or higher concentrations when compared with the shake-flask and purge and trap extraction methods, indicating more complete extraction or less loss during transfer and/or storage. The purge and trap method provided false negatives (i.e. non-detects) due to inadequate preservation, incomplete extraction, and the elevated detection limit for TCE. The necessity for field preservation was examined by comparing crushed rock samples preserved in methanol in the field to samples unpreserved in the field with a laboratory addition of methanol less than 12 hours later. Chapter 3 creates high resolution porosity and bulk density logs by using selected geophysical logging tools in combination with core derived physical properties for the purpose of calculating porewater concentrations from total contaminant mass concentrations obtained from the rock core VOC method and sample specific rock properties relevant to the conversion. This is beneficial because total mass estimates obtained from the rock core VOC method are not necessarily indicative of the groundwater concentrations given the presence of solid organic carbon controlled sorption. Chapter 4 is a demonstration of the discrete fracture network approach (Parker 2007) applied to the Guelph field site with emphasis on the insights gained through high resolution contaminant profiles generated from cored holes in or near the source area and along a transect. Together, these four chapters present a framework for investigating VOC contamination in fractured sedimentary rocks and with emphasis on evaluating recent advances in the rock core VOC methodology in a field site context.

The objective of this study was to compare microwave assisted extraction (MAE) and conventional extraction methods for the extraction of total phenolic compounds (TPC) from tomato and sour cherry pomace. Antiradical efficiency (AE) of the extracts and also the concentration of phenolic compounds were determined. In MAE, the effects of microwave power (400 and 700 W), solvent type (water, ethanol and ethanol-water mixture at 1:1 v/v), extraction time (8-20 min) and solvent to solid ratio (10, 20 and 30 ml/g) were studied to observe the change of TPC and AE of the extracts. Conventional extraction was conducted for 6 h using different solvent to solid ratios (10, 20 and 30 ml/g) and solvent types (water, ethanol and ethanol-water mixture at 1:1 v/v). When the power increased from 400 W to 700 W, TPC and AE values increased. In MAE, maximum TPC and AE values were obtained at a solvent to solid ratio of 20 ml/g. The highest TPC and AE values were obtained when the ethanol-water mixture was used for both MAE and conventional extraction. The highest TPC and AE of tomato pomace extracts was determined as 3.76 mg gallic acid equivalent, GAE/g sample and 4.84 mg 1,1-diphenyl-2-picrylhydrazyl, DPPH/g sample, respectively in MAE using power level of 700 W, ethanol-water mixture, solvent to solid ratio of 20 ml/g and extraction time of 14 min. The major phenolic acids detected in tomato pomace extract were gentisic acid and vannilic acid. For sour cherry pomace extracts, the highest TPC and AE was found as 14.14 mg GAE/g sample and 28.32 mg DPPH/g sample, respectively in MAE using power level of 700 W, solvent to solid ratio of 20 ml/g, ethanol-water mixture and extraction time of 12 min. Epicatechin was found to be the major phenolic acid in sour cherry pomace. There was no significant difference in different extraction methods in terms of TPC. On the other hand, AE value and concentration of major phenolic acids of tomato and sour cherry pomace increased when MAE was used.

A celulose das árvores do gênero Eucalyptus é um dos principais elementos de interesse econômico desse vegetal. Suas folhas, apesar de conter óleo essencial (OE), caracterizam-se como um subproduto da indústria de processamento de papel e celulose. Assim, pesquisas com relação à recuperação dessa biomassa tornam-se importantes, principalmente, do ponto de vista ambiental e econômico. Tradicionalmente, a extração de OEs ocorre pelo processo de hidrodestilação (HD), o qual necessita de longos tempos de extração. Visando superar essa restrição, a tecnologia de extração assistida por micro-ondas (Microwave Assisted Extraction - MAE) vem sendo desenvolvida e aplicada. O objetivo principal deste estudo foi avaliar o processo de extração de OE de folhas de eucalipto, empregando os métodos de extração HD e MAE. Para esse processo em escala de bancada, desenvolveu-se um aparato de extração por meio da adaptação de um forno micro-ondas doméstico. Inicialmente, analisou-se o rendimento de OE das matrizes de subprodutos de folhas de eucalipto das espécies Eucalyptus saligna, E. urohpylla e E. urophylla x globulus geradas a partir de uma indústria de celulose. Os resultados apontaram que a espécie E. urophylla x globulus apresentou maior teor de OE (2,16±0,02%), sendo a espécie escolhida para a aplicação da tecnologia MAE. Na segunda etapa do estudo, fez-se uma avaliação dos efeitos dos fatores do processo MAE, avaliando os fatores razão sólido:solvente (1:1; 1:1,5 e 1:2), potência do micro-ondas (680, 850 e 1.020 W) e tempo de extração total (20, 40, 60 min) no rendimento de OE. Desse modo, as condições ideais do processo foram determinadas como: razão sólido:solvente de 1:2, potência de 680 W e tempo de extração total de 60 minutos. Para essas condições, realizou-se o estudo cinético e modelagem matemática com a avaliação dos modelos de primeira ordem, segunda ordem, Peleg e Patricelli. No estudo cinético, o tempo total do processo MAE para a obtenção do rendimento de 1,8±0,1% foi apenas 60 minutos, tempo 57% inferior ao observado no método HD para igual rendimento (140 minutos). Dentre os modelos cinéticos estudados, o modelo de Patricelli foi o que apresentou melhor ajuste aos dados experimentais da extração HD (R² igual 0,9904 e RMSE igual 0,0016) e da extração MAE (R² igual 0,9962 e RMSE igual 0,0006). Por fim, as análises energéticas e de impacto ambiental também indicaram o método MAE como uma tecnologia mais ambientalmente amigável do que a HD, tornando-se atrativa para o setor industrial. Com base nos resultados obtidos, pode-se concluir que a extração de OE da matriz estudada proporcionou a reutilização de um subproduto industrial, sugerindo uma alternativa de exploração e agregando valor ao mesmo. / The cellulose from trees of the genus Eucalyptus is the main industrial product of this species. Its leaves, although containing essential oil (EO), are characterized as a by-product from the pulp and paper processing industry. Thus, researches about the recovery of this biomass are important, mainly from the environmental and ecological point of view. Traditionally, the extraction of EO occurs by hydrodistillation (HD), process that requires long extraction times. In order to overcome this restriction, microwave assisted extraction (MAE) has been developed and applied. The main objective of this study was to evaluate the extraction process of eucalyptus EO, using the HD and MAE methods. For this laboratory-scale process, an extraction apparatus was developed through the adaption of a domestic microwave oven. Initially, the yield of EO by-products of eucalyptus leaves of the species Eucalyptus saligna, E. urophylla and E. urophylla x globulus from a cellulose industry were analyzed. The results showed that the species E. urophylla x globulus presented the highest EO content (2.16 ± 0.02%), being the species chosen for the application of the MAE technology. In the second stage of the study, an evaluation of the effects of MAE process factors was performed, analyzing the factors ratio solid:solvent (1:1, 1:1,5 and 1:2), microwave power (680, 850 and 1.020 W) and total extraction time (20, 40, 60 min) in the EO yield. Thus, the ideal process conditions were determined as: ratio solid:solvent of 1:2, power of 680 W and total extraction time of 60 minutes. For these conditions, a kinetic study and a mathematical modeling were performed evaluating the first-order, second-order, Peleg and Patricelli models. In the kinetic study, the total time of the MAE process to obtain the yield of 1.8 ± 0.1% was only 60 minutes, 57% lower than the HD method for the same yield (140 min). Among the kinetic models studied, the Patricelli model presented the best fit to the experimental data of the HD extraction (R² equal to 0.9904 and RMSE equal to 0.0016) and MAE extraction (R² equal to 0.9962 and RMSE equal to 0.0006). Finally, the energy and environmental impact analyzes also indicated the MAE method more environmentally friendly than HD, being attractive for the industrial sector. Based on the results, it is possible to conclude that the extraction of EO from the studied matrix provided the reuse of an industrial by-product, suggesting an exploration alternative adding value to this residue.

152 f. / Submitted by Ana Hilda Fonseca (anahilda@ufba.br) on 2013-04-04T15:44:44Z No. of bitstreams: 1 TESE COMPLETA_SONILDA TEIXEIRA.pdf: 3246757 bytes, checksum: c41c8741042ef35b54690019e768753b (MD5) / Approved for entry into archive by Ana Hilda Fonseca(anahilda@ufba.br) on 2013-05-09T16:28:03Z (GMT) No. of bitstreams: 1 TESE COMPLETA_SONILDA TEIXEIRA.pdf: 3246757 bytes, checksum: c41c8741042ef35b54690019e768753b (MD5) / Made available in DSpace on 2013-05-09T16:28:03Z (GMT). No. of bitstreams: 1 TESE COMPLETA_SONILDA TEIXEIRA.pdf: 3246757 bytes, checksum: c41c8741042ef35b54690019e768753b (MD5) Previous issue date: 2009 / CAPES / Amostras de material particulado (PM10) foram coletadas no Recôncavo Baiano (RB) e em uma estação controle (Arembepe), de Agosto de 2007 a Abril de 2008, utilizando um amostrador de grandes volumes. Foram medidas as concentrações dos 16 HPAs classificados como poluentes prioritários pela Agência de Proteção Ambiental dos Estados Unidos (US-EPA), em duas campanhas de amostragem intensivas, nas estações chuvosa e seca, pelo período de 24 h durante 5-6 dias consecutivos, nos três sítios localizados na parte norte e nordeste da Baía de Todos os Santos (BTS) e em Arembepe (litoral norte da Bahia) tomado como sítio controle. Os filtros de fibra de vidro foram extraídos por microondas (MAE) utilizando um protocolo otimizado no qual a extração ocorreu em 10 min e consumiu 20 mL de DCM/acetona (1:1) antes da análise por cromatografia a gás/espectrometria de massas com detector de massas (GC/MS/MS). O somatório das concentrações médias dos 16 HPAs variou de 0,036 ng m-3 (Arembepe) a 108 ng m-3 (próximo a refinaria de petróleo e indústria de eletrodos de Carbono), apresentando uma variação sazonal (razão inverno/verão) na faixa de 0,2-306. Os HPAs potencialmente carcinogênicos representaram 53-74% da concentração total nos sítios do RB. Os HPAs predominantes foram os de alta massa molecular, do Fluoranteno ao Benzo(ghi)perileno, representando 90-99 % do total de HPAs no RB. Em Candeias as concentrações elevadas encontradas no inverno foram provavelmente causadas por emissões locais de fontes estacionárias. Para facilitar a identificação das fontes de HPAs no PM10 foi aplicada a análise de componentes principais (PCA) juntamente com o estudo das razões diagnósticas entre HPAs específicos. Na região estudada as emissões veiculares e industriais foram as principais contribuintes para os HPAs associados ao PM10. As concentrações de benzo(a)pireno equivalente (BaPeq) foram estimadas usando a relação de fatores de equivalência tóxica (TEFs) com valores de 0,1 a 22 ng m-3. Concentrações elevadas de BaPeq para os HPAs de 5 a 6 anéis no ar ambiente alertam para uma situação de aumento de riscos para a saúde humana e para a qualidade ambiental na região do RB, principalmente em Candeias e Madre de Deus / Salvador

Os cálices do hibisco possuem uma grande quantidade de compostos bioativos responsáveis pela sua atividade antioxidante. O presente trabalho teve como objetivos a obtenção de extratos contendo esses compostos bioativos em solução aquosa com 2 % de ácido cítrico por extração assistida por micro-ondas (EAM) e o encapsulamento desses extratos por atomização e liofilização utilizando polidextrose (PD), proteína isolada do soro de leite (WPI) e a mistura destes na concentração de 10 %. Previamente foram estudados três métodos de extração, o primeiro usando somente EAM a 200, 300 e 700 W de potência, e tempos de 2, 5 e 8 minutos; o segundo consistiu de dois períodos, a extração aquosa ácida com tempos de 1, 2, 4, 6, 18 e 24 horas seguida de EAM nas potências de 200, 300 e 700 W; o terceiro consistiu de EAM seguida de extração aquosa ácida, nos mesmos tempos e potências citados para o segundo método. Os resultados indicaram que a melhor condição do primeiro método foi a 700 W e 8 min, do segundo método realizada a 6 horas de extração aquosa ácida, seguida de EAM a 700 W por 8 min e do terceiro método, EAM a 700 W por 8 min seguida de 6 horas de extração aquosa ácida. Quando os três métodos foram comparados, a melhor condição de extração foi aquela obtida no terceiro método: 1,63 mg delfinidina-3-sambubiosídeo · g-1; 29,62 mg EAG · g-1; 133,25 μmol ET · g-1 para antocianinas, fenólicos totais e atividade antioxidante por ABTS, respectivamente. Para avaliar o efeito da extração obtida somente por EAM, os extratos obtidos por extração exaustiva com metanol por 25 min e EAM a 700 W e 8 min foram quantificados por HPLC-DAD-ESI-MS/MS, sendo encontrados 13 compostos (6 ácidos fenólicos, 2 antocianinas e 5 flavonóides derivados da quercetina, kaempferol e miricetina). Os compostos fenólicos majoritários foram o ácido 3-cafeoilquínico (2,58 e 1,32 mg · g-1) e ácido 5-cafeoilquínico (1,71 e 0,90 mg · g-1) para extração exaustiva e EAM, respectivamente. Esse mesmo extrato (700 W e 8 min) foi encapsulado por atomização (160 °C) e liofilização (- 68 °C por 54 horas). Os pós obtidos foram avaliados quanto aos teores de compostos fenólicos totais, antocianinas monoméricas totais, atividade antioxidante (ABTS, DPPH e HRSA), medidas por análises espectrofotométricas, atividade de água, umidade, higroscopicidade, solubilidade, eficiência de encapsulação, cor, análise termogravimétrica, temperatura de transição vítrea, espectroscopia de infravermelho com transformada de Fourier (FTIR) e microestrutura (MEV). Os pós atomizados tiveram menor atividade de água (0,14 a 0,17), umidade (3,4 a 4,5 %), higroscopicidade (23,9 a 34,1 %), solubilidade (86 a 98,2 %) e eficiência de encapsulação (51,62 a 84,52 %) do que os pós liofilizados. Os resultados do FTIR mostraram que os encapsulantes não interagiram quimicamente, visto que não foram observados mudanças na frequência dos picos; as provas termogravimétricas indicaram que os pós apresentaram a mesma tendência nas perdas de massa. Na análise de microestrutura foi observado um melhor desempenho nas micropartículas atomizadas com PD, as quais mostraram partículas mais esféricas e sem tendência de atração e aderência entre si. Foram obtidas retenções de 38 a 77 % para antocianinas monoméricas totais, 42 a 89 % para compostos fenólicos totais, e entre 33 e 90 % para atividade antioxidante nos pós obtidos. O pó encapsulado liofilizado com 10 % de polidextrose mostrou uma maior retenção de antocianinas (77 %), atividade antioxidante por DDPH (90 %) e HRSA (74 %), entretanto com maior higroscopicidade (39,4 %). As provas aceleradas de estocagem (umidades relativas de 75 e 90 % em temperaturas de 40 e 60 °C) realizadas em todos os pós encapsulados, após 30 dias, indicaram que o tratamento liofilizado com 10 % de PD foi o que apresentou melhores resultados a essas condições, retendo 75 % dos compostos fenólicos, com atividades antioxidantes medidas por ABTS, DPPH e HRSA de 75, 90 e 74 %, respectivamente, existentes no extrato original. O pó obtido tem potencial para aplicação em alimentos, portanto, devido ao hibisco ser uma matriz com ampla composição de compostos bioativos. / The hibiscus calyces contend a high quantity of bioactive compounds responsible for their antioxidant activity. The present paper was aimed the production of extracts containing those bioactive compounds in acidified aqueous solution 2 % of citric acid by microwave assisted extraction (MAE) and the encapsulation of those extracts by spray drying and freeze-drying using polydextrose (PD), whey protein isolate (WPI) and their mixture in the concentration of 10 %. Previously three methods of extraction were studied, the first using only MAE at 200, 300 and 700 W of power, and times of 2, 5 and 8 minutes; the second consisted of two steps, the acid aqueous extraction with times of 1, 2, 4, 6, 18 and 24 hours followed by MAE at the powers of 200, 300 and 700 Watts; the third consisted of MAE followed by acid aqueous extraction, in the same times and powers mentioned for the second method. The results indicated that the best condition of the first method was 700 W and 8 minutes, the second method performed at 6 hours of acid aqueous extraction, followed by MAE at 700 W for 8 minutes and the third method, MAE at 700 W for 8 minutes followed by 6 hours of acid aqueous extraction. When the three methods are compared, the best condition of extraction was obtained in the third method: 1.63 mg delphinidin-3-sambubioside · g-1; 29.62 mg GAE · g-1; 133.25 μmol TE · g-1 for total monomeric anthocyanins, total phenolic compounds and antioxidant activity by ABTS, respectively. To evaluate the effect of the extraction obtained only by MAE, the extracts obtained by exhaustive extraction with methanol for 25 minutes and MAE at 700 W and 8 minutes were quantified by HPLC-DAD-ESI-MS/MS, was found 13 compounds (6 phenolic acids, 2 anthocyanins and 5 flavonoids derived from quercetin, kaempferol and myricetin). The phenolic compounds majorities were acid 3-caffeoylquinic (2.58 e 1.32 mg · g-1) and acid 5-caffeoylquinic (1.71 e 0.90 mg · g-1) for exhaustive extraction and MAE, respectively. That same extract (700 W and 8 minutes) was encapsulated by spray drying (160 ºC) and freeze-drying (- 68 °C for 54 hours). The obtained powders were evaluated about the levels of total phenolic compounds, total monomeric anthocyanins, antioxidant activity (ABTS, DPPH e HRSA), measured by spectrophotometric analysis, water activity, moisture, hygroscopicity, solubility, encapsulation efficiency, color, thermogravimetric analysis, glass transition temperature, Fourier transform infrared spectroscopy (FTIR) and microstructure (MEV). The spray dried powders had lower water activity (0.14 to 0.17), moisture (3.4 to 4.5 %), hygroscopicity (23.9 to 34.1 %), solubility (86 to 98.2 %) and encapsulation efficiency (51.62 to 84.52 %) than the freeze-dried powders. The results of FTIR showed that the encapsulants did not interact chemically, since changes were not observed on the frequency of the peaks; the thermogravimetric tests indicated that the powders presented the same tendency on the mass loss. On the microstructure analysis a better perform was observed on the spray dried microparticles with PD, which showed more spherical particles and with no tendency of attraction and adherence between them. Were obtained retentions of 38 to 77 % for total monomeric anthocyanins, 42 to 89 % for total phenolic compounds and between 33 and 90 % for antioxidant activity in the obtained powders. The encapsulated power by freeze-drying, with 10 % of polydextrose, was showed higher retention of anthocyanins (77 %), antioxidant activity by DDPH (90 %) and HRSA (74 %), however with higher hygroscopicity (39.4 %). The accelerated tests of storage (relative humidity of 75 and 90 % in temperatures of 40 and 60 ºC) performed in all the encapsulated powders, after 30 days, indicated that the freeze-drying treatment with 10 % of PD has the best behavior in those conditions, retaining 75 % of the phenolic compounds, with antioxidant activities measured by ABTS, DPPH and HRSA of 75, 90 and 74 %, respectively, present in the original extract. The obtained powder has potential for application in foods, therefore, due to the hibiscus being a matrix with ample composition of bioactive compounds.

A celulose das árvores do gênero Eucalyptus é um dos principais elementos de interesse econômico desse vegetal. Suas folhas, apesar de conter óleo essencial (OE), caracterizam-se como um subproduto da indústria de processamento de papel e celulose. Assim, pesquisas com relação à recuperação dessa biomassa tornam-se importantes, principalmente, do ponto de vista ambiental e econômico. Tradicionalmente, a extração de OEs ocorre pelo processo de hidrodestilação (HD), o qual necessita de longos tempos de extração. Visando superar essa restrição, a tecnologia de extração assistida por micro-ondas (Microwave Assisted Extraction - MAE) vem sendo desenvolvida e aplicada. O objetivo principal deste estudo foi avaliar o processo de extração de OE de folhas de eucalipto, empregando os métodos de extração HD e MAE. Para esse processo em escala de bancada, desenvolveu-se um aparato de extração por meio da adaptação de um forno micro-ondas doméstico. Inicialmente, analisou-se o rendimento de OE das matrizes de subprodutos de folhas de eucalipto das espécies Eucalyptus saligna, E. urohpylla e E. urophylla x globulus geradas a partir de uma indústria de celulose. Os resultados apontaram que a espécie E. urophylla x globulus apresentou maior teor de OE (2,16±0,02%), sendo a espécie escolhida para a aplicação da tecnologia MAE. Na segunda etapa do estudo, fez-se uma avaliação dos efeitos dos fatores do processo MAE, avaliando os fatores razão sólido:solvente (1:1; 1:1,5 e 1:2), potência do micro-ondas (680, 850 e 1.020 W) e tempo de extração total (20, 40, 60 min) no rendimento de OE. Desse modo, as condições ideais do processo foram determinadas como: razão sólido:solvente de 1:2, potência de 680 W e tempo de extração total de 60 minutos. Para essas condições, realizou-se o estudo cinético e modelagem matemática com a avaliação dos modelos de primeira ordem, segunda ordem, Peleg e Patricelli. No estudo cinético, o tempo total do processo MAE para a obtenção do rendimento de 1,8±0,1% foi apenas 60 minutos, tempo 57% inferior ao observado no método HD para igual rendimento (140 minutos). Dentre os modelos cinéticos estudados, o modelo de Patricelli foi o que apresentou melhor ajuste aos dados experimentais da extração HD (R² igual 0,9904 e RMSE igual 0,0016) e da extração MAE (R² igual 0,9962 e RMSE igual 0,0006). Por fim, as análises energéticas e de impacto ambiental também indicaram o método MAE como uma tecnologia mais ambientalmente amigável do que a HD, tornando-se atrativa para o setor industrial. Com base nos resultados obtidos, pode-se concluir que a extração de OE da matriz estudada proporcionou a reutilização de um subproduto industrial, sugerindo uma alternativa de exploração e agregando valor ao mesmo. / The cellulose from trees of the genus Eucalyptus is the main industrial product of this species. Its leaves, although containing essential oil (EO), are characterized as a by-product from the pulp and paper processing industry. Thus, researches about the recovery of this biomass are important, mainly from the environmental and ecological point of view. Traditionally, the extraction of EO occurs by hydrodistillation (HD), process that requires long extraction times. In order to overcome this restriction, microwave assisted extraction (MAE) has been developed and applied. The main objective of this study was to evaluate the extraction process of eucalyptus EO, using the HD and MAE methods. For this laboratory-scale process, an extraction apparatus was developed through the adaption of a domestic microwave oven. Initially, the yield of EO by-products of eucalyptus leaves of the species Eucalyptus saligna, E. urophylla and E. urophylla x globulus from a cellulose industry were analyzed. The results showed that the species E. urophylla x globulus presented the highest EO content (2.16 ± 0.02%), being the species chosen for the application of the MAE technology. In the second stage of the study, an evaluation of the effects of MAE process factors was performed, analyzing the factors ratio solid:solvent (1:1, 1:1,5 and 1:2), microwave power (680, 850 and 1.020 W) and total extraction time (20, 40, 60 min) in the EO yield. Thus, the ideal process conditions were determined as: ratio solid:solvent of 1:2, power of 680 W and total extraction time of 60 minutes. For these conditions, a kinetic study and a mathematical modeling were performed evaluating the first-order, second-order, Peleg and Patricelli models. In the kinetic study, the total time of the MAE process to obtain the yield of 1.8 ± 0.1% was only 60 minutes, 57% lower than the HD method for the same yield (140 min). Among the kinetic models studied, the Patricelli model presented the best fit to the experimental data of the HD extraction (R² equal to 0.9904 and RMSE equal to 0.0016) and MAE extraction (R² equal to 0.9962 and RMSE equal to 0.0006). Finally, the energy and environmental impact analyzes also indicated the MAE method more environmentally friendly than HD, being attractive for the industrial sector. Based on the results, it is possible to conclude that the extraction of EO from the studied matrix provided the reuse of an industrial by-product, suggesting an exploration alternative adding value to this residue.