Novel cookie formulation with defatted sesame flour: Evaluation of its technological and sensory properties. Changes in phenolic profile, antioxidant activity, and gut microbiota after simulated gastrointestinal digestion.

Defatted sesame flour (DSF), a coproduct of the sesame oil extraction process, is often discarded despite having high polyphenol content. The aim of this study was to improve the antioxidant properties of cookies with increasing amounts of DSF (5, 10, and 20%) and study its impact on processing and gastrointestinal digestion. Besides, we evaluated the effect of this incorporation on the technological and sensory properties of cookies. The formulation with 10% (SFC10) showed technological quality similar to control, and was the most accepted by consumers. After baking, 13 out of 25 polyphenols from DSF were observed, and only 19% of the initial SFC10 polyphenols would be potentially absorbed after digestion. Besides, the addition of DSF benefits the microbiota composition after colonic fermentation. In conclusion, supplementation with 10% of DSF in cookies improves sensorial acceptance and antioxidant properties, without affecting the technological ones.

Identification of chia, flax and sesame seeds authenticity markers by NMR-based untargeted metabolomics and their validation in bakery products containing them.

Chia, flax, and sesame seeds are considered superseeds due to their beneficial nutritional properties, and they are frequently included as functional ingredients in foods. Authenticity markers of these seeds, including bakery products containing them, have been identified by both liquid and gas chromatography coupled to mass spectrometry (LC-MS/MS and GC-MS/MS, respectively) targeted metabolomics. However, there are no reports describing the use of nuclear magnetic resonance (NMR) spectroscopy based metabolomics to identify authenticity markers in either the raw seeds or foods containing them. We herein report the application of an untargeted NMR-based metabolomics workflow to the identification of authenticity markers for the three seeds. Seven markers, belonging to the families of polyphenols and cyanogenic glycosides, allowed good differentiation of the raw materials. Validation in cookies containing different seed percentages showed that two markers resisted the processing stage, making them feasible authenticity markers for the food trade.

Comparative metabolite fingerprinting of chia, flax and sesame seeds using LC-MS untargeted metabolomics.

Chia, flax, and sesame seeds are well known for their nutritional quality and are commonly included in bakery products. So far, the development of methods to verify their presence and authenticity in foods is a requisite and a raised need. In this work we applied untargeted metabolomics to propose authenticity markers. Seeds were analyzed by HPLC-MS/MS and 9938 features in negative mode and 9044 in positive mode were obtained by Mzmine. After isotopes grouping, alignment, gap-filling, filtering adducts, and normalization, PCA was applied to explore the dataset and recognize pre-existent classification patterns. OPLS-DA analysis and S-Plots were used as supervised methods. Twenty-five molecules (12 in negative mode and 13 in positive mode) were selected as discriminant for the three seeds, polyphenols and lignans were identified among them. To the best of our knowledge, this is the first approach using non-target HPLC-MS/MS for the authentication of chia, flax and sesame seeds.

Comparative Metabolomics and Molecular Phylogenetics of Melon (Cucumis melo, Cucurbitaceae) Biodiversity.

The broad variability of Cucumis melo (melon, Cucurbitaceae) presents a challenge to conventional classification and organization within the species. To shed further light on the infraspecific relationships within C. melo, we compared genotypic and metabolomic similarities among 44 accessions representative of most of the cultivar-groups. Genotyping-by-sequencing (GBS) provided over 20,000 single-nucleotide polymorphisms (SNPs). Metabolomics data of the mature fruit flesh and rind provided over 80,000 metabolomic and elemental features via an orchestra of six complementary metabolomic platforms. These technologies probed polar, semi-polar, and non-polar metabolite fractions as well as a set of mineral elements and included both flavor- and taste-relevant volatile and non-volatile metabolites. Together these results enabled an estimate of "metabolomic/elemental distance" and its correlation with the genetic GBS distance of melon accessions. This study indicates that extensive and non-targeted metabolomics/elemental characterization produced classifications that strongly, but not completely, reflect the current and extensive genetic classification. Certain melon Groups, such as Inodorous, clustered in parallel with the genetic classifications while other genome to metabolome/element associations proved less clear. We suggest that the combined genomic, metabolic, and element data reflect the extensive sexual compatibility among melon accessions and the breeding history that has, for example, targeted metabolic quality traits, such as taste and flavor.

Defatted chia flour as functional ingredient in sweet cookies. How do Processing, simulated gastrointestinal digestion and colonic fermentation affect its antioxidant properties?

The aim of this work was to improve the antioxidant quality of cookies using defatted chia flour (DCF), which is a by-|product of the food industry. We prepared cookies containing DFC (5, 10 and 20%), and evaluated the technological and sensory qualities of cookies. Additionally, we verified the effects of processing and simulated gastrointestinal digestion on polyphenols content. The addition of DFC did not affect the technological quality of cookies, with the exception of color. Furthermore, cookies supplemented with 10% DFC were sensorial preferred over the others. The addition of DFC increased the polyphenol content and the in vitro antioxidant capacity of cookies. Besides, the simulated gastrointestinal digestion suggested that 73% of total polyphenols could be absorbed in the intestine, showing an antioxidant effect greater than expected, also showing prebiotic effects. Supplementation of cookies with 10% DFC could be recommended to improve antioxidant quality without reducing the technological or sensorial properties.

Targeted metabolomics to assess the authenticity of bakery products containing chia, sesame and flax seeds.

Food fraud is perpetrated with increasing frequency along the food chain, triggering the need for new and modern tools to detect food authenticity. Chia, flax and sesame seeds are well known for the good nutritional characteristics of their oils, but there is a lack of knowledge regarding the authenticity of these seeds and food products containing them as well. In the present work, we propose a method based on targeted metabolomics to identify the polyphenols present in seeds, which can be used as markers of authenticity. We tentatively identified 44 polyphenols in the different seeds by HPLC-DAD-ESI-qTOF (MS/MS). Chemometrics allowed the selection of 12 compounds, which are nominated as novel markers for seed authentication. Some of these compounds were also found in a lab-scale preparation of cookies supplemented with the studied seeds. The proposed chemical markers resisted the baking process, representing good candidates to be used in the authentication of raw material and bakery products containing these seeds.

Discovery of food identity markers by metabolomics and machine learning technology.

Verification of food authenticity establishes consumer trust in food ingredients and components of processed food. Next to genetic or protein markers, chemicals are unique identifiers of food components. Non-targeted metabolomics is ideally suited to screen food markers when coupled to efficient data analysis. This study explored feasibility of random forest (RF) machine learning, specifically its inherent feature extraction for non-targeted metabolic marker discovery. The distinction of chia, linseed, and sesame that have gained attention as "superfoods" served as test case. Chemical fractions of non-processed seeds and of wheat cookies with seed ingredients were profiled. RF technology classified original seeds unambiguously but appeared overdesigned for material with unique secondary metabolites, like sesamol or rosmarinic acid in the Lamiaceae, chia. Most unique metabolites were diluted or lost during cookie production but RF technology classified the presence of the seed ingredients in cookies with 6.7% overall error and revealed food processing markers, like 4-hydroxybenzaldehyde for chia and succinic acid monomethylester for linseed additions. RF based feature extraction was adequate for difficult classifications but marker selection should not be without human supervision. Combination with alternative data analysis technologies is advised and further testing of a wide range of seeds and food processing methods.

Photoinduced Synthesis of Dibenzofurans: Intramolecular and Intermolecular Comparative Methodologies.

The SRN1 reaction has been used as a powerful tool for the synthesis of heterocycles, and only a few studies about photoinduced intramolecular cyclization to generate a new C-O bond by a radical pathway have been reported. This work introduces two strategies for the synthesis of substituted dibenzofurans by electron transfer (eT) reactions. The first one is a three-step process that comprises bromination of o-arylphenols, Suzuki-Miyaura cross-coupling and photoinduced cyclization in order to obtain the above-mentioned products. The second one is a metal-free procedure and does not require any photocatalyst. Different solvents were tested, and the yields ranged from low to moderate. A comparison was established between both methodologies, showing that the second one is the most suitable for the synthesis of dibenzofurans.

Photoinduced nucleophilic substitution of iodocubanes with arylthiolate and diphenylphosphanide ions. Experimental and computational approaches.

A new synthetic route to modify the cubane nucleus is reported here. Methyl-4-iodocubane-1-carboxylate (1) and 1,4-diiodocubane (2) were employed as reagents to react with arylthiolate and diphenylphosphanide ions under irradiation in liquid ammonia and dimethylsulphoxide. The reactions proceed to afford thioaryl- and diphenylphosphoryl- cubane derivatives in moderate to good yields. It is also found that the monosubstituted product with retention of the second iodine is an intermediate compound. Mechanistic aspects are supported by DFT calculations.