Perfluorooctane sulfonate (PFOS) is widely used in industrial products and is potentially dangerous to the aquatic environment due to not being broken down whether by chemical or biological means, having a half-life of more than 41 years and disrupting hormones. Hexabromocyclododecane (HBCD) is the third most used brominated flame retardant and is of environmental concern as it bioaccumulates and magnifies in the food chain and is highly toxic to aquatic organisms. The purpose of this study was to examine the effect of PFOS and HBCD on the embryos of rainbow trout (Onchorhynchus mykiss) by analyzing lipid profiles with UHPLC/Q-TOF-MS. The fish embryos were treated with various concentrations of PFOS and HBCD (0.058-58 μg/l and 0.014-14 μg/l respectively) with DMSO as carrier solvent and then extracted after homogenization with 0.9% NaCl-solution followed by addition of ISTD mixture, methanol, methyl tert-butyl ether (MTBE) and MQ-water. The raw data was processed with MZmine-2.32. 153 lipids were identified with the main lipids consisting of glycerophospholipids and triacylglycerols. A two-tailed t-test was used to study the impact of the chemical exposure on the embryos, where p-values below 0.05 were lipids considered as significant change. The HBCD exposure caused significant change in various triacylglycerols, whereas PFOS exposure caused significant change in triacylglycerols as well as in glycerophospholipids such as PC(O-38:5) and LPC(20:4). The results were in alignment with previous studies.

The widespread use of pesticides in agriculture has brought many benefits such as, increasing quantity and quality of crops grown. However, there is a concern regarding to the presence of pesticide residues in the consumed manufactured food products. Due to this, it is necessary to monitor pesticides in these products in order to verify compliance with maximum residue limits. Wine is a beverage obtained from grape must, but the grapes grown for this purpose are susceptible to pest attack and the occurrence of fungal diseases. Since the wine quality is related to the grapes quality, its production is dependent on the use of pesticides. Currently, the most useful way to determine the pesticides residues in food is the application of multiresidue methods that allow the determination of several compounds from different classes in a single analytical process. Based on that, the aim of this work was to evaluate two multiresidue methods for the extraction of pesticides in wine, one of them being based on the QuEChERS method and the dispersive liquid-liquid microextraction with the use of demulsifying solvent (SD-DLLME). Parameters that affect the extraction efficiency of both methods were studied and after established the best extraction conditions the methods were validated. The use of ultra-high performance liquid chromatography coupled to tandem mass spectrometry (UHPLC-MS/MS) allowed to perform the determination with high selectivity and sensitivity. For the QuEChERS method, 97 compounds were validated and the limit of quantification of the method (LOQ) ranged from 10 to 20 μg L-1. For SD-DLLME, 74 compounds were validated and LOQ were between 0.1 and 0.2 μg L-1. Among the compounds not validated by SD-DLLME are compounds with polar characteristics, not suitable for this technique. Pesticides residues of different classes were found in the samples the concentrations of 0.8 to 55.3 μg L-1. In view of the results obtained, the use of SD-DLLME proved to be a viable alternative to the QuEChERS method for the multiresidue determination of pesticides in wine. / O uso generalizado de agrotóxicos na agricultura trouxe muitos benefícios em relação ao aumento da quantidade e qualidade das culturas produzidas. Entretanto, existe uma preocupação com relação à presença de resíduos de agrotóxicos nos alimentos e produtos comerciais consumidos. Devido a isso, torna-se necessário o monitoramento de agrotóxicos nesses produtos a fim de verificar a observância dos limites máximos de resíduos. O vinho é uma bebida obtida a partir do mosto da uva, porém as uvas cultivadas para esse fim são suscetíveis ao ataque de pragas e a ocorrência de doenças fúngicas. Uma vez que a qualidade do vinho depende fortemente da qualidade das uvas, a sua produção é dependente do uso de agrotóxicos. Atualmente, a maneira mais útil para determinação de resíduos de agrotóxicos em alimentos é a aplicação de métodos multirresíduo que permitam a determinação de inúmeros compostos, de diversas classes, em um único processo analítico. Pensando nisso, esse trabalho teve como objetivo a avalição de dois métodos de extração multirresíduo de agrotóxicos em vinho, sendo um deles baseado no método QuEChERS e outro na técnica de extração denominada microextração líquido-líquido dispersiva com uso de solvente demulsificante (SD-DLLME). Os parâmetros que afetam a eficiência de extração foram estudados para ambos e depois de encontradas as melhores condições de extração os mesmos foram validados. A determinação por cromatografia líquida de ultra-alta eficiência acoplada à espectrometria de massas em série (UHPLC-MS/MS) permitiu a realização das análises com alta seletividade e sensibilidade. Para o método QuEChERS foram validados 97 compostos sendo que o limite de quantificação do método (LOQm) variou de 10 a 20 μg L-1. Para a SD-DLLME, 74 compostos foram validados e o LOQm entre 0,1 e 0,2 μg L-1. Dentre os compostos que não foram validados pela SD-DLLME estão compostos com características polares, não adequados para essa técnica. Os métodos validados foram utilizados para a determinação de agrotóxicos em amostras de vinho. Foram encontrados resíduos de agrotóxicos de diferentes classes nas concentrações de 0,8 a 55,3 μg L-1. Tendo em vista os resultados obtidos, a utilização da SD-DLLME demonstrou ser uma alternativa viável ao método QuEChERS para determinação multirresíduo de agrotóxicos em vinho.

Submitted by Maiara Cristina Gonçalves null (maiara.sp@hotmail.com) on 2017-10-31T22:26:38Z No. of bitstreams: 1 Maiara_C_Gonçalves_Dissertaçãof.pdf: 10457679 bytes, checksum: a5a48ce58f99b4fe8a29392db8f2e4f5 (MD5) / Approved for entry into archive by LUIZA DE MENEZES ROMANETTO (luizamenezes@reitoria.unesp.br) on 2017-11-13T13:01:38Z (GMT) No. of bitstreams: 1 goncalves_mc_me_bot.pdf: 10457679 bytes, checksum: a5a48ce58f99b4fe8a29392db8f2e4f5 (MD5) / Made available in DSpace on 2017-11-13T13:01:38Z (GMT). No. of bitstreams: 1 goncalves_mc_me_bot.pdf: 10457679 bytes, checksum: a5a48ce58f99b4fe8a29392db8f2e4f5 (MD5) Previous issue date: 2017-08-31 / Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES) / Objetivo da pesquisa foi avaliar o processo de beneficiamento primário de Passiflora incarnata realizado no município de Botucatu com a inclusão de um sistema de monitoramento da temperatura e umidade de baixo custo, por meio de um software open-source em um secador artesanal á lenha e a avaliação do processamento póscolheita da biomassa de P. incarnata, quantificando teor de vitexina por CLUE-EM. O trabalho foi desenvolvido no sítio Dois Irmãos, entre as coordenadas geográficas, latitude 22º56’49,27” Sul e longitude 48º34’42,80” Oeste, aos 765 m de altitude no distrito de Rubião Júnior, bairro rural Chaparral. Acompanhou-se a colheita e o beneficiamento de P. incarnata durante dois anos (2015 e 2016). A metodologia utilizada foi a de observação direta. A estrutura do secador confeccionado pelo produtor familiar de alvenaria (barro-cimento), reutilizando uma construção que já existia na área. Para a avaliação do teor de vitexina foram escolhidos e marcados seis indivíduos de P. incarnata e coletados durante as três épocas de colheita de 2016 (abril, setembro e novembro) e três tratamentos prévios à secagem de fragmentação: parte aérea não fragmentada (NF); fragmentada média, de 1 cm a 5 cm (FM), e fragmentada pequena, abaixo de 0,5 cm (FP). As análises de CLUE-EM foram realizadas em espectrômetro de massas Accela (Thermo Scientific® ) modelo LCQ Fleet com Ion Trap 3D via análise de injeção de fluxo (FIA) e ionização por eletronebulização com separações cromatográficas realizadas em coluna de fase reversa (C18) e a fase móvel composta de uma mistura de MeOH:H2O. A desidratação da parte aérea do P. incarnata ocorre, em média, durante cerca de 22 horas e meia, parando no período noturno por (11 horas) atingindo umidade relativa máxima de 73,8 % e mínima de 9,6 % e temperaturas máxima e mínima, respectivamente, de 53,5 e 20,9° C. Durante todo processo de desidratação o secador manteve a temperatura interna acima da temperatura do ambiente e a umidade relativa do ar abaixo da umidade do ambiente cumprindo sua função mesmo nos momentos que não foi alimentado por lenha. Apesar da grande variação nos teores de vitexina do tratamento não fragmentado e da segunda época de colheita e a média dos tratamentos não apresentaram diferenças significativas entre os tipos de fragmentação pré-secagem e teores de vitexina, sendo a fragmentação recomendada para facilitar o processo de secagem da espécie. / The objective of this research was to evaluate the process of primary processing of Passiflora incarnata in a low cost temperature and humidity monitoring system, which was carried out in Botucatu by means of an open-source software in a wood-fired drier and the evaluation of the post-harvest processing of the P. incarnata biomass by the vitexin content by UHPLC-MS with a data metabolic approach.The work was developed in Dois Irmãos, between the geographical coordinates, latitude 22º56'49.27 "South and longitude 48º34'42.80" West, at 765m altitude in the district of Rubião Júnior, rural district Chaparral. The experiment was conducted with different seasons of harvest and beneficiation of P. incarnata during two years (2015 and 2016).The methodology used was direct observation and photographic record. The structure of the dryer made by the producer was masonry (clay-cement), reused a construction that already existed in the area. Six individuals of P. incarnata were used to evaluate the vitexin content during the three harvest seasons in 2016 (april, september and november) and three treatments prior to fragmentation drying: nonfragmented aerial part (NF); Fragmented medium from 1 cm to 5 cm (FM) and small fragmented, below 0.5 cm (FS). The UHPLC-MS analysis was performed on an Accela mass spectrometer (Thermo Scientific ®) LCQ Fleet model with Ion Trap 3D via flow injection analysis (FIA) and electrospray ionization with reverse phase (C18) column chromatographic separations and the mobile phase composed of a mixture of MeOH:H2O. The dehydration of the shoot of the wild passion fruit occurred for twenty two and a half hours, the relative humidity reached at 73.8% (maximum) and 9.6% (minimum), the temperature kept between 53.5 and 20.9° C. With the dehydration process the internal temperature of dryer kept above of ambient temperature , whiule the air relative humidity stayed below of the ambient humidity, which guaranteed its function even without fueled by firewood accidentally.

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No. of bitstreams: 2 Dissertação - Flávia Soares Vieira - 2018.pdf: 5162109 bytes, checksum: 753fa227b88042b5bfa2c68b011d6345 (MD5) license_rdf: 0 bytes, checksum: d41d8cd98f00b204e9800998ecf8427e (MD5) Previous issue date: 2018-07-19 / Coordenação de Aperfeiçoamento de Pessoal de Nível Superior - CAPES / Biodiesel production has been increasing every year, which has generated surpluses of glycerin, the main co-product of the transesterification reaction. In the search for applications to this surplus, microbial fermentation has been highlighted as an alternative to add value to this co- product. In this process, microorganisms are used to convert this abundant carbon source into compounds of high economic value, including organic acids and polyols. However, there are still some technological challenges, such as low yield during the fermentation processes and high dependence of new analytical methods, more sensitive and selective, able to identify and quantify the compounds produced. The objective of this work was to establish new analytical methodologies to identify and quantify compounds from bioconversion processes involving the production of organic acids and polyols. To guarantee the quantification of the target compounds, methods based on ultra-high- performance liquid chromatography (UHPLC) were developed and the photodiode array (PDA) and mass spectrometry (MS) detectors were evaluated as alternatives for the monitoring of these two classes of chemical compounds. The analytes investigated in this study were short chain organic acids: citric acid, fumaric acid, glyceric acid, kojic acid, lactic acid, muconic acid, oxalic acid, propionic acid, succinic acid, xylonic acid; and polyols with spatial isomers, including polyols with 4 carbons (C4: erythritol and threitol), 5 carbons (C5: arabitol, ribitol, xylitol), and 6 carbons (C6: dulcitol, iditol, mannitol, sorbitol) and 7 carbons (C7: volemitol). The UHPLC-PDA method developed for the analysis of organic acids was validated by parameters of linearity, limit of detection and quantification, precision and accuracy. The analytical curves showed good linearity with determination coefficients (R²) higher than 0.999 for all organic acids. Precision and accuracy were adequate with intra-day and inter-day variation coefficients below 4.06% and recovery ranged from 94.90% to 109.63%. The developed UHPLC- MS methods presented greater sensitivity and selectivity in the detection of organic acids and polyols, being able to monitor these analytes even in low quantity. The analytical methods developed in this work are crucial tools in the selection or screening of promising microorganisms for low added value substrates conversion and important to optimize biotechnological processes for production of these compounds of interest. / A produção de biodiesel tem aumentado a cada ano, o que vem gerando excedentes de glicerina, principal coproduto do processo de transesterificação. A biotecnologia se destaca como alternativa promissora para agregação de valor à glicerina. Em processos de fermentação, os microrganismos são utilizados para converter essa abundante fonte de carbono em compostos de maior interesse econômico, como ácidos orgânicos e polióis. No entanto, ainda há alguns desafios tecnológicos, como o baixo rendimento dos processos e a falta de métodos analíticos sensíveis e seletivos capazes de identificar e quantificar os compostos produzidos. O objetivo deste trabalho foi estabelecer metodologias analíticas para identificar e quantificar compostos obtidos a partir de processos de bioconversão, tais como ácidos orgânicos e polióis. Para garantir a quantificação destas substâncias-alvo, métodos baseados em cromatografia líquida de ultra-alta eficiência (UHPLC) acoplada aos detectores de arranjo de fotodiodos (PDA) e de espectrometria de massas (MS) foram avaliados como alternativas para o monitoramento dessas duas classes de compostos químicos. Os analitos investigados nesse estudo foram ácidos orgânicos de cadeia curta, incluindo: ácido cítrico, ácido fumárico, ácido glicérico, ácido kójico, ácido lático, ácido mucônico, ácido oxálico, ácido propiônico, ácido succínico, ácido xilônico; e polióis, estereoisômeros contendo 4 carbonos (C4: eritritol e treitol), 5 carbonos (C5: arabitol, ribitol, xilitol), 6 carbonos (C6: dulcitol, iditol, manitol, sorbitol) e com 7 carbonos (C7: volemitol). O método UHPLC-PDA desenvolvido para análise de ácidos orgânicos foi validado pelos parâmetros de linearidade, limite de detecção e quantificação, precisão e exatidão. As curvas analíticas mostraram boa linearidade com coeficientes de determinação (R²) maiores que 0,999 para todos os ácidos orgânicos. A precisão e exatidão demonstraram ser adequadas com coeficientes de variação intra-dia e inter-dia inferiores a 4,06%, e a recuperação variou de 94,90% a 109,63%. Os métodos de UHPLC-MS desenvolvidos apresentaram maior sensibilidade e seletividade na detecção de ácidos orgânicos e polióis, sendo capaz de monitorar esses analitos mesmo eles estando em baixa quantidade. Os métodos analíticos desenvolvidos neste trabalho são ferramentas cruciais na seleção ou triagem dos microrganismos promissores para conversão de substratos de baixo valor agregado e importantes para a etapa de otimização dos processos biotecnológicos de produção desses compostos de interesse.

Ultra-high performance liquid chromatography (UHPLC) provides a considerable increase in throughput compared to HPLC and a reduced solvent consumption. The implementation of UHPLC in pharmaceutical analysis, e.g. quality control, has accelerated in recent years and there is currently a mix of HPLC and UHPLC instrumentation within pharmaceutical companies. There are, however, technical and regulatory challenges converting a HPLC method to UHPLC making it difficult to take full advantage of UHPLC in regulatory-focused applications like quality control in pharmaceutical production. Using chromatographic modelling and fundamental theory, this thesis investigated method conversion between HPLC and UHPLC. It reports on the influence of temperature gradients due to viscous heating, pressure effects and stationary phase properties on the separation performance. It also presents a regulatory concept for less regulatory interaction for minor changes to approved methods to support efficient life cycle management. The higher pressure in UHPLC gave a retention increase of up to 40% as compared to conventional HPLC while viscous heating, instead, reduced retention and the net result was very solute dependent. Selectivity shifts were observed even between solutes with similar structure when switching between HPLC and UHPLC and an experimental method to predict such selectivity shifts was therefore developed. The peak shape was negatively affected by the increase in pressure for some solutes since secondary interactions between the solute and the stationary phase increased with pressure. With the upcoming ICH Q12 guideline, it will be possible for the industry to convert existing methods to UHPLC in a more flexible way using the deeper understanding and the regulatory concept presented here as a case example. / Ultra-high performance liquid chromatography (UHPLC) provides a considerable increase in throughput compared to conventional HPLC and a reduced solvent consumption. The implementation of UHPLC in pharmaceutical analysis has accelerated in recent years and currently both instruments are used. There are, however, technical and regulatory challenges converting a HPLC method to UHPLC making it difficult to take full advantage of UHPLC in regulatory-focused applications like quality control in pharmaceutical production. In UHPLC, the column is packed with smaller particles than in HPLC resulting in higher pressure and viscous heating. Both the higher pressure and the higher temperature may cause changes in retention and selectivity making method conversion unpredictable. Using chromatographic modelling and fundamental theory, this thesis investigates method conversion between HPLC and UHPLC. It reports on the influence of temperature gradients due to viscous heating, pressure effects and stationary phase properties on the separation performance. It also presents a regulatory concept for less regulatory interaction for minor changes to approved quality control methods and how predicable method conversion is achieved by improved understanding.

(EN) This dissertation thesis contains scientific results achieved in the field of analytical chemistry, particularly liquid chromatography. The major part of the results has been published in prestigious international journals in five papers. In addition to that, relevant yet unpublished results have been included as well. In general terms, the work presented here contributed to the concerted efforts to tackle the current lack of novel antibiotics. Specifically, high-performance liquid chromatography (HPLC) and ultra high-performance liquid chromatography (UHPLC) techniques coupled to a variety of detection systems have been employed for analysis of antibiotics and actinomycete secondary metabolites. The first thematic part describes the development of liquid chromatography methods for analysis of lincomycin precursors, lincomycin precursor analogues, and lincomycin derivatives. The methods have been applied to study lincomycin biosynthetic pathway and obtain improved lincomycin derivatives by mutasynthesis. The second thematic part aims at investigating alternative approaches for analysis of antibiotics. Firstly, the core-shell particle and the sub-2 μm particle chromatographic columns were compared. The core-shell particle columns compatible with HPLC proved to be a convenient alternative to the...

Modern separation and spectrometric techniques for biological sample lipidom investigation Due recent progress in field of mass spectrometry the lipidomics, part of metabolomics, is increasing its importance for broad fields of biological study. The aim of this study is to test the lipid extraction techniques and to optimize the preseparation and separation of lipids suitable for mass spectrometry detection. The fragmentation patterns of four, the most abundant lipid classes of glycerolipids (PC, PE, TG, DG), were acquired for the proposed system. These patterns were compared with literature. The most appropriate method for extraction was declared technique according Folch based on methanol and chloroform solution. The preseparation due SPE method is very useful tool for lipid determination. The optimized were focused to reach higher recovery especially in polar lipid fraction. Proposed HPLC system is based on methanol with ammonium buffer, water and isopropanol. The testing was done on three columns with different type of sorbents (Gemini, Syncronis and Kinetex). The separation was evaluated according mass spectrometer response, shape and wide of particular analytes peaks. Composition contains 20% of water was determinate as the best and also the best separation was achieved by Kinetex column. The proposed...

The aim of this study is forced oxidative degradation of active pharmaceutical ingredient abacavir, used to treat HIV-infected patients. A fast and sensitive method for the determination of abacavir and its degradation products by ultra-high performance liquid chromatography has been developed and validated, that made it possible to evaluate the oxidation stability of abacavir and Ziagen tablets. Suitable chromatographic separation was achieved using a Kinetex C18 column and gradient elution with a mobile phase consisting of acetonitrile and ammonium acetate (c = 20 mmol dm−3 , pH = 7.0). The total run time was 11 minutes. The determination of abacavir and its degradation products was performed by a photodiode array detector at λ = 254 nm. The optimized method for the determination of abacavir and its degradation products was applied to study the oxidation of abacavir by both traditional and electrochemical approaches. The forced degradation study in solution revealed abacavir instability in the presence of 3% hydrogen peroxide and during electrochemical oxidation. The study found that excipients in the tablet suppress the degradation of abacavir by approximately 10 %. Abacavir is oxidized by 15 % by hydrogen peroxide after 24 hours at 25 řC, after 1.5 hours at 50 řC and after 5 minutes at...

Per- and polyfluoroalkyl substances (PFAS) encompass a large group of manufactured compounds that have been used in various production processes such as food packaging, commercial products, workplaces, homes, water supplies, and food. PFAS are persistent, resistant to degradation, and can bioaccumulate. Although an exposure limit that predicts adverse health effects has yet to be determined, the Center for Disease Control and Prevention’s 2015-16 health survey found average blood levels of 4.72 ng/ml for PFOS and 1.56 ng/ml for PFOA. The objective of this research was to evaluate the use of laminar flow tandem mass spectrometry following solid phase extraction (SPE) using weak anion exchange (WAX) properties on the detection and quantitation of PFAS compounds. Seven-point calibration standards applied to this research were prepared using certified reference materials (Wellington Laboratories, Ontario, CA), and calibrators were run without sample extraction. The concentrations varied slightly based on the PFAS analyte of interest. All samples and quality controls were prepared by spiking certified reference material (Wellington Laboratories) into pooled human serum (BioIVT, Westbury, NY, USA). A laminar flow QSight®220 ultra-high pressure liquid chromatography-tandem mass spectrometer (LC-MS/MS, PerkinElmer, Waltham, MA, USA) was equipped with a Selectra C18 100 x 2.1mm x 3μm (UCT, Bristol, PA, USA) column with a Brownlee C18 delay column (PerkinElmer) and followed the LC-MS/MS parameters developed for the method. Extraction was accomplished using a WAX SPE column (UCT, ECWAX053) by first conditioning the columns with 1 mL of methanol (Fisher Scientific, Fair Lawn, NJ, USA) followed by 1 mL of 100 mM pH 7 phosphate buffer (Acros Organics, Geel, Belgium, EU). Samples were loaded onto the column at a rate of 1-2 mL/min. The SPE cartridges were washed with 1 mL of 100 mM pH 7 phosphate buffer and 1 mL of millipore water (Millipore Milli- Q Ultrapure Type 1 water system, Millipore Sigma, Burlington, MA, USA), then dried under full flow for 5 minutes. Elution was carried out with 2.5mL of a 98:2 methanol: OptimaTM grade ammonium hydroxide (Fisher Scientific) solution. The eluted samples were then evaporated to dryness using a MULTIVAP® Nitrogen Evaporator (Organomation,Berlin,MA,USA) at 55°C and 5psi. All samples were reconstituted in 100 μL of a 96:4 methanol:water solution. The parameters assessed followed Academy Standards Board Standard 036: Standard Practices for Method Validation in Forensic Toxicology, including matrix interferences, limit of detection (LOD), limit of quantitation (LOQ), a recovery study, and a calibration model. The results of the study were gathered from the following eleven analytes: PFBA, PFBS, PFHxA, PFHpA, PFHxS, PFOA, PFOS, PFNA, PFDA, PFUnA, and PFDoA. Depending on the analyte, a lower LOQ was established at 0.16 – 1.75ng/mL and an upper LOQ at 43.75 – 51.41 ng/mL. Based on the established linear calibration model an LOD in the range of 0.11 - 0.51 ng/mL was achieved. All eleven PFAS analytes showed an acceptable bias of ±20%. All analytes showed a between-run precision (%CV) in an acceptable range of ±20%. No matrix interferences were detected. The average recovery for SPE ranges from 77.64- 104.73% with recovery of 77.64% for PFBS, 83.89% for PFBA, and 95.64-104.73% for PFHxA, PFHpA, PFHxS, PFOA, PFOS, PFNA, PFDA, PFUnA, and PFDoA. Utilizing the UCT WAX SPE column, good recovery for the PFAS compounds was demonstrated. Further, the extraction technique was efficient for high throughput analysis with the extraction time comparable to other traditional SPE methods. The total analytical run time of 11 minutes using the QSight®220 coupled with the UCT Selectra C18 100 x 2.1mm x 3μm column allowed for adequate re-equilibration and system washes to prevent carryover and contamination of these persistent pollutants with excellent chromatography. Having the ability to efficiently and accurately quantify PFAS compounds in biological matrices will allow for better understanding of prevalence, bioaccumulation in biological matrices, and will aid in understanding how these concentrations relate to various health outcomes.

A geração de resíduos sólidos pelas atividades agroindustriais tem criado a demanda por um reaproveitamento tecnológico desses materiais. Assim, o objetivo deste trabalho foi avaliar o potencial bioativo e tecnológico de resíduos agroindustriais, como fontes naturais de compostos fenólicos com atividade antioxidante. Foram analisados resíduos agroindustriais vinícolas, de indústrias produtoras de polpas congeladas de frutas (açaí, cajá, cupuaçu e graviola) e provenientes do beneficiamento de café e de laranja. Inicialmente, foi realizado um estudo para a determinação das condições ótimas de extração, empregando planejamento experimental multivariado com delineamento composto central rotacional, cujos resultados foram avaliados empregando a técnica de superfície de resposta. Na sequência, foram feitos a triagem dos resíduos, baseada na atividade antioxidante, e a caracterização fenólica dos extratos hidroalcoólicos obtidos dos resíduos agroindustriais. De acordo com os resultados de atividade antioxidante, engaço de uva da variedade Chenin Blanc (EC) e semente de açaí (SA) foram os resíduos selecionados, os quais seguiram para as etapas de concentração e fracionamento bioguiado de sua(s) molécula(s) bioativa(s), as quais foram posteriormente identificadas por UHPLC-ESI-LTQ-MS. Extratos brutos e concentrados foram avaliados in vitro quanto à capacidade de desativação de espécies reativas de oxigênio (radicais peroxila, ânion superóxido e ácido hipocloroso) e então, aplicados em óleo de soja, emulsão e suspensão de lipossomos, a fim de se avaliar a efetividade desses extratos como antioxidante natural em matrizes lipídicas. Concentrações intermediárias de etanol (40-60%) e alta temperatura (96°C), exceto para semente de açaí (25°C), foram as condições ótimas para a extração de antioxidantes dos resíduos agroindustriais. Epicatequina, ácido gálico, catequina e procianidina B1 foram os compostos de maior ocorrência, quando avaliados pela técnica de HPLC-DAD. O EC apresentou a maior atividade antioxidante global e SA a maior atividade entre os resíduos de polpas de frutas, laranja e café. A concentração dos extratos brutos de EC e SA, pela resina Amberlite XAD®-2, produziu aumento significativo da atividade antioxidante. Além disso, extratos brutos e concentrados apresentaram atividade antiproliferativa e anti-inflamatória. Os extratos concentrados foram fracionados por meio de Sephadex LH-20, a partir da qual foi possível identificar quatro frações de maior bioatividade para o EC e três para o SA. Procianidina B1, catequina, epicatequina e resveratrol foram identificados no extrato concentrado e frações de EC. Dezoito procianidinas poliméricas, catequina, epicatequina foram os principais compostos identificados em SA, por meio de UHPLC-ESI-LTQ-MS. Resveratrol também foi encontrado em SA pela primeira vez. Quando avaliados em óleo de soja, EC e SA demonstraram atividade pro-oxidante. Contudo, elevada atividade antioxidante foi verificada quando essas amostras foram aplicadas em sistemas lipídicos coloidais, pois retardaram o consumo de oxigênio em uma emulsão óleo/água e o período de indução na produção de dienos conjugados em uma suspensão de lipossomos. Portanto, os resíduos agroindustriais EC e SA possuem potencial tecnológico de reaproveitamento industrial podendo ser considerados possíveis matérias-primas para a obtenção de extratos ricos em antioxidantes ou pela extração de antioxidantes naturais de uso pelas indústrias farmacêutica e/ou de alimentos. / The solid waste generation by agroindustrial activities have created the demand for a technology reuse of these materials. The objective of this study was to evaluate the bioactive and technological potential of agroindustrial residues as sources of phenolic compounds with antioxidant activity. Agroindustrial residues from wineries, from industries producing frozen fruit pulps (acai, caja, cupuaçu and soursop) and from the processing of coffee and orange, were analyzed. Initially, a study using a multivariate experimental planning with central composite rotatable design was performed, whose results were evaluated by response surface technique. After, it was made the screening based on the antioxidant activity and the phenolic characterization of hydroalcoholic extracts of optimized agroindustrial residues. According to the results obtained for the antioxidant activity the residues grape stem from the variety Chenin Blanc (EC) and açaí seed (SA) were selected and followed to the steps of concentration and bioguided fractionation of their(s) molecule(s) bioactive(s), which were subsequently identified by UHPLC-ESI-LTQ-MS. Crude and concentrated extracts were evaluated in vitro for the deactivation capability of reactive oxygen species (peroxyl radicals, superoxide and hypochlorous acid) and then applied to soybean oil, emulsion and liposome suspension in order to evaluate the effectiveness these extracts as natural antioxidant in lipid matrices. Intermediate concentrations of ethanol (40-60%) and high temperature (96 °C), except for acai seed (25 °C) were the optimal conditions for the extraction of antioxidants from agroindustrial residues. Epicatechin, gallic acid, catechin and procyanidin B1 compounds were the most frequent molecules, when assessed by HPLC-DAD. The EC had the highest overall antioxidant activity and SA the greatest activity between residues of fruit pulp, orange and coffee. Concentration of the crude extracts of EC and SA, by Amberlite XAD®-2 resin, produced a significant increase in antioxidant activity. Furthermore, crude and concentrated extracts showed antiproliferative and anti-inflammatory activity. The concentrated extracts were fractionated by Sephadex LH-20, from which it was possible to identify four fractions of greater bioactivity for the EC and three for SA. Procyanidin B1, catechin, epicatechin and resveratrol were identified in the concentrated extract and EC fractions. Eighteen polymeric procyanidins, catechin, epicatechin were the major compounds identified in SA by UHPLC-ESI-LTQ-MS. Resveratrol has also been found for the first time in SA. When evaluated in soybean oil, EC and SA demonstrated pro-oxidant activity. However, high antioxidant activity was observed when these samples were evaluated on lipid colloidal systems, for delayed oxygen consumption in an emulsion oil/water and the induction period in the production of conjugated dienes in a liposome suspension. Therefore, the agroindustrial residues EC and SA have technological potential for industrial reuse and, thus, can be considered as raw material for obtaining antioxidant-rich extracts or by extraction of natural antioxidants useful for pharmaceutical and/or food industries.