Thermophysical properties of blends composed of Amazonian fats and soybean oil.

Thermophysical properties of blends composed of soybean oil and fats obtained from fruits and seeds from Brazilian Amazonian region (Murumuru, Tucuma, and Bacuri) were investigated, looking for more sustainable alternatives to the mostly used industrial fats, for applications in product formulation. Fatty acid (FA) and triacylglycerol composition, nutritional indexes, solid fat content (SFC), compatibility, consistency, melting, and crystallization profiles were determined. Soybean oil increased blends' unsaturated FA profile, leading to lower SFC, but higher nutritional quality. Fats' melting profiles were significantly altered with soybean oil addition: temperatures decreased with the increase in oil content. Iso-solids diagrams showed that lipids were compatible, which is a technological advantage. SFC and consistency profiles suggested that tucuma and murumuru fats could be used as hardstocks for lipid products, and bacuri fat could be applied in products such as margarine and spreads. Blends could improve fats' spreadability and other technological properties, which is promising for applications in products formulation.

Solid-liquid equilibria of triacylglycerols and vitamin E mixtures.

Oils and fats are important ingredients for food and pharmaceutical industries. Their main compounds, such as triacylglycerols (TAG), are responsible for determining their physical properties during food storage and consumption. Lipid-rich foods are also sources of minority compounds, which is the case of vitamin E, mainly represented by (±)-α-tocopherol. These compounds can interact with the main lipid molecules in food formulation leading to modification on lipids' physicochemical properties during processes, storage, as well as during digestion, possibly altering their nutritional functionalities, which is the case of vitamin E antioxidant abilities, but also their solubility in the systems. In this case, the study of the phase-behavior between (±)-α-tocopherol and lipid compounds can elucidate these physicochemical changings. Therefore, this work was aimed at determining the solid-liquid equilibrium (SLE) of binary mixtures of TAG (tripalmitin, triolein and tristearin) and (±)-α-tocopherol including the complete description of their phase diagrams. Melting data were evaluated by Differential Scanning Calorimetry, Microscopy, X-Ray Diffraction, and thermodynamic modeling by using Margules, UNIFAC, and COSMO-SAC models. Experimental results showed that systems presented a monotectic-like behavior, with a significant decreasing in TAG melting temperature by the addition of (±)-α-tocopherol. This high affinity and attractive strengths between these molecules were also observed by thermodynamic modeling, whose absolute deviations were below 2 %. Micrographs and X-ray diffraction evidenced the possible formation of solid solutions. Both behaviors are interesting by avoiding phase separation on food in solid and liquid phases, possibly improving the antioxidant role the (±)-α-tocopherol in lipid-base systems.

Evaluating the in vitro digestion of lipids rich in medium-chain fatty acids (MCFAs) using dynamic and static protocols.

Investigating the digestion of lipids is paramount for developing new lipid-based products. This work evaluated the gastrointestinal (GI) digestion of medium-chain fatty acids (MCFAs) rich lipids. The dynamic GI in vitro system was used to simulate gastric, duodenal, jejunal, and ileal GI tract portions. Results from the dynamic protocol were compared against static in vitro assays and GC analyses were conducted to assess the FA profile of FFA released during digestion. Caprylic and capric acids released during the gastric digestion of MCT oil varied from 61-63% and 36-38% of total esterified FA, respectively. Lauric acid was the most representative FFA released (31-54%) during the gastric digestion of coconut oil samples. It was observed that the gastric digestion phase plays a crucial role in the MCFA lipolysis and the lipase activity restricted the amount of free MCFA liberated during the GI digestion, resulting in incomplete lipids hydrolysis.

Circular Economy in the Food Chain: Production, Processing and Waste Management.

Food processing, from agricultural production to domestic consumption, is responsible for generating great amounts of waste per year, resulting in soil, water, and air pollution. These pollutants, together with the uses of petrochemical process inputs such as solvents, additives, or fuels, increase the food chain's environment impacts resulting in wasted resources. In response to this scenario, the circular economy (CE) theory is presented in literature as a liable alternative for the design of more sustainable production chains. In this context, this work was aimed at evaluating the literature's approach on the CE concept within the food processing and food waste management. The works show the centrality of "food waste" as a focus for the application of the CE. However, despite the relevance of management, reuse, or valuation of food waste, particularly due to its contribution to carbon footprint and decrease of food safety, studies have found other strategies for improvement of CE in the food chain. In this case, works in literature were allocated within the framework presented by the Ellen Macarthur Foundation called ReSOLVE, with proposals for modification of production chain to promote the CE. Among the proposals, one should highlight: modification of productive systems for mitigation of environmental impacts and greenhouse emissions, processes optimization for decreasing the use of natural resources and wastes, use of 4.0 Industry such as IoT, big data, or machine learning techniques for improvement of the whole supply chain, development of collaborative platforms for production and market, use of residues or co-products by design of intra- or inter-chain loops, and exchange of process or inputs with high environmental impacts for greener ones.

Phytosterols and γ-Oryzanol as Cholesterol Solid Phase Modifiers during Digestion.

Literature reports that ingestion of phytosterols and γ-oryzanol contributes to cholesterol lowering. Despite in vivo observations, thermodynamic phase equilibria could explain phenomena occurring during digestion leading to such effects. To advance the observations made by previous literature, this study was aimed at describing the complete solid-liquid phase equilibrium diagrams of cholesterol + phytosterol and γ-oryzanol systems by DSC, evaluating them by powder X-ray, microscopy, and thermodynamic modeling. Additionally, this study evaluated the phenomena observed by an in vitro digestibility method. Results confirmed the formation of solid solution in the cholesterol + phytosterols system at any concentration and that cholesterol + γ-oryzanol mixtures formed stable liquid crystalline phases with a significant melting temperature depression. The in vitro protocol supported the idea that the same phenomena can occur during digestion in which mechanochemical forces were probably the mechanisms promoting cholesterol solid phase changes in the presence of such phytocompounds. In this case, these changes could alter cholesterol solubility and possibly its absorption in the gastrointestinal lumen.

Solid-liquid equilibrium of free form of oil contaminants (3-MCPD and glycidol) in lipidic systems.

Esters of 3-monochloropropane-1,2-diol (3-MCPD) and glycidol are reported vegetable fats and oils contaminants formed during processing. During digestion, esterified forms are hydrolyzed making the free forms, with high toxicity to human health, possibly available in the digestive system, which could depend, among other factors, on the phase condition stablished in the gastrointestinal tract between contaminants and lipids. Therefore, this work was aimed at evaluating the solid-liquid equilibrium (SLE) of binary and pseudobinary mixtures of fatty acids (palmitic, oleic and stearic), triacylglycerols (tripalmitin, triolein and tristearin) and a partial acylglycerols, with 3-MCPD and glycidol, by differential scanning calorimetry (DSC) and thermodynamic modeling with Margules 2 and 3 suffixes, UNIFAC and ideal models. Melting properties of the contaminants were determined by DSC thermograms, with microstructure micrographs and compared to some predictive group contribution models (GC). 14 complete SLE phase diagrams could be determined. Results showed that the lipid compounds had high affinity with the free contaminants with probably the formation of liquid crystalline structures and/or solid solutions. The Margules 3 suffixes model showed the best fit with the lowest average relative deviations, no higher than 1%, although the parameters probably incorporated the non-ideality promoted by the crystalline phase behavior. The formation of mesophases and/or solid solutions with very high melting temperature probably means a difficulty of separating the contaminants from the lipid matrix in which, on the other hand, could avoid separation process or affect (probably decreasing) their absorption during digestion.

Ionic liquids and deep eutectic solvents as sustainable alternatives for efficient extraction of phenolic compounds from mate leaves.

Mate leaves are highly appreciated in south and central America as food ingredient for tea preparation. Their nutritional importance, due to their high content of polyphenols and other nutraceuticals, has been drawing attention worldwide, especially to produce extracts and biopharmaceuticals. However, the extraction of such nutraceuticals using conventional processes/solvents might impact their profile/concentration. Ionic liquids (ILs) and deep eutectic solvents (DES) have been recognized as green solvents, and more recently the naturally-derived have stood out. In this work, we investigated the use of bioethanol, cholinium chloride ([Ch]Cl), Ch-based DES and less expensive protic ILs derived from acetic acid, in aqueous systems at different concentrations, as potential sustainable alternatives over conventional solvents and more expensive aprotic ILs for the extraction of polyphenols from mate leaves. Simply adding the [Ch]Cl in aqueous-ethanolic mixtures at 50% improved extraction efficiency (∼35 mg/g) in comparison to conventional solvents (∼7-29 mg/g). However, IL (∼41-66 mg/g) and DES (∼47-55 mg/g) systems presented better performance, being the former presenting the best results at 75% (∼66 mg/g). The extraction yield was also related to water concentration, which is interesting to reduce viscosity and IL/DES cost for a more cost-efficient extraction and was also supported by results obtained using COSMO-SAC. Therefore, the low-cost protic IL and DES are promising sustainable solvent alternatives over conventional solvents/ILs for extraction of polyphenols from mate leaves.

Enzymatic Degumming of Rice Bran Oil Using Different Commercial Phospholipases and Their Cocktails.

Rice bran oil is a highly nutritious vegetable oil, as it is rich in tocols and γ-oryzanol. Degumming is the first step in the vegetable oil refining process, and its main objective is the removal of phospholipids or gums. In the present study, enzymatic degumming trials were performed on crude rice bran oil using the phospholipases PLA1, Purifine® PLC, their mixture (PLA1/PLC), and a cocktail known as Purifine® 3G. Enzymatic degumming applying 50 mg/kg of PLA1 for 120 min resulted in a residual phosphorus content of 10.4 mg/kg and an absolute free fatty acid increase of 0.30%. Enzymatic degumming applying 300 mg/kg of Purifine® PLC for 120 min at 60 °C resulted in a residual phosphorus content of 67 mg/kg and an absolute diacylglycerol increase of 0.41%. The mixture of phospholipases and the cocktail presented approximately 5 mg/kg of residual phosphorus content after the reaction times. For all degumming processes, the preservation of minor components such as tocols and γ-oryzanol were observed. These results indicate that the use of enzyme mixtures or their cocktails to attain low phosphorus content and high diacylglycerol/free fatty acid conversion during enzymatic degumming is a viable alternative.

Subacute toxicity assessment of biobased ionic liquids in rats.

Ionic liquids (ILs) derived from compounds obtained from natural sources, such as fatty acids (FAs) have attracted the interest of the scientific and industrial communities because of their sustainable appeal and possible low toxic effects or nontoxicity. These aspects open new perspective of applications in other fields, which demands a better comprehension of their toxicity. This work evaluated the subacute toxicity of bis(2-hydroxyethyl)ammonium carboxylates in Wistar rats, considering the alkyl chain length of FAs (capric and oleic acids), and the concentration (0.16%, 1.6% or 3.2%, wIL/wOil) of ILs added in diets. The blood serum of the rats was evaluated in relation to total cholesterol, triglycerides, aspartate aminotransferase (AST), alanine aminotransferase (ALT), alkaline phosphatase (ALP) and γ-glutamyl transferase. Lipid peroxidation was determined in plasma, liver and kidney tissues by determining the level of thiobarbituric acid reactive substances. Histological analyses of the liver and kidney tissues were performed in order to evaluate morphological changes. No signal of toxicity was observed according to lipid peroxidation. Triglycerides increased with the increasing of the concentration and alkyl chain length of the IL, but no difference in serum level of lipid peroxidation was observed. This behavior may be attributed to the amphiphilic nature of FAs based ILs, which might facilitate lipid digestion. However, more studies are necessary in order to understand such behavior. Therefore, the synthesis of ILs from FAs, has been evaluated as a strategy to produce compounds with low or without toxicity for the agro-food, pharmaceutical or cosmetic industries.

Phase equilibrium and physical properties of biobased ionic liquid mixtures.

Protic ionic liquid crystals (PILCs) obtained from natural sources are promising compounds due to their peculiar properties and sustainable appeal. However, obtaining PILCs with higher thermal and mechanical stabilities for product and process design is in demand and studies on such approaches using this new IL generation are still scarce. In this context, this work discloses an alternative way for tuning the physicochemical properties of ILCs by mixing PILs. New binary mixtures of PILs derived from fatty acids and 2-hydroxy ethylamines have been synthesized here and investigated through the characterization of the solid-solid-[liquid crystal]-liquid thermodynamic equilibrium and their rheological and critical micellar concentration profiles. The mixtures presented a marked nonideal melting profile with the formation of solid solutions. This work revealed an improvement of the PILCs' properties based on a significant increase in the ILC temperature domain and the obtainment of more stable mesophases at high temperatures when compared to pure PILs. In addition, mixtures of PILs also showed significant changes in their non-Newtonian and viscosity profile up to 100 s-1, as well as mechanical stability over a wide temperature range. The enhancement of the physicochemical properties of PILs here disclosed by such an approach leads to more new possibilities of their industrial application at high temperatures.

Phase Behavior and Physical Properties of New Biobased Ionic Liquid Crystals.

Protic ionic liquids (PILs) have emerged as promising compounds and attracted the interest of the industry and the academy community, due to their easy preparation and unique properties. In the context of green chemistry, the use of biocompounds, such as fatty acids, for their synthesis could disclose a possible alternative way to produce ILs with a low or nontoxic effect and, consequently, expanding their applicability in biobased processes or in the development of bioproducts. This work addressed efforts to a better comprehension of the complex solid-[liquid crystal]-liquid thermodynamic equilibrium of 20 new PILs synthesized by using fatty acids commonly found in vegetable oils, as well as their rheological profile and self-assembling ability. The work revealed that their phase equilibrium and physical properties are significantly impacted by the structure of the ions used for their synthesis. The use of unsaturated fatty acids and bis(2-hydroxyethyl)ammonium for the synthesis of these biobased ILs led to a drastic decreasing of their melting temperatures. Also, the longest alkyl chain fatty acids promoted higher self-assembling and more stable mesophases. Besides their sustainable appeal, the marked high viscosity, non-Newtonian profile, and very low critical micellar concentration values of the PIL crystals here disclosed make them interesting renewable compounds with potential applications as emulsifiers, stabilizers, thickeners, or biolubricants.

Solid-liquid equilibria of binary mixtures of fluorinated ionic liquids.

Within ionic liquids, fluorinated ionic liquids (FILs) present unique physico-chemical properties and potential applications in several fields. However, the melting point of these neoteric compounds is usually higher due to the presence of fluorine atoms. This drawback may be resolved by, for instance, mixing different FILs to create eutectic mixtures. In this work, binary mixtures of fluoro-containing and fluorinated ionic liquids were considered with the aim of decreasing their melting temperatures as well as understanding and characterizing these mixtures and their phase transitions. Five FILs were selected, allowing the investigation of four binary mixtures, each of them with a common ion. Their solid-liquid and solid-solid equilibria were studied by differential scanning calorimetry and the non-ideality of the mixtures was investigated. Overall, a variety of solid-liquid equilibria with systems exhibiting eutectic behavior, polymorphs with solid-solid phase transitions, and the formation of intermediate compounds and solid solutions were surprisingly found. In addition to these intriguing behaviours, novel FILs with lower melting temperatures were obtained by the formation of binary systems, thus enlarging the application range of FILs at lower temperatures.

The Crystal-T algorithm: a new approach to calculate the SLE of lipidic mixtures presenting solid solutions.

Lipidic mixtures present a particular phase change profile highly affected by their unique crystalline structure. However, classical solid-liquid equilibrium (SLE) thermodynamic modeling approaches, which assume the solid phase to be a pure component, sometimes fail in the correct description of the phase behavior. In addition, their inability increases with the complexity of the system. To overcome some of these problems, this study describes a new procedure to depict the SLE of fatty binary mixtures presenting solid solutions, namely the "Crystal-T algorithm". Considering the non-ideality of both liquid and solid phases, this algorithm is aimed at the determination of the temperature in which the first and last crystal of the mixture melts. The evaluation is focused on experimental data measured and reported in this work for systems composed of triacylglycerols and fatty alcohols. The liquidus and solidus lines of the SLE phase diagrams were described by using excess Gibbs energy based equations, and the group contribution UNIFAC model for the calculation of the activity coefficients of both liquid and solid phases. Very low deviations of theoretical and experimental data evidenced the strength of the algorithm, contributing to the enlargement of the scope of the SLE modeling.