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This article belongs to the Proceedings of IV Conference Ia ValSe-Food CYTED and VII Symposium Chia-Link. The cooked Andean cereals can be considered a good source of minerals, contributing to the recommended daily intakes as observed in previous works. This study evaluated quinoa, amaranth, and buckwheat’s chemical and nutritional compositions and their bioaccessibility through an in vitro gastric digestion simulation to understand their dietary changes. ICP-OES was used to quantify the mineral profile, and the impact of cooking on bioaccessibility was evaluated using multivariate statistical analysis. In this context, the contents of some essential minerals (potassium, magnesium, calcium, zinc, copper, iron and manganese) were evaluated. The lowest cooking losses were noted for calcium in quinoa (67%), and the highest was found for zinc in buckwheat (73%). The calcium and manganese concentration varied considerably with boiling among Andean cereals. For copper, magnesium, iron and manganese, was observed a higher bioaccessibility in cooked quinoa and amaranth. The lowest bioaccessibility was detected for phosphorus in the boiled quinoa fraction (36%). The results highlight the need to consider the losses in bioavailability for minerals during digestion and the related influence on the estimation of proper nutrient intake. These results contribute to understanding the bioaccessibility of minerals in cooked Andean cereals and the changes in these nutrient contents through the boiling process. Other ongoing cooking processes lead to a scientific recommendation of the best cooking method for boosting nutrient intake. This work was supported by grant Ia ValSe-Food-CYTED (119RT0567). info:eu-repo/semantics/publishedVersion

Orientador: Marco Aurélio Zezzi Arruda Dissertação (mestrado) - Universidade Estadual de Campinas, Instituto de Química Resumo: A soja é uma das culturas mais importantes e de maior valor econômico mundial, e por apresentar, entre outras características, excelentes qualidades nutricionais, se encontra difundida em todo o mundo, na alimentação humana e animal. Atualmente, a maior parte de sua produção utiliza sementes transgênicas. No entanto, ainda há muito a se conhecer de sobre as diferenças nutricionais entre as variedades transgênicas e não-transgênicas. Por isso, este trabalho consiste no estudo da diferenciação, em termos de bioacessibilidade, de metais entre a soja transgênica (Glicinemax(L). Merril) e não transgênica, mediante o estudo nutricional comparativo. As sementes de soja das variedades MSOY8200 (NT, não trasgênica) e MSOY7211RR (T, transgênica) são cultivadas em diferentes períodos de semeadura (precursoras, inverno e verão), e comparadas levando-se em conta o conteúdo total de Cu, Fe, Mn e Zn. Na correlação entre os cultivos do mesmo período, são encontradas diferenças estatisticamente significativas nas concentrações totais dos metais, entre as sementes T e NT. Para a avaliação da bioacessibilidade é empregado o método unificado de simulação gastrointestinal in vitro, UBM, para a obtenção das frações bioacessíveis gástricas e gastrointestinais. Na fração gástrica são obtidas as maiores porcentagens da fração bioacessível dos analitos, sendo que estas variam de 106% (Mn) a 38% (Fe) em sementes de soja NT, e de 107% (Mn) a 26% (Fe) para sementes de soja T. No entanto, nas condições gastrointestinais é observada a diminuição da porcentagem da fração solúvel de Fe (9-14%), Mn (27-41%) e Zn (7-38%), enquanto para o Cu são encontradas as maiores porcentagens de bioacessibilidade (73-98%). Por último, é realizado o estudo da bioacessibilidade em soja T e NT e empregando um Sistema de Análise por Injeção Sequencial de microfiltração para detecção on-line por ICP OES, proposto pela primeira vez, onde são obtidos os perfis cinéticos das extrações gastrointestinais dos metais em estudo para as sementes cultivadas na época do verão. As recuperações para o Cu, Fe e Mn variaram de 87% a 118% para semente de soja NT e de 95 a 100% para a semente de soja T. Esse procedimento apresenta-se adequado, possibilitando avaliar a bioacessibilidade gastrointestinal dos analitos nas sementes de soja T e NT Abstract: The soy (Glicinemax(L). Merril) is one of the most important crops and with highest economic worth in the world, among other characteristics, it has excellent nutritional qualities, is widespread throughout the world and is part of the alimentary habits of humans and animals. At present, the most of its production uses transgenic soybeans. However, there is a lot to know about the nutritional differences between the transgenic variety and not transgenic. That is why this work consist in the study of the differentiation, in terms of bioaccesibility, of the metals between transgenic and non transgenic soybean, through a comparative nutritional study. Soybeans seeds of the varieties MSOY8200 (NT, non transgenic) and M7211RR (T, transgenic) are cultivated in different seasons (precursors soybean seeds, winter and summer), and compared through the total content of Cu, Fe, Mn and Zn. In the correlation between the crops of the same season, some significant statistical differences in the concentration of the metals are found between the T and NT soybeans. For the evaluation of the bioaccessibility, a unified method of gastrointestinal simulation, in vitro UBM, was used in order to obtain the gastric and gastrointestinal bioaccessibility fraction. In the gastric fraction the highest percentage of bioaccessible fraction of the analytes is obtained, from 106% (Mn), 38% (Fe) in NT soybeans seeds and 107% (Mn), 26% (Fe) for T soybean seeds. However, in the gastrointestinal conditions a decrease on the percentage of the soluble fraction of Fe (9-14%), Mn (27-41%) and Zn (7-38%) is observed, while for Cu the highest percentages of bioaccessibility (73-98%) is found. Finally, a study of the bioaccessibility in T and NT soybeans seeds, is implemented using a sequential injection analysis system based on microfiltration for on-line detection by ICP OES, which is proposed by the first time. In this system the kinetic profiles of the gastrointestinal extractions of the metals studied for soybean seeds cultivated in summer are obtined. The recoveries for Cu, Fe and Mn have variations from 87% to 118% in NT soybean seeds and from 95% to 100% for T soybean seeds. This procedure is prone in evaluating the gastrointestinal bioaccessibility of the analytes in the T and NT soybean seeds Mestrado Química Analítica Mestra em Química FAPESP 2013/02809-1 BEPE 2014/19369-7

Orientador: Juliana Azevedo Lima Pallone Dissertação (mestrado) - Universidade Estadual de Campinas, Faculdade de Engenharia de Alimentos Resumo: A maioria das frutas cítricas do Brasil é beneficiada em suco, gerando resíduos, utilizados para extrair outros subprodutos de valor. O resíduo possui baixo valor agregado, sendo comercializado como pellets para ração. Seu aproveitamento na alimentação humana é uma alternativa, agregando valor e contribuindo com nutrientes necessários a saúde. Este trabalho objetivou verificar o potencial de minerais de importância para a saúde humana em resíduo de frutas cítricas, sua bioacessibilidade e avaliar se existem diferenças desses nutrientes durante os meses de safra. Foi realizada a otimização e validação de um método para a determinação de cálcio, ferro, zinco e magnésio em resíduo de laranja (pêra e hamlin), limão (taiti e siciliano) e misturas (laranja pêra, hamlin e limão taiti), por espectroscopia de absorção atômica com chama (FAAS). Determinou-se a composição centesimal dos resíduos, realizou-se tratamento térmico nessas amostras e avaliou-se as frações bioacessíveis nas amostras cruas e cozidas. A otimização foi realizada por planejamento experimental e a melhor condição de mineralização foi: 6g de amostra e 8mL de HNO3. Todas as condições estudadas na validação do método foram atendidas. Os teores médios de cálcio, ferro, magnésio e zinco foram 6827,60µg/g, 116,37µg/g, 915,49µg/g e 7,37µg/g, respectivamente. Portanto, uma porção de 100g de bagaço fornece 68,27%, 35,21%, 83,12% e 10% da IDR de cálcio, magnésio, ferro e zinco, respectivamente, sendo assim o bagaço de citrus pode ser considerado fonte de Ca, Fe e Mg. A PCA realizada mostrou que apesar das diferenças na composição de minerais das amostras de diferentes safras, não há uma separação entre laranjas, limões e misturas quanto a composição de macronutrientes. Na avaliação da composição centesimal, as amostras de resíduo de laranja, limão e mistura apresentaram em média 9,3g/100g de umidade, 5,51g/100g de proteínas, 2,92g/100g de cinzas, 2,87g/100g de lipídios, 55g/100g de fibras totais e 23,25g/100g de carboidratos. As frações de fitatos não foram detectados. O percentual de ferro solúvel variou de 19,36-77,33% nas amostras cruas, e de 52,80-68,42% nas amostras cozidas. O ferro dialisado variou de 5,59-25,26% em amostras cruas e de 13,06-69,06% em amostras cozidas. O Ca solúvel foi de 33,34-40,16% nas amostras cruas e de 38,99-55,50% nas amostras cozidas; o Ca dialisado nas amostras cruas foi de 19,32-26,13%, enquanto nas cozidas o percentual foi de 14,71-21,44%. O Mg solúvel variou de 29,95- 85,38% em amostras cruas e de 63,10-94,20% nas cozidas, já o Mg dialisado variou de 46,29-54,08% em amostras cruas e de 34,42-62,51% nas cozidas. O cozimento aumentou a solubilidade de Fe no limão e o Fe dialisado na mistura e no limão; aumentou a solubilidade do Ca, mas diminuiu a fração de Ca dialisada. No Mg foi observado aumento na fração solúvel e dialisável durante o cozimento, exceto para a amostra de laranja cozida que teve um decréscimo na fração dialisada. A avaliação das características físico-químicas do resíduo de citrus e dos minerais bioacessíveis indicando potencial para ser usado na alimentação humana ou ser incorporado a outros produtos, contribuindo com nutrientes para a dieta e agregando valor a esse subproduto Abstract: Most citrus fruits in Brazil is benefited in juice, generating waste used to extract other valuable by-products. The residue has low added value, being marketed as pellets to feed. Its use in food is an alternative, adding value and contributing nutrients necessary for health. This study aimed to verify the importance of mineral potential for human health residue of citrus fruits, its bioaccessibility and evaluate whether there are differences of these nutrients during the months of harvest. Optimization and validation of a method for the determination of calcium was carried out, iron, zinc and magnesium as an orange residue (pear and hamlin), lemon (taiti and sicilian) and mixtures (orange pear, hamlin and lime tahiti) spectroscopy of flame atomic absorption (FAAS). It was determined the chemical composition of the waste, there was heat treated in these samples and evaluated the bioaccessibility in raw and cooked samples. The optimization was conducted by the experimental design and condition the best mineralization was 6g sample and 8ml of HNO3. All conditions studied in method validation were met. The average levels of calcium, iron, magnesium and zinc were 6827,60?g/g, 116,37?g/g, 915,49?g/g and 7,37?g/g, respectively. Therefore, a portion 100g pomace gives 68.27%, 35.21%, 83.12% and 10% RDI of calcium, magnesium, iron and zinc, respectively, thus the citrus pulp can be considered source Ca, Fe, and Mg. The PCA performed showed that despite the differences in the mineral composition of samples of different vintages, there is a separation of oranges, lemons and mixtures as macronutrient composition. In assessing the chemical composition, the orange residue samples, and lemon mixture had an average 9,3g/100g of moisture, 5,51g/100g of protein, 2,92g/100g ash, 2.87g/100g of lipids, 55g/100g of fiber and total 23,25g/100g of carbohydrates. The phytate fractions were not detected. The iron soluble percentage ranged from 19.36 to 77.33% in the raw samples, and 52.80 to 68.42% in cooked samples. The dialysate iron ranged from 5.59 to 25.26% in raw samples and from 13.06 to 69.06% in baked samples. The soluble Ca was 33.34 to 40.16% in the raw samples and from 38.99 to 55.50% in cooked samples; Ca dialysate in the raw samples was 19.32 to 26.13%, while in cooked the percentage was 14.71 to 21.44%. The soluble Mg ranged from 85.38% in raw samples and boiled at 63.10 to 94.20%, as Mg dialysate ranged from 46.29 to 54.08% in raw samples and 34, 42 to 62.51% in cooked. Cooking increased the Fe solubility in lemon and Fe dialysate in the mix and lemon; increased solubility of Ca but decreased the fraction of Ca dialyzed. In Mg was observed increase in the soluble fraction and dialyzed during cooking, except for the baked orange sample had a decrease in the dialyzed fraction. The evaluation of the physico-chemical characteristics of citrus residue and bioaccessibility of minerals indicating the potential to be used as food or be incorporated into other products, contributing nutrients to the diet and adding value to this by-product Mestrado Ciência de Alimentos Mestra em Ciência de Alimentos CNPQ 145659/2014-3

Mestrado em Engenharia Alimentar - Instituto Superior de Agronomia Micro and macroalgae are photosynthetic organisms of large abundance and diversity that contain a variety of compounds with high bioactivity and nutritional value. These compounds have been receiving an increasing interest of researchers due to their potentially positive effect on human health. This has also led to the development of applications for algal biomass, ranging from animal feed to cosmetics, pharmaceuticals, and functional foods. The use of algae biomass in the food industry is still a new concept with the potential to produce healthy foods with added nutritional and bioactive compounds. Although there are many countless studies that support the health benefits of algae, few studies quantify the bioavailability of those nutritional compounds. In vitro digestion methods currently being used for studying the bioaccessibility of said nutrients and bioactive compounds, allowing a better understanding of how those compounds can be used. In this work two algae species, microalgae Skeletonema sp. and macroalgae Cystoseira abies-marina, that are not thoroughly studied were analysed regarding their proximal composition, lipid composition, element composition, phenolic content and relevant bioactivities, as well as their bioaccessibility, in order to understand their potential to be incorporated in food products. Two food products enriched in algae, sauce and cookies, were prepared and analysed, displaying a higher content in polyphenols and higher antioxidant activity than the control in the bioaccessible fraction. The high arsenic concentration found in the macroalgae is also observed in food products prepared with this species requiring a speciation study to assess the risk to human health. The mixture of the food ingredients with Skeletonema sp. was beneficial for the bioaccessibility of monounsaturated fats in sauces, which increased with the incorporation of the microalgae. This work reinforced that incorporating algae in food products can be advantageous, thereby paving the way for effective and marketable functional foods N/A

Este trabalho descreve métodos de determinação de cromo e manganês nas frações bioacessíveis de suplementos alimentares, como hipercalóricos, whey protein e protein bar por espectrometria de absorção atômica em forno de grafite (GFAAS). Para o desenvolvimento dos métodos, as frações bioacessíveis foram submetidas à digestão assistida por radiação micro-ondas e posterior otimização instrumental das temperaturas de pirólise e atomização. Para o manganês, nas amostras de whey protein e protein bar, obteve-se as mesmas temperaturas de pirólise e atomização: 1100 e 1600 °C, respectivamente; para hipercalóricos foi empregado o uso de modificador químico, Mg(NO3)2, e suas temperaturas de pirólise e atomização foram de 1200 e 1700 °C, respectivamente. Para o cromo, não foi preciso o uso de modificador e as temperaturas de pirólise e atomização otimizadas foram as mesmas para as três amostras: 1500 e 2300 °C, respectivamente. A exatidão dos métodos foi investigada através de ensaios de adição e recuperação de analito, apresentando para o manganês valores na faixa de 84 a 113% e para o cromo, valores entre 101 e 116%. A precisão dos métodos também foi avaliada, mostrando desvios padrões relativos menores que 15%. A massa característica (m0), limites de detecção (LD) e quantificação (LQ) para os métodos de cromo foram de 1,9 pg, 0,07 μg g-1 e 0,2 μg g-1, respectivamente; para manganês em hipercalórico os valores obtidos foram de 1,8 pg, 0,03 e 0,08 μg g-1; já em whey protein e protein bar os mesmos foram de 4,2 pg, 0,12 μg g-1 e 0,3 μg g-1. Os métodos desenvolvidos foram aplicados em 12 amostras de suplementos alimentares, sendo 4 de hipercalóricos, 3 de whey protein e 5 de protein bar. Foram observados valores de porcentagem de bioacessibilidade para cromo: 12% em whey protein, 16% em protein bar e, 39 e 49% em hipercalóricos. Em contrapartida, somente uma amostra de whey protein apresentou porcentagem bioacessível não significativa para manganês, e os resultados variaram de 6 até 99%. This study describes methods for the determination of two minerals, chromium and manganese, in the bioaccessible fractions of food supplements, like hypercaloric, whey protein and protein bars, by graphite furnace atomic absorption spectrometry. For the development of the methods, the bioaccessible fractions were submitted to digestion assisted by microwave radiation and posterior instrumental optimization of pyrolysis and atomization temperatures. For manganese, whey protein and protein bars samples obtained the same pyrolysis and atomization temperatures: 1100 and 1600 °C, respectively; for hypercaloric, the use of the modifier Mg(NO3)2 was employed and the pyrolysis and atomization temperatures were 1200 and 1700 °C, respectively. For chromium, it was not necessary the modifier and the pyrolysis and atomization temperatures for the three types of samples were 1500 and 2300 °C, respectively. The accuracy of the methods were investigated through addition and recovery tests; for manganese the study showed reveries in a range of 84 to 113% and for chromium in a range of 101 to 116%. The precision of the methods was also evaluated and presented relative standard deviation values smaller than 15%. The characteristic mass (mo), limits of detection (LD) and quantification (LQ) for chromium were 1,9 pg, 0,07 i_tg g-1 and 0,2 i_tg g-1, respectively; for manganese, in hypercaloric the values found were 1,8 pg, 0,03 and 0,08 i_tg g-1; and finally, in whey protein and protein bars the values were 4,2 pg, 0,12 ilg g-1 and 0,3 ilg g-1. The developed methods were applied to 12 food supplement samples, being 4 of hypercaloric, 3 of whey protein and 5 of protein bars. Four of those samples presented chromium bioaccessible percentage: 49 and 39% in hypercaloric, 12% in whey protein and 16% in protein bars. On the other hand, only one sample of whey protein did not present significant manganese bioaccessible percentage, varying in a range of 6 to 99%.

et al., There is an increased interest in secondary plant metabolites, such as polyphenols and carotenoids, due to their proposed health benefits. Much attention has focused on their bioavailability, a prerequisite for further physiological functions. As human studies are time consuming, costly, and restricted by ethical concerns, in vitro models for investigating the effects of digestion on these compounds have been developed and employed to predict their release from the food matrix, bioaccessibility, and assess changes in their profiles prior to absorption. Most typically, models simulate digestion in the oral cavity, the stomach, the small intestine, and, occasionally, the large intestine. A plethora of models have been reported, the choice mostly driven by the type of phytochemical studied, whether the purpose is screening or studying under close physiological conditions, and the availability of the model systems. Unfortunately, the diversity of model conditions has hampered the ability to compare results across different studies. For example, there is substantial variability in the time of digestion, concentrations of salts, enzymes, and bile acids used, pH, the inclusion of various digestion stages; and whether chosen conditions are static (with fixed concentrations of enzymes, bile salts, digesta, and so on) or dynamic (varying concentrations of these constituents). This review presents an overview of models that have been employed to study the digestion of both lipophilic and hydrophilic phytochemicals, comparing digestive conditions in vitro and in vivo and, finally, suggests a set of parameters for static models that resemble physiological conditions. © 2014 Institute of Food Technologists®., The authors also acknowledge support from Fundaçâo para a Ciência e a Tecnologia under grants PEstOE/EQB/LA0004/2011 and SRFH/BPD/84618/2012 (CNS), to the Scottish Government Strategic Research and Partnership Programmes (GJM), to the European Commission for financial support of EUBerry FP7 KBBE-2010–4 265942 (CNS), EtherPaths FP7-KBBE-222639 (AMA), and to the Spanish MINECO (Grants: AGL2009–13361-C02–02, AGL2012–35814, RM2011–00003–00–00 and Consolider Ingenio 2010 FUN-C-FOOD-CSD2007–00063) (TR).

Mestrado em Engenharia Alimentar - Processamento de Alimentos - Instituto Superior de Agronomia This work investigates the effect of a drastic cooking treatment in chemical composition, particularly, on lipid profile of two species of farmed fish, salmon and meagre, and quantifies the percentage of each fatty acid bioacessibility on these two species in each culinary treatment. To this end, are used methodologies for extracting total lipids (TL), based on the techniques of Bligh & Dyer (1959), for thin layer chromatography and the transesterification of fatty acid methyl esters (FAME - Fatty Acid Methyl Esters). It is verified that the culinary treatment promotes the moisture loss and, consequent, concentration of the fatty acids from the food, although this effect is not uniform for all fatty acids or to both species concerned. Regarding the bioaccessibility it turns out that the fatty acids more bioaccessible on the salmon, are the polyunsaturated fatty acids with a percentage of 67.40% to 60.72% in raw and grilled and within these, docosahexanoic acid is the most bioaccessíble with a percentage of 92.30% in raw salmon and 60.22% on grilled salmon. In the meagre, the fatty acids more bioaccessible are the saturated, with 86.51% in raw and 56.28% in raw and grilled, thus revealing the consumption of salmon is more healthier

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Mestrado em Engenharia Alimentar - Instituto Superior de Agronomia The black scabbard fish is greatly appreciated by the Portuguese population. However, it has generally high levels of mercury (Hg). The aim of this study was to determine the bioaccessibility of mercury in this species subjected to different culinary treatments (fried, grilled and steamed). The content of Hg and the proximate chemical composition were quantified in raw and cooked samples and the samples were also subjected to simulated digestive tract. The results revealed that the culinary treatments affected the chemical composition of black scabbard fish due to water loss and consequent concentration of other nutrients. All biometric parameters analyzed did not influence the Hg content. However, for culinary treatments, grilled fish showed higher levels of Hg, with 80% of samples above the limit set by the EU. The values of provisional tolerable weekly intake showed that fried, boiled and steamed black scabbard fish should be moderately eaten by pregnant women and children as they are particularly vulnerable to the toxic effects of Hg. A higher Hg bioaccessibility was observed in raw fish samples compared to cooked samples. Intestine was the digestion step where bioaccessible Hg reached the highest levels for absorption. The results indicate that frying cooking induce lower Hg bioacessibility, thus representing a lower risk for consumers.