Avaliação dos compostos fenólicos e atividade antioxidante in vitro de chás : classificação, modelagem e otimização por técnicas quimiométricas

Orientador : Prof. Dr. Charles Windson Isidoro HaminiukCo-orientador : Prof. Dr. Daniel GranatoSupervisora internacional: Profª. Drª. Trust BetaTese (doutorado) - Universidade Federal do Paraná, Setor de Tecnologia, Programa de Pós-Graduação em Engenharia de Alimentos. Defesa: Curitiba, 23/10/2015Inclui referências : fls. 105-122Resumo: Os chás são as bebidas não alcoólicas mais consumidas no mundo depois da água, e tem ganhado muita atenção por promoverem benefícios a saúde. Entre os efeitos benéficos incluem os efeitos anti-mutagênicos, anti-câncer e anti-apoptótica, neuroprotetivo, hiperglicêmico e anti-hiperglicêmico, antioxidante, antimicrobiano e anti-inflamatório. Estas atividades biológicas estão associadas em parte a atividade antioxidante dos compostos químicos presentes nos chás, especialmente flavonoides e ácidos fenólicos (Capítulo 1). O objetivo deste trabalho foi avaliar os compostos fenólicos e atividade antioxidante in vitro de chás consumidos no Brasil. No Capítulo 2, 51 chás brasileiros de oito diferentes espécies (Camellia sinensis, Peumus boldus, Matricaria recutita, Baccharis trimera, Cymbopogon citratus, Pimpinella anisum, Mentha piperita e Ilex paraguariensis) foram analisados nos termos dos compostos fenólicos, cor e atividade antioxidante in vitro medida por FRAP e DPPH. Os dados foram tratados usando PCA, HCA e LDA. Os resultados de ácido gálico, catequina, epicatequina, procianidina B2, quercitrina e cafeína mostraram uma correlação significativa (p 0,80). Uma otimização simultânea foi realizada usando a função de desejabilidade e a condição ótima para maximizar a extração de epicatequina, epigalocatequina galato, epicatequina galato, assim com a atividade antioxidante (DPPH e FRAP) foi sugerida. Portanto, no Capítulo 3 os resultados mostraram que o chá branco foi o melhor para obter o maior teor de antioxidantes, desta forma o Capítulo 4 foi destinado a otimizar a extração dos compostos antioxidantes deste (chá branco) por um planejamento Box-Behnker e os compostos foram identificados por LC-DAD-MS/MS. Todos os modelos propostos foram capazes de explicar mais de 85% da variação dos dados e a simultânea otimização realizada usando DPPH, ABTS, FRAP, (-)-epigalocatequina galato e (-)-epicatequina sugeriu o tempo de 10 min, a temperatura de 66 °C e a solução de 30% etanol como o ponto ótimo de extração. Os principais compostos identificados por espectroscopia de massa foram o ácido gálico, ácido 5-galoilquínico, cafeína, teobromina, galocatequina, epigalocatequina, epicatequina, epigalocatequina galato, e epicatequina galato. Portanto, este estudo mostrou que diferentes determinações analíticas associadas às ferramentas quimiométricas podem ser usadas para explorar e classificar as amostras, e podem ser usadas para processos de extração de compostos bioativos de plantas. Palavras-Chaves: análise multivariada, superfície de resposta, flavonoides, cromatografia líquida de alta eficiência.Abstract: Tea is the second most consumed beverage aside from water, and has gained much attention due to its health-promoting benefits. Among the benefit effects include antimutagenic, anticancer and anti apoptotic, neuroprotective, hypoglycemic and antihyperglycemic, antioxidant, antimicrobial, and anti inflammatory. These biological activities are associated in part to the antioxidant activity of chemical compounds present in teas, especially flavonoids and phenolic compounds (Chapter 1). The aim of this study was to evaluate the phenolic compounds and in vitro antioxidant activity of teas consumed in Brazil. In the Chapter 2, 51 Brazilian teas of eight different species (Camellia sinensis, Peumus boldus, Matricaria recutita, Baccharis trimera, Cymbopogon citratus, Pimpinella anisum, Mentha piperita and Ilex paraguariensis) were analyzed in terms of the phenolic compounds, color, and in vitro antioxidant activity using FRAP and DPPH. The dataset was analyzed using PCA, HCA, and LDA. Gallic acid, catechin, epicatechin, procyanidin B2, quercetrin, and caffeine displayed a significant correlation (p 0.80). A simultaneous optimization was performed using the desirability function and optimum point to maximize the extraction of epicatechin, epigallocatechin gallate, epicatechin gallate, as well as the antioxidant activity (DPPH and FRAP) was suggested. Therefore, in the Chapter 3 the results showed up that white tea was the best solution for obtaining the higher content of antioxidant compounds, then the Chapter 4 was destined to optimize the extraction of antioxidant compounds from white tea by Box-Behnken design and the compounds were identified by LC-DAD-MS/MS. All mathematical models proposed were able to explain up more that 85% of data variation and the optimization performed using DPPH, ABTS, FRAP, (-)-epigallocatechin gallate, and (-)-epicatechin gallate suggested the time of 10 min, temperature of 66 °C and the 30% ethanol solution as optimum point. The principal compounds identified in the optimum point by mass spectrometry were gallic acid, 5-galloylquinic acid, caffeine, theobromine, gallocatechin, epigallocatechin, epicatechin, epigallocatechin gallate, and epicatechin gallate. Nevertheless, this study showed that different analytical determination associated chemometrics tools can be used to explore and classify the samples, thus it can be used for extraction processes of bioactive compounds of plant samples. Keywords: multivariate analysis, response surface methodology, flavonoids, high liquid performance chromatography

Diversificação de negócios na propriedade frutícola: processamento de maçã / Business diversification in fruit property: apple processing

A pomicultura nacional está passando por uma transição importante, influenciada pela crise econômica do país e por mudanças climáticas que afetam diretamente o custo de produção das principais cultivares, Gala e Fuji (> 90% da produção). A necessidade em utilizar novas cultivares mais adaptáveis aos efeitos do clima, com baixo custo de produção e aceitação sensorial pelos consumidores, torna-se mais evidente a cada safra. A diversificação de produção, a fim de agregar valor à matéria prima através da fabricação de produtos convencionais e inovadores com qualidade, consiste em uma alternativa para enfrentar os baixos preços do quilo da fruta pago aos produtores. Portanto, o setor de produção deve quebrar paradigmas e se reinventar através de estratégias para introdução no comércio de cultivares com dupla aptidão, tanto para o consumo in natura quanto para o processamento industrial.  

Effect of mash maceration and ripening stage of apples on phenolic compounds and antioxidant power of cloudy juices: A study using chemometrics

AbstractThe effects of different enzymatic preparations on total phenolic content, phenolic profile (HPLC), and ferric reducing antioxidant power (FRAP) of cloudy juices from Lis Gala and Fuji Suprema apples varieties, at three ripening stages (unripe, ripe and senescent) were investigated using Principal Component Analysis and Hierarchical Cluster Analysis. The commercial preparations enzymatic (Ultrazym® AFPL; Pectinex® Ultra Clear; Pectinex® SMASH XXL; Panzym® YieldMASH) increased the total phenolic compounds and ferric reducing capacity of the cloudy juice from unripe and ripe Lis Gala (respectively by 67 and 49% for unripe apples, and 28 and 33% for ripe apples) and unripe Fuji Suprema apples (23 and 55%), while for the ripe Fuji Suprema apples only Pectinex® Ultra Clear and Panzym® YieldMASH had this effect. No significant (p > 0.05) was observed on senescent stage, whatever the enzymatic preparation. Enzymatic preparations could increase phenolic compounds concentration and antioxidant capacity of cloudy apple juice, but this effect depended on the maturity of the apples

Influence of processing on the quality of pomaceas juice (Pyrus communis and Malus domestica)

Pear (Pyrus communis), which is intensively cultivated in subtropical and temperate climates, has recently attained the 3rd position in the world fruit ranking, just after apple and peach. This fruit exhibits certain similarities to apple with respect to the pulp, but pear is used as a raw material only when apple is no longer available, which suggests that the same technology line may be utilized. Both fruits do have processing compatibilities, and it is permissible to add pear juice to apple juice at levels defined by law. Quality indicators, such as pH, total acidity, total phenolic compounds and antioxidant activity were used. The simple sugar analysis clearly defines fructose as the main component in pear juice, and lower figures were found when enzymatic processing was used. Color intensity measured instrumentally was much greater in pear juice with all processing methods and in apple juice when an enzymatic method was used. The results clearly indicate proper ways of processing pear and apple, aiming to have better products, as the grinding and extraction processing steps surely affect the fruit juice quality

APPLE PULP ENZYME TREATMENT WITH ULTRAZYM®AFP-L AND PANZYM®YIELDMASH

The present study aimed to verify the influence of the enzymatic preparations Ultrazym®AFP-L and Panzym®YieldMASH over the yield and chemical quality of apple juice. The process was optimised according to two parameters: temperature and enzyme concentration in a one hour-long run. The results of physical and chemical analysis were further submitted to multivariate statistical procedure aimed at pattern recognition. The exploratory and classificatory modeling discriminated the samples with 100 % correlation. The results of the experimental factorial design pointed to enzyme concentration as being the main factor that increased the yield. The concomitant observation of data using Principal Component Analisys (PCA) exploratory tools showed the tendency to separate the control samples according to higher content of phenolic compounds, glucose, pH and colour; the Ultrazym® AFP-L samples according to total acidity; and the Panzym®YieldMASH samples according to higher sugar content. It was concluded that the utilization of industrial enzymes in apple processing increases the yield of juice and decreases the amount of pomace