This study reports the synthesis and characterization of a Ni/Zn layered double hydroxide salt intercalated with acetate ions and the subsequent replacement of the acetate ions with molybdate ions via an ion exchange reaction, conducted at two different pH values. Regardless of the pH employed during the synthesis, the basal spacing in the Ni/Zn layered double hydroxide salt decreased from 13.08 Å to approximately 9.5 Å, which agreed with intercalation of hydrated molybdate anions. The non-calcined material and the material submitted to heat treatment at 250 °C (basal spacing reduced to 7.35 Å, due to dehydration) were tested as catalyst for the methyl transesterification of soybean oil. Like sodium molybdate in homogeneous media, the solid materials were active catalysts. After reaction at 120 °C for 4 h, the materials afforded high conversions at an alcohol/soybean oil molar ratio of 35:1 and preserved the structure after three consecutive uses. In conclusion, intercalation of molybdate anion into the layered double hydroxide salt proved to be an efficient alternative to support the active species and transform a soluble catalyst into a solid with application in heterogeneous catalysis.

Isopropyl octanoate is an ester used in the formulation of cosmetics, foods, medicines, and other products. The peculiar thermodynamic and kinetic factors, allied with the demand for the applications mentioned above, justify the development of an optimized process for its synthesis. In the present article, the esterification of octanoic acid with isopropanol while using zinc n-octanoate as catalyst is reported. A factorial design was employed where variables such as molar ratio (alcohol:acid), percentage of catalyst (in relation to the acid mass) and temperature were investigated. It was observed that zinc octanoate showed promising catalytic activity, especially at 165 °C, with molar ratios of 8:1 and 6:1, and with 7 and 10% of catalyst, where conversions up to 75% were observed. Optimized conditions for the production of isopropyl octanoate were determined to be 165 °C, 6:1 molar ratio and 5.97% of catalyst.

Currently there is a crescent interest regarding the use of vegetable by-products for food fortification, in order to improve its nutritional quality. Cassava leaves are suitable as nutritional additives, however their cyanide content must be reduced to below 10 mg kg-1 of dry product. Thus, it was developed a method in drying laboratory oven which is able to reduce 99.85% of cyanide present in manioc leaves (from 35 mg kg-1 to 0.05 mg kg-1) while being 509% faster than the traditional method, and without substantial loss of omega-3 fatty acids and β-carotene.

Response surface methodology was used to optimize the total phenolic content (TPC) result in white rice, using a new methodology that employed Fast Blue BB (FBBB) reagent, which reacts more specifically with phenolic compounds, along with direct QUENCHER procedure. This is the first time in which such conciliation between FBBB reagent and QUENCHER was done. The obtained model allowed to evaluate how the factors influenced the method linearity (R2), improving the choice of the optimal system condition. Furthermore, the similarity between experimental results and values generated by the model indicated the method validity within the studied region. Thus, the optimal condition determined in the present work was 30 min reaction time, 0.17 mL FBBB reagent and use of 5% NaOH as the catalyst for the reaction. This optimized condition suggested that the combination of the method, which used FBBB reagent and the direct QUENCHER procedure, was rapid and effective, yielding high TPC values (1488.73 mg of gallic acid equivalent per 100 g).

A 22 factorial design (two factors with two levels, in triplicate) was performed to investigate the influence of factors A (soybean oil content in supplemented diet, at 2.1 and 4.2%) and B (time of treatment, 15 and 30 days) in three responses [(a) total n-3 fatty acids; (b) n-6/n-3 ratio; and (c) polyunsaturated fatty acids (PUFA)/saturated fatty acids (SFA) ratio] from lipids of Nile tilapia submitted to experimental treatment. Normality of residuals was assessed through statistical tests. Factors A and B were significant in all obtained regression models, while AB interaction was not a significant contributor for PUFA/SFA response. ANOVA and response surfaces obtained from factorial design indicated best results in tilapia that received the diet containing 4.2% of soybean oil during 30 days.

The compound extraction is an important step before analyzing composition of samples with antioxidant capacity. Several extraction conditions can be employed (temperature, polarity of solvent and extraction time, for example), and the chosen variables exert great influence upon final results. Thus, in order to execute an efficient extraction, it is needed to manage them with rigor. In this work, a new device was designed and tested. The Prompt, TOugh and eCO-friendly (PTOCO) system is the first equipment in mini-scale that allows a good control of antioxidants extraction conditions. It is a simple and cheap device that only needs small amounts of sample and solvent to obtain sufficient volumes of extract for application in routine analytical methods. Twenty experiments from an experimental design were executed using only 0.5 g of oregano and 60 mL of water. The total antioxidant capacity assays, as well as the mass spectra, confirmed the extraction efficiency.

É altamente desejável desenvolver testes analíticos com resultados de elevada qualidade e reduzir o tempo que é utilizado para esta finalidade. Neste contexto, um novo método de metilação de ácidos graxos assistido por ultra-som, rápido e eficiente para obtenção de ésteres com melhor qualidade para análise de alimentos, foi otimizado e validado através da aplicação da metodologia de superfície de resposta, sendo obtido um tempo de esterificação ideal de 11,72 min, 71% mais rápido do que o melhor método, que é comumente utilizado para esta finalidade. O novo processo de metanólise pode ser eficazmente aplicado a amostras com ácidos graxos livres e os teores de umidade superior a 10 e 5%, respectivamente, sem o risco de oxidação de compostos durante o processo.

Actually, it is highly desirable to develop analytical assays with high quality results, while reducing the amount of time which is used for this finality. In this context, a new, fast and efficient ultrasound-assisted fatty acid methylation method, specially focused to obtain esters with better quality for food analysis, was optimized and validated through the application of response surface methodology, and an optimum esterification time of 11.72 min was achieved, 71% faster than the best method which is commonly used for this purpose. The new methanolysis procedure can be effectively applied to samples with free fatty acid and moisture contents up to 10 and 5% m/v, respectively, without risks of compound oxidation during the process.

Este trabalho avaliou o efeito da suplementação com extrato etanólico de resíduo de acerola (EEAR) na capacidade antioxidante de filés de tilápias no intervalo de 60 dias. Diferentes metodologias foram utilizadas seguindo procedimento QUENCHER e foram analisadas as frações hidrofílicas e lipofílicas do ensaio de capacidade de absorção de oxigênio radical (ORAC FL). A composição em ácidos graxos também foi avaliada, sendo observadas elevadas concentrações dos ácidos linoleico e oleico nos filés, assim como, razões ácidos graxos poli-insaturados/ácidos graxos saturados (PUFA/SFA) satisfatórias. Os maiores valores de capacidade antioxidante nos ensaios 2,2-difenil-1-picrilhidrazil (DPPH) e capacidade redutora de ferro (FRAP) (1778,87 e 4892,77 µmol capacidade antioxidante equivalente ao Trolox (TEAC) g-1, respectivamente) foram encontrados em 15 dias e esses ensaios apresentaram o maior valor de correlação (R = 0,9388). O ensaio ORAC FL indicou que a fração hidrofílica é a maior contribuinte na capacidade antioxidante total (TAC). Dessa forma, o significativo aumento observado na capacidade antioxidante torna a suplementação com EEAR uma potente ferramenta na elevação da capacidade antioxidante dos filés.

This work evaluated the effect of supplementation with ethanolic extract of acerola fruit residue (EEAR) on the antioxidant capacity of tilapia fillets over a period of 60 days. Different methodologies were used following the QUENCHER procedure, and the hydrophilic and lipophilic fractions of the oxygen radical absorbance capacity (ORAC FL) assay were analysed. The fatty acid composition was also evaluated, as high concentrations of linoleic and oleic acids were observed in the fillets, as well as satisfactory polyunsaturated fatty acids/saturated fatty acids (PUFA/SFA) ratios. The highest antioxidant capacities in 2,2-diphenyl-1-picrylhydrazyl (DPPH) and ferric reducing antioxidant power (FRAP) assays (1778.87 and 4892.77 µmol Trolox equivalent antioxidant capacity (TEAC) g-1, respectively) were found at 15 days, and these trials showed the highest correlation coefficient (R = 0.9388). The ORAC FL assay indicated that the hydrophilic fraction is the largest contributor to the total antioxidant capacity (TAC). Thus, the significant increase observed in antioxidant capacity makes supplementation with EEAR a potent tool in the elevation of the antioxidant capacity of tilapia fillets.

Cada matriz alimentar é única. Os antioxidantes endógenos de um produto de panificação não estudados podem mostrar diferentes respostas para atividade antioxidante total (TAA)/resistência a oxidação forçada (ROF) do que é esperado para outros alimentos reportados na literatura. Neste contexto, um design Box-Behnken e estudos de correlação foram aplicados para obter mais informações sobre como compostos antioxidantes específicos afetam o TAA/ROF em pães com sementes de chia e folhas de cenoura. Hipóteses de sinergismo/antagonismo entre os compostos estudados foram elucidadas para tentar justificar os resultados obtidos. Neste tipo específico de amostra, carotenóides e colesterol tiveram as maiores relações com resultados de ensaios de TAA, bem como com pontos de indução provenientes do equipamento Oxitest®, enquanto que α-tocoferol e fitosteróis mostraram correlações negativas. Compostos fenólicos não tiveram nenhuma influência no sistema porque o cozimento em alta temperatura das amostras destruiu grande parte desses analitos.

Each food matrix is unique. Thus, the endogenous antioxidants of an underexplored bakery product might show different responses regarding free radical scavenging/resistance to forced oxidation than what is expected for other foods previously reported in the literature. In this context, a Box-Behnken design and correlation studies were applied in order to obtain more information about how specific antioxidants affect the total antioxidant activity (TAC) and the degree of forced oxidation in white breads with chia seeds and carrot leaves. Hypotheses of synergism/antagonism between the studied compounds were also elucidated in order to justify the obtained results. In this specific sample type, carotenoids and cholesterol showed the greatest relationships with results from TAC assays, as well with induction points using Oxitest® equipment, while α-tocopherol and phytosterols showed negative correlations. Phenolic compounds did not have any influence on the system because the baking procedure at high temperature had severe impacts on them.

O perfil de ácidos graxos (AG) é um parâmetro importante de qualidade e tipificação para alimentos em geral. Esses perfis funcionam como uma espécie de "impressão digital", e podem ser úteis para monitorar fraudes e deterioração em diversos tipos de alimentos. Para os óleos vegetais, o perfil de AG é geralmente determinado após hidrólise, metilação e análise por cromatografia gasosa (CG). Neste trabalho, a metilação do óleo de soja por métodos de catálise básica e ácida foi monitorada por CG-DIC e também por espectrometria de massas ambiente com ionização sonic-spray (EASI-MS). Os principais parâmetros monitorados por EASI-MS foram o perfil de AG e a possível geração de hidroperóxidos dos ésteres metílicos, que foram comparados. O método catalisado por base mostrou-se superior em relação aos demais, por ser mais barato, menos tóxico, não originar produtos de oxidação e ter maior rendimento (95,66% m/m contra 92,86% e 94,51% dos métodos catalisados por ácido).

The fatty acids (FA) profile is an important parameter for quality control and typification for foods in general. These profiles work as a sort of "fingerprint", and may be useful to monitor frauds and deterioration of diverse types of foods. For vegetable oils, the FA profile is commonly determined after hydrolysis, methylation and gas chromatography (GC) analysis. In this work, the acid and base-catalyzed soybean oil methylation methods was monitored via GC-FID and also by ambient sonic-spray ionization mass spectrometry (EASI-MS). The base-catalyzed method is much superior regarding other esterification assays, because it is cheaper, less toxic, no oxidation products are formed and its reaction yield is greater (95.66% m/m against 92.86% and 94.51% from acid-catalyzed methylation methods, respectively).

Este estudo avaliou a composição centesimal de ácidos graxos e a atividade antioxidante total de pães utilizando um design Box-Behnken composto de quinze experimentos e três fatores. Os pães estudados tiveram parte do seu tempo de cozimento alterado, assim como parte da sua farinha de trigo substituída por sementes de chia e folhas de cenoura. Os resultados de capacidade antioxidante de cada experimento foram superiores aos obtidos para um pão controle (495,33 µmol TEAC g-1 para ensaio DPPH e 413,85 µmol TEAC g-1 para ensaio FRAP), mostrando níveis de aumento de até 97 e 102% para os ensaios DPPH e FRAP, respectivamente. Os pães modificados também mostraram aumentos de até 216,69 e 18,88% na quantidade de ácido alfa-linolênico e na razão PUFA:SFA, respectivamente, em relação ao mesmo pão controle (este com 34,03 mg g-1 de ácido alfa-linolênico e razão de 2,86), bem como máxima redução de 70,01% na razão omega-3:omega-6 (15,59 para o pão controle).

This work determined the proximate/fatty acid composition and the antioxidant activity of breads using a Box-Behnken design composed of fifteen experiments and three factors. The studied breads had altered baking times and the wheat flour was partially substituted by chia seeds and carrot leaves. Total antioxidant capacity results were superior to those obtained from control bread (495.33 µmol TEAC g-1 for DPPH assays and 413.85 µmol TEAC g-1 for FRAP assays), showing increased levels of 97 and 102% for DPPH and FRAP assays, respectively. The addition of chia seeds and carrot leaves led to maximal alpha-linolenic acid increase of 216.69% and maximum PUFA:SFA ratio increase of 18.88% in relation to control bread (this with alpha-linolenic acid amount of 34.03 mg g-1 total lipid and a 2.86 ratio value), as well as a maximum omega-3:omega-6 ratio reduction of 70.01% (15.59 ratio value for control bread).

Este estudo avaliou a composição proximal, quantificação de ácidos graxos, atividade antioxidante por diferentes metodologias empregando procedimento Quencher e o conteúdo de fenólicos totais em diferentes cultivares brasileiros de feijão. As amostras apresentaram altas concentrações em ácidos graxos poli-insaturados, tais como ácido linoleico (191,54 a 329,50 mg g-1 de lipídios totais) e ácido α-linolênico (228,03 a 367,27 mg g-1 de lipídios totais). As razões dos somatórios de ácidos graxos ômega 6 e 3 foram baixas, entre 0,71 e 1,12. Em relação aos ensaios de atividade antioxidante, as cultivares apresentaram maiores resultados pela técnica de ácido 2,2-azinobis (3-etilbenzotiazolino-6-sulfônico) (ABTS), de 2401,34 a 4394,80 µmol equivalente Trolox g-1. Os menores resultados foram observados no ensaio de poder antioxidante de redução do ferro (FRAP), de 530,93 a 1440,13 µmol equivalente Trolox g-1. Os resultados dos ensaios 2,2-difenil-1-picrilhidrazilo (DPPH) e ABTS apresentaram a maior correlação (r = 0,619). As cultivares também apresentaram altas concentrações em compostos fenólicos totais, que variaram de 81,85 a 173,65 mg equivalente ácido gálico 100g-1.

This study quantified fatty acids and evaluated the proximate composition, antioxidant activity paired with Quencher procedure and total phenolic compounds in Brazilian bean cultivars. The samples showed high amounts of polyunsaturated fatty acids, such as linoleic acid (191.54 to 329.50 mg g-1 of total lipids) and α-linolenic acid (228.03 to 367.27 mg g-1 of total lipids). The obtained ratios between Omega 6 and 3 fatty acids were low, between 0.71 and 1.12. In relation to antioxidant activity assays, the cultivars showed the best results upon employing the 2,2-azinobis (3-ethyl-benzothiazoline-6-sulfonic acid) (ABTS) method (2401.34 to 4394.80 µmol Trolox equivalent g-1). The lowest results were observed in the ferric reducing antioxidant power (FRAP) assays, 530.93 to 1440.13 µmol Trolox equivalent g-1. The results from 2,2-diphenyl-1-picrylhydrazyl (DPPH) and ABTS methods showed the greatest correlation between themselves (r = 0.619). High concentrations of total phenolic compounds were also detected in the studied cultivars, which varied from 81.85 to 173.65 mg gallic acid equivalent 100g-1.

Este trabalho investigou a qualidade lipídica de leites processados por quantificação de ácidos graxos. Dez amostras de leite em pó integral de vaca e duas de cabra foram submetidas à extração de lipídios totais e à preparação dos ésteres metílicos de ácidos graxos. Estes foram separados em cromatógrafo a gás. A variação da quantidade de ácidos graxos por gramas de lipídios para compostos poliinsaturados, ômega 6, ômega 3 e ácido linoléico conjugado, foi respectivamente: 25,20-46,67, 12,82-31,45, 1,77-7,65 e 7,77-11,60 mg g-1. A razão n-6/n-3 foi menor para os leites em pó de vaca (2,85-6,07) em relação aos de cabra (11,31-12,75) e a quantidade de ácidos graxos trans variou de 0,09 a 0,17 g por porção de 26 g. As amostras apresentaram ácidos graxos essenciais ômega 6 e ômega 3, isômeros do ácido linoléico conjugado e quantidade de ácidos graxos trans em conformidade com a legislação brasileira.

This work investigated of the lipid quality of processed milks by fatty acid quantification. Ten samples of dry whole milk from cow and two from goat were submitted to total lipid extraction and to fatty acid methyl ester synthesis. Then, the synthesized products were separated in a gas chromatograph. The variation of the fatty acid per total lipid gram for polyunsaturated compounds, omega-6, omega-3 and conjugated linoleic acid, was 25.20-46.67, 12.82-31.45, 1.77-7.65 and 7.77-11.60, respectively. The n-6/n-3 ratio for the cow powdered milk samples (2.85-6.07) was lesser reagarding goat milk samples (11.31-12.75) and the trans fatty acid amount varied from 0.09 to 0.17 g per 26 g portion. Essential fatty acids from the omega-3 and omega-6 groups were present in every sample, besides conjugated linoleic acid isomers. The trans fatty acid contents of the samples is in accordance with the Brazilian legislation.