Identification and antioxidant activity determination of carotenoids and anthocyanins from fruits

Orientador: Adriana Zerlotti MercadanteTese (doutorado) - Universidade Estadual de Campinas, Faculdade de Engenharia de AlimentosResumo: Considerando a importancia de carotenoides e antocianinas, tanto como pigmentos naturais como pelas suas propriedades antioxidantes, este trabalho foi desenvolvido com o objetivo de avaliar, por meio de cromatografia liquida de alta eficiencia acoplada aos detectores arranjo de diodos e espectrometro de massas (HPLC-DAD-MS/MS), a composicao de carotenoides e antocianinas em nespera, jaca e jambolao, bem como estudar a atividade antioxidante apresentada por esses pigmentos em diferentes sistemas. Em funcao da coloracao desses frutos, apenas o jambolao foi submetido a analise de antocianinas. Cinco cultivares brasileiros de nespera foram avaliados: Centenaria, Mizauto, Mizuho, Mizumo e Nectar de Cristal. De vinte e cinco carotenoides separados, vinte e tres foram identificados, sendo que os principais foram all-trans-?-caroteno (19-55 %), alltrans-?-criptoxantina (18-28 %), 5,6:5¿,6¿-diepoxi-?-criptoxantina (9-18 %) e 5,6- epoxi-?-criptoxantina (7-10 %). Os conteudos de carotenoides totais variaram entre 196 ?g/100 g (cv. Nectar de Cristal) e 3020 ?g/100 g (cv. Mizumo). Os cultivares Mizauto, Mizuho, Mizumo e Centenaria apresentaram valores de provitamina A entre 89 e 162 ?g RAE/100 g e podem ser considerados uma boa fonte desta pro-vitamina. Nos tres lotes de jaca analisados, quatorze dos dezoito carotenoides identificados foram relatados pela primeira vez, sendo que os principais foram all-trans-luteina (24-44 %), all-trans-?-caroteno (24-30 %), alltrans-neoxantina (4-19 %), 9-cis-neoxantina (4-9 %) e 9-cis-violaxantina (4-10 %). O lote A apresentou o menor conteudo de carotenoides totais (34,1 ?g/100 g) e o menor valor de pro-vitamina A (0,8 ?g RAE/100 g), enquanto nos lotes B e C, os conteudos de carotenoides totais foram de 129,0 e 150,3 ?g/100 g e os valores de pro-vitamina A foram 3,3 e 4,3 ?g RAE/100 g, respectivamente. Os frutos de jambolao apresentaram dois carotenoides principais: all-trans-luteina (43,7 %) e all-trans-?-caroteno (25,4 %). A composicao de antocianinas foi marcada pela presenca de diglucosideos de cinco das seis agliconas comumente encontradas em alimentos, sendo que as principais antocianinas foram delfinidina 3,5- diglucosideo (45 %), petunidina 3,5-diglucosideo (32 %) e malvidina 3,5- diglucosideo (15 %). Esse padrao tambem foi observado para outros flavonoides, onde os principais compostos identificados foram diglucosideos de diidromirecetina, metil-diidromirecetina e dimetil-diidromirecetina, alem de mirecetina glucosideo e um ester de galoil-glucose. A atividade antirradical ABTS?+ (2,2¿-azinobis-(3-etilbenzotiazolina-6-acido sulfonico)) do extrato funcional rico em antocianinas, obtido de frutos de jambolao, foi dependente do pH do meio, com valores de TEAC (capacidade antioxidante equivalente a Trolox) entre 4,8 ?mol Trolox/g fruta (pH 1,0) e 12,7 ?mol Trolox/g fruta (pH 5,0). Esse extrato funcional apresentou cerca de 60 % de protecao ao dimetilantraceno frente a oxidacao por oxigenio singlete, em condicoes de pH 1,0 e 3,0, sendo essa atividade superior aquela apresentada por outras frutas vermelhas. Padrao de cianidina 3-glucosideo foi incorporado em lipossomas unilamelares grandes (LUV) preparados em duas condicoes diferentes de pH (3,1 e 7,4), sendo esses sistemas submetidos a oxidacao induzida por AAPH (diidrocloreto de ?,?¿-azodiisobutiramidina) a 37 °C. Observou-se que as formas de cianidina 3-glucosideo presentes no meio com pH 7,4 (hemiacetais e/ou chalconas e bases quinonoidais), com EC50 = 9,3 ???1,3 ?mol/L (concentracao de antioxidante necessaria para obter 50 % de protecao), apresentaram uma atividade 2,6 vezes maior que as formas presentes no meio com pH 3,1 (maior proporcao de cation flavilium e hemiacetais), cujo EC50 foi de 23,6 ???0,9 ?mol/L. Por fim, padroes de carotenoides, trolox e tocoferol foram microencapsulados com dois materiais de parede diferentes, goma arabica (GA) e maltodextrina (MD), por meio da tecnica de spray-drying. Quando comparada a MD, a parede de GA formou dominios hidrofobicos mais rigidos e compactos, melhorando a solubilizacao de moleculas apolares e reduzindo a acessibilidade de moleculas de oxigenio. Devido a efeitos de compartimentalizacao das moleculas de antioxidante nas microcapsulas (MC), as constantes de desativacao total (kQ) de oxigenio singlete (1O2) foram cerca de duas ordens de magnitude menores nas solucoes de MC, quando comparadas aos valores de kQ em meio homogeneoAbstract: Considering the importance of carotenoids and anthocyanins, as both natural pigments and antioxidants, the present study was carried out to evaluate, by high-performance liquid chromatography connected to a photodiode array and a mass spectrometry detector (HPLC-DAD-MS/MS) the composition of carotenoids and anthocyanins from loquat, jackfruit and jambolao fruits, as well as to study the antioxidant activity showed by these pigments in different systems. Due to the colour of these fruits, only jambolao was submitted to anthocyanin analysis. Five loquat cultivars from Brazil were evaluated: Centenaria, Mizauto, Mizuho, Mizumo and Nectar de Cristal. Twenty five carotenoids were separated, and twenty three of them were identified. The main carotenoids were all-trans-?-carotene (19-55 %), all-trans-?-cryptoxanthin (18-28 %), 5,6:5¿,6¿-diepoxy-?-cryptoxanthin (9-18 %) and 5,6-epoxy-?-cryptoxanthin (7-10 %). The total carotenoid contents ranged from 196 ?g/100 g (cv. Nectar de Cristal) to 3020 ?g/100 g (cv. Mizumo). Cultivars Mizauto, Mizuho, Mizumo and Centenaria showed provitamin A values between 89 and 162 ?g RAE/100 g, and can be considered good source of this provitamin. In the three analyzed batches of jackfruit, fourteen of the eighteen identified carotenoids were reported for the first time in this fruit. The major carotenoids were all-trans-lutein (24-44 %), all-trans-?-carotene (24-30 %), all-trans-neoxanthin (4-19 %), 9-cisneoxanthin (4-9 %) and 9-cis-violaxanthin (4-10 %). Batch A showed the lowest total carotenoid content (34.1 ?g/100 g) and provitamin A value (0.8 ?g RAE/100 g), whereas for batches B and C, respectively, the total carotenoid contents were 129.0 and 150.3 ?g/100 g and the provitamin A values were 3.3 and 4.3 ?g RAE/100 g. The jambolao fruits showed two main carotenoids: all-trans-lutein (43.7 %) and all-trans-?-carotene (25.4 %). The anthocyanin composition was marked by the presence of diglucosides of five among the six aglycones that are commonly found in foods. The major anthocyanins were delphinidin 3,5-diglucoside (45 %), petunidin 3,5-diglucoside (32 %) and malvidin 3,5-diglucoside (15 %). This pattern was also observed for other flavonoids, where the main identified compounds were diglucosides of dihydromyricetin, methyl-dihydromyricetin, and dimethyldihydromyricetin, in addition to myrecetin glucoside and a galoyl-glucose ester. The scavenging capacity of ABTS?+ (2,2'-azinobis(3-ethylbenzthiazoline-6-sulphonic acid)) showed by the anthocyanin-rich functional extract from jambolao fruits, was dependent on the medium pH, showing TEAC (Trolox equivalent antioxidant capacity) values between 4.8 ?mol Trolox/g fruit (pH 1.0) and 12.7 ?mol Trolox/g fruit (pH 5.0). This functional extract showed about 60 % of protection on dimethylantracene oxidation by singlet oxygen, in pH conditions of 1.0 and 3.0, being this activity higher than those showed by other red fruits. Cyanidin 3-glucoside standard was incorporated to large unilamelar liposomes (LUV) prepared at two different pH conditions (3.1 and 7.4). These systems were submitted to oxidation induced by AAPH (?,?¿-azodiisobutyramidine dihydrochloride) at 37 °C. The cyanidin 3-glucoside forms present in the medium at pH 7.4 (hemiacetals and/or chalcones and quinonoidal bases), with EC50 = 9.3 ???1.3 ?mol/L (antioxidant concentration required for 50 % protection), showed na activity 2.6 times higher than that showed by the forms present at pH 3.1 (higher proportion of flavylium cation and hemiacetals), whose EC50 was 23.6 ???0.9 ?mol/L. Finally, carotenoids, trolox and tocopherol standards were microencapsulated with two different wall materials, gum arabic (GA) and maltodextrin (MD), by the spraydrying technique. GA wall formed more rigid and compacted hydrophobic domains than those in the MD microcapsules, improving the solubilization of apolar molecules and reducing the accessibility of oxygen molecules. Due to compartmentalization effects of antioxidant molecules in the microcapsules (MC), the quenching rate constants (kQ) of singlet oxygen (1O2) were reduced almost twoorders of magnitude in MC solutions as compared with those observed in homogenous media. was also observed for other flavonoids, where the main identified compounds were diglucosides of dihydromyricetin, methyl-dihydromyricetin, and dimethyldihydromyricetin, in addition to myrecetin glucoside and a galoyl-glucose ester. The scavenging capacity of ABTS?+ (2,2'-azinobis(3-ethylbenzthiazoline-6-sulphonic acid)) showed by the anthocyanin-rich functional extract from jambolao fruits, was dependent on the medium pH, showing TEAC (Trolox equivalent antioxidant capacity) values between 4.8 ?mol Trolox/g fruit (pH 1.0) and 12.7 ?mol Trolox/g fruit (pH 5.0). This functional extract showed about 60 % of protection on dimethylantracene oxidation by singlet oxygen, in pH conditions of 1.0 and 3.0, being this activity higher than those showed by other red fruits. Cyanidin 3-glucoside standard was incorporated to large unilamelar liposomes (LUV) prepared at two different pH conditions (3.1 and 7.4). These systems were submitted to oxidation induced by AAPH (?,?¿-azodiisobutyramidine dihydrochloride) at 37 °C. The cyanidin 3-glucoside forms present in the medium at pH 7.4 (hemiacetals and/or chalcones and quinonoidal bases), with EC50 = 9.3 ???1.3 ?mol/L (antioxidant concentration required for 50 % protection), showed an activity 2.6 times higher than that showed by the forms present at pH 3.1 (higher proportion of flavylium cation and hemiacetals), whose EC50 was 23.6 ???0.9 ?mol/L. Finally, carotenoids, trolox and tocopherol standards were microencapsulated with two different wall materials, gum arabic (GA) and maltodextrin (MD), by the spraydrying technique. GA wall formed more rigid and compacted hydrophobic domains than those in the MD microcapsules, improving the solubilization of apolar molecules and reducing the accessibility of oxygen molecules. Due to compartmentalization effects of antioxidant molecules in the microcapsules (MC), the quenching rate constants (kQ) of singlet oxygen (1O2) were reduced almost twoorders of magnitude in MC solutions as compared with those observed in homogenous mediaDoutoradoDoutor em Ciência de Alimento

Pequi: a Brazilian fruit with potential uses for the fat industry

Pequi is a native fruit from Brazil, found in the Amazon, Caatinga, Cerrado and Atlantic Rain Forest regions. It is one of the main plants with great potential for sustainable use in Central Brazil. Among 16 species comprising Caryocar genus, three are highlighted: C. brasiliense, C. villosum, and C. coriaceum, of economic importance for families in small communities of Brazilian Cerrado. They are generally organized in cooperatives and use the leaves for preparing medicinal extracts, and the fruits for culinary purposes. When the sale of fresh fruits is reduced, they produce and commercialize fruit preserves, and liqueur products, as well as extract the oil. Harvesting of mature fruits after falling from the tree while keeping some fruits at the plant is the best way for its sustainable production. The internal mesocarp contains from 36 to 66% dry weight of oil having traditional culinary, medicinal and cosmetic uses. This oil has 60% of oleic acid and 35% palmitic acid, thus suitable for industrial fat hardstocks. The presence of the triacylglycerols POO and POP makes the oil of interest for cosmetic and food industries. Both pulp and kernel oils have been studied for their health effects. By physical, enzymatic or chemical modification, the oil has shown potential uses as cocoa butter substitute and zero trans fat product

Roasting process affects the profile of diterpenes in coffee

FAPESP - FUNDAÇÃO DE AMPARO Á PESQUISA DO ESTADO DE SÃO PAULOCNPQ - CONSELHO NACIONAL DE DESENVOLVIMENTO CIENTÍFICO E TECNOLÓGICOCAPES - COORDENAÇÃO DE APERFEIÇOAMENTO DE PESSOAL DE NÍVEL SUPERIORThere is no consensus in the literature regarding the decrease of kahweol and cafestol contents during coffee roasting, but it has been reported that these compounds can undergo dehydration under heat. Kahweol and cafestol were quantified in Arabica and Robusta coffees with different roasting degrees (2, 4, 6, 8 and 10 min at 230 °C). The structures of the diterpenes and the presence of derivative compounds were determined by liquid chromatography with UV–Vis and mass spectrometry detection. In the dark roast samples, dehydro derivatives were found. The roasting process influenced the level of diterpenes in both species of coffee, but the effect was dependent on the intensity of the process. Cafestol and kahweol were degraded (general losses from 60 to 75 % on a lipid basis) to dehydrocafestol and dehydrokahweol, respectively, after 8 min of process, which corresponds to the commercial roasting degree. On the other hand, the amounts of cafestol and kahweol (mg/100 g of coffee) remained stable during the roasting process due to relative increase in lipid concentration.There is no consensus in the literature regarding the decrease of kahweol and cafestol contents during coffee roasting, but it has been reported that these compounds can undergo dehydration under heat. Kahweol and cafestol were quantified in Arabica and Robusta coffees with different roasting degrees (2, 4, 6, 8 and 10 min at 230 °C). The structures of the diterpenes and the presence of derivative compounds were determined by liquid chromatography with UV-Vis and mass spectrometry detection. In the dark roast samples, dehydro derivatives were found. The roasting process influenced the level of diterpenes in both species of coffee, but the effect was dependent on the intensity of the process. Cafestol and kahweol were degraded (general losses from 60 to 75 % on a lipid basis) to dehydrocafestol and dehydrokahweol, respectively, after 8 min of process, which corresponds to the commercial roasting degree. On the other hand, the amounts of cafestol and kahweol (mg/100 g of coffee) remained stable during the roasting process due to relative increase in lipid concentration.2396961970FAPESP - FUNDAÇÃO DE AMPARO Á PESQUISA DO ESTADO DE SÃO PAULOCNPQ - CONSELHO NACIONAL DE DESENVOLVIMENTO CIENTÍFICO E TECNOLÓGICOCAPES - COORDENAÇÃO DE APERFEIÇOAMENTO DE PESSOAL DE NÍVEL SUPERIORFAPESP - FUNDAÇÃO DE AMPARO Á PESQUISA DO ESTADO DE SÃO PAULOCNPQ - CONSELHO NACIONAL DE DESENVOLVIMENTO CIENTÍFICO E TECNOLÓGICOCAPES - COORDENAÇÃO DE APERFEIÇOAMENTO DE PESSOAL DE NÍVEL SUPERIO

Roasting process affects the profile of diterpenes in coffee

There is no consensus in the literature regarding the decrease of kahweol and cafestol contents during coffee roasting, but it has been reported that these compounds can undergo dehydration under heat. Kahweol and cafestol were quantified in Arabica and Robusta coffees with different roasting degrees (2, 4, 6, 8 and 10 min at 230 °C). The structures of the diterpenes and the presence of derivative compounds were determined by liquid chromatography with UV–Vis and mass spectrometry detection. In the dark roast samples, dehydro derivatives were found. The roasting process influenced the level of diterpenes in both species of coffee, but the effect was dependent on the intensity of the process. Cafestol and kahweol were degraded (general losses from 60 to 75 % on a lipid basis) to dehydrocafestol and dehydrokahweol, respectively, after 8 min of process, which corresponds to the commercial roasting degree. On the other hand, the amounts of cafestol and kahweol (mg/100 g of coffee) remained stable during the roasting process due to relative increase in lipid concentration239961970CONSELHO NACIONAL DE DESENVOLVIMENTO CIENTÍFICO E TECNOLÓGICO - CNPQCOORDENAÇÃO DE APERFEIÇOAMENTO DE PESSOAL DE NÍVEL SUPERIOR - CAPESFUNDAÇÃO DE AMPARO À PESQUISA DO ESTADO DE SÃO PAULO - FAPESPnão temnão temnão te

Diversity between Jatropha curcas L. accessions based on oil traits and X-ray digital images analysis from it seeds

<div><p>Abstract Jatropha curcas L. is a species with high potential for the biodiesel production. Therefore, the oil yield and quality from it seeds should be known. This study aimed to estimate the correlation between morphological traits, yield and oil quality evaluated in the seeds, to know the genetic diversity between J. curcas accessions and it behavior regarding to three harvest seasons. For this purpose, X-ray digital images from seeds of 18 accessions were obtained, and the seeds analyzed for external and internal morphological aspects. The same seeds were analyzed for oil yield and quality. In general, the results concerning diversity indicated a narrow genetic base. More rounded and very long seeds had lower oil yield. Larger seeds presented higher oil yield only when their internal cavity was filled by their endosperm. Most of the accessions showed variation regarding the size of the endosperm, yield and oil quality between harvest seasons.</p></div