Resveratrol-loaded octenyl succinic anhydride modified starch emulsions and hydroxypropyl methylcellulose (HPMC) microparticles: Cytotoxicity and antioxidant bioactivity assessment after in vitro digestion.

Hydroxypropyl methylcellulose (HPMC)-based microparticles and modified starch emulsions (OSA-MS) were loaded with resveratrol and characterized regarding their physicochemical and thermal properties. Both delivery systems were subject to an in vitro gastrointestinal digestion to assess the bioaccessibility of resveratrol. In addition, cell-based studies were conducted after in vitro digestion and cytotoxicity and oxidative stress were assessed. HPMC-based microparticles displayed higher average sizes (d) and lower polydispersity index (PDI) (d = 948 nm, PDI < 0.2) when compared to OSA-MS-based emulsions (d = 217 nm, PDI < 0.3). Both proved to protect resveratrol under digestive conditions, leading to an increase in bioaccessibility. Resveratrol-loaded HPMC-microparticles showed a higher bioaccessibility (56.7 %) than resveratrol-loaded emulsions (19.7 %). Digested samples were tested in differentiated co-cultures of Caco-2 and HT29-MTX, aiming at assessing cytotoxicity and oxidative stress, and a lack of cytotoxicity was observed for all samples. Results displayed an increasing antioxidant activity, with 1.6-fold and 1.4-fold increases over the antioxidant activity of free resveratrol, for HPMC-microparticles and OSA-MS nanoemulsions, respectively. Our results offer insight into physiological relevancy due to assessment post-digestion and highlight the protection that the use of micro-nano delivery systems can confer to resveratrol and their potential to be used as functional food ingredients capable of providing antioxidant benefits upon consumption.

Oleogels and Organogels: A Promising Tool for New Functionalities.

Growing awareness concerning human health and sustainability has been continually driving the need to change consumers' habits and develop new bio-based and environmentally friendly materials that could be used in new product formulations [...].

Gelation Behavior and Stability of Multicomponent Sterol-Based Oleogels.

Novel fat mimetic materials, such as oleogels, are advancing the personalization of healthier food products and can be developed from low molecular weight compounds such as γ-oryzanol and ß-sitosterol. Following molecular assembly, the formation of a tubular system ensues, which seems to be influenced by elements such as the oleogelators' concentration and ratio, cooling rates, and storage periods. Sterol-based oleogels were formulated under distinct environmental conditions, and a comprehensive study aimed to assess the effects of the mentioned factors on oleogel formation and stability, through visual observation and by using techniques such as small-angle X-ray scattering, X-ray diffraction, confocal Raman spectroscopy, rheology, and polarized microscopy. The long, rod-like conformations, identified by small-angle X-ray scattering, showed that different cooling rates influence oleogels' texture. Raman spectra showed that the stabilization time is associated with the interfibrillar aggregation, which occurred differently for 8 and 10 wt%, with a proven relationship between ferulic acid and the tubular formation. This report gives fundamental insight into the critical point of gelation, referring to the time scale of the molecular stabilization. Our results verify that understanding the structuring mechanisms of oleogelation is decisive for the processing and manufacturing of novel foods which integrate oleogels in their structure.

Performance of Gelatin Films Reinforced with Cloisite Na+ and Black Pepper Essential Oil Loaded Nanoemulsion.

The concern about consuming eco-friendly products has motivated research in the development of new materials. Therefore, films based on natural polymers have been used to replace traditional polymers. This study consists of a production of films based on gelatin reinforced with black pepper essential oil-loaded nanoemulsions and Cloisite Na+. The films were characterized by water vapor permeability, mechanical and thermal properties, surface contact angle, X-ray diffraction and scanning electron microscopy. It was observed that the films containing the nanoemulsion have higher permeability values and an increase in their mechanical resistance. The addition of nanoclay contributed to an increase in the surface hydrophobicity of the film and an increase in the tensile strength, at break, by about 150%. The addition of essential oil nanoemulsions led to an increase in thermal stability. The presence of clay dispersion contributed to the formation of a surface that was slightly rougher and grainier. The addition of the black pepper essential oil nanoemulsion resulted in an increase in porosity of the gelatin matrix. Through X-ray diffraction analysis, it was possible to conclude that both the polymeric gelatin matrix and the essential oils nanoemulsion are intercalated with the clay dispersion.

Oleogel-Based Systems for the Delivery of Bioactive Compounds in Foods.

Oleogels are semi-solid materials containing a large fraction of liquid oil entrapped in a network of structuring molecules. In the food industry, these formulations can be used to mimic fats and to deliver bioactive compounds. In the last decade, there has been increasing interest in these structures, not only from a scientific point of view, i.e., studying new molecules, methodologies for gelification, and new structures, but also from a technological point of view, with researchers and companies exploring these structures as a way to overcome certain challenges and/or create new and innovative products. One of the exciting applications of oleogels is the delivery of functional molecules, where the incorporation of oil-soluble functional compounds can be explored not only at the macroscale but also at micro- and nanoscales, resulting in different release behaviors and also different applications. This review presents and discusses the most recent works on the development, production, characterization, and applications of oleogels and other oleogel-based systems to deliver functional molecules in foods.

Polysaccharide-Based Multilayer Nano-Emulsions Loaded with Oregano Oil: Production, Characterization, and In Vitro Digestion Assessment.

The food industry has increased its interest in using "consumer-friendly" and natural ingredients to produce food products. In the case of emulsifiers, one of the possibilities is to use biopolymers with emulsification capacity, such as octenyl succinic anhydride modified starch, which can be used in combination with other polysaccharides, such as chitosan and carboxymethylcellulose, in order to improve the capacity to protect bioactive compounds. In this work, multilayer nano-emulsion systems loaded with oregano essential oil were produced by high energy methods and characterized. The process optimization was carried out based on the evaluation of particle size, polydispersity index, and zeta potential. Optimal conditions were achieved for one-layer nano-emulsions resulting in particle size and zeta potential of 180 nm and -42 mV, two layers (after chitosan addition) at 226 nm and 35 mV, and three layers (after carboxymethylcellulose addition) of 265 nm and -1 mV, respectively. The encapsulation efficiency of oregano essential oil within nano-emulsions was 97.1%. Stability was evaluated up to 21 days at 4 and 20 °C. The three layers nano-emulsion demonstrated to be an efficient delivery system of oregano essential oil, making 40% of the initial oregano essential oil available versus 13% obtained for oregano essential oil in oil, after exposure to simulated digestive conditions.

Graphene Oxide Increases Corneal Permeation of Ciprofloxacin Hydrochloride from Oleogels: A Study with Cocoa Butter-Based Oleogels.

In this work, oleogels of cocoa butter (CB), rice bran oil (RBO), and graphene oxide (GO) were prepared. The prepared oleogels were subjected to various characterization techniques such as bright-field microscopy, X-ray diffraction (XRD), crystallization kinetics, differential scanning calorimetry (DSC), and mechanical studies. The influence of increasing GO content on the in vitro drug release and ex vivo corneal permeation of the model drug (ciprofloxacin HCl-CPH) from the oleogels was also investigated. Bright-field micrographs showed that increment in GO content reduced the size of the globular particles of CB. XRD analysis revealed that CB was crystallized in its ß' and ß polymorphic forms in the oleogels, which was in agreement with thermal studies. The mechanical characterization demonstrated that the presence of GO improved the elastic nature and stress-bearing properties of the oleogels. Moreover, GO altered the crystallization kinetics of CB in the oleogels in a composition-dependent manner. The in vitro release of CPH from the oleogels occurred through either Fickian diffusion or fat network relaxation or a combination thereof. Furthermore, the inclusion of GO enhanced the ex vivo permeation of CPH molecules across the caprine cornea. Hence, we concluded that the prepared oleogels could be explored as potential delivery systems for ophthalmic applications.

Green synthesis of lignin nano- and micro-particles: Physicochemical characterization, bioactive properties and cytotoxicity assessment.

Lignin particles (LPs) have gained prominence due to their biodegradability and bioactive properties. LP production at nano and micro scale produced from organosolv lignin and the understanding of size's effect on their properties is unexplored. This work aimed to produce and characterize lignin nanoparticles and microparticles using a green synthesis process, based on ethanol-solubilized lignin and water. Spherical shape LPs, with a mean size of 75 nm and 215 nm and with a low polydispersity were produced, as confirmed by transmission electron microscopy and dynamic light scattering. LPs thermal stability improved over raw lignin, and the chemical structure of lignin was not affected by the production method. The antimicrobial tests proved that LPs presented a bacteriostatic effect on Escherichiacoli and Salmonella enterica. Regarding the antioxidant potential, LPs had a good antioxidant activity that increased with the reaction time and LPs concentration. LPs also presented an antioxidant effect against intracellular ROS, reducing the intracellular ROS levels significantly. Furthermore, the LPs showed a low cytotoxic effect in Caco-2 cell line. These results showed that LPs at different scales (nano and micro) present biological properties and are safe to be used in different high value industrial sectors, such as biomedical, pharmaceutical and food.

Characterization of Enriched Meat-Based Pâté Manufactured with Oleogels as Fat Substitutes.

Nowadays, one of the strongest factors affecting consumers' choice at the moment of purchasing food products is their nutritional features. The population is increasingly aware of the diet-health relationship and they are opting for a healthy lifestyle. Concerns with the increasing number of heart-related diseases, which are associated to the consumption of fats, are placing the functional food market in a relevant growth position. Considering that, our goal was to develop, under semi-industrial processing conditions, a healthy meat-based spreadable product (pâté) with reduced fat content through replacement of pork fat by healthier structured oil. Beeswax was used to develop an edible oleogel based on linseed oil with a high content of linolenic acid. A decrease of the hardness and adhesivity was verified for pâtés with oleogel incorporation. Linseed oil inclusion was the main factor leading to an increase of polyunsaturated fatty acids (PUFA) content in pâté samples. A decrease up to 90% in the n-6/n-3 (omega-6/omega-3) ratio can signify a better nutritional value of the obtained pâté samples, which can result in a possible upsurge in omega-3 bioavailability through digestion of these pâtés. This could be an interesting option for the consumption of n-3 polyunsaturated fatty acids, targeting, for example, the reduction of cardiovascular diseases.

Evaluation of linseed oil oleogels to partially replace pork backfat in fermented sausages.

BACKGROUND: Nowadays, fat replacement in meat products is a matter of concern in the meat industry. The objective of this study was to evaluate the replacement of pork backfat with two oleogels of linseed in dry-cured sausages. RESULTS: Five batches of dry-cured sausages were prepared with two oleogels, a mixture of γ-oryzanol and ß-sitosterol (SO) and beeswax (B), at two levels of replacement (20% and 40%) (SO-20, SO-40, B-20, and B-40, respectively) and a control batch. The fatty acid profile improved in terms of nutrition: the polyunsaturated fatty acid / saturated fatty acid (PUFA/SFA) and n-6/n-3 ratio was about 1.41 and 0.93 for the higher levels of replacement, SO-40 and B-40, respectively. Quality parameters such as pH and color also changed with the inclusion of oleogels, resulting in changes in the sensory quality. CONCLUSION: Oleogels based on linseed enabled the replacement of pork backfat in fermented sausages. Depending on the level of fat substitution, such oleogels could replace fat in dry-cured sausages at the industrial level. © 2019 Society of Chemical Industry.

Strategy towards Replacing Pork Backfat with a Linseed Oleogel in Frankfurter Sausages and its Evaluation on Physicochemical, Nutritional, and Sensory Characteristics.

Different health institutions from western countries ha-ve recommended a diet higher in polyunsaturated fats, especially of the n-3 family. However, this is not a trivial task, especially for meat-processing sectors. The objective of this work was to assess the influence of replacing pork backfat with linseed oleogel on the main quality parameters of frankfurters. The frankfurters were formulated by the pork backfat replacement of 0% (control), 25% (SF-25), and 50% (SF-50), using a linseed oleogel gelled with beeswax. The determination of quality parameters (pH, colour, chemical composition, and texture parameters), the fatty acid profile, and the sensory evaluation was carried out for each batch. The fatty acid profile was substantially improved, and the saturated fatty acid (SFA) content was reduced from 35.15g/100g in control sausages to 33.95 and 32.34g/100 g in SF-25 and SF-50, respectively, and more balanced ratios n-6/n-3 were achieved. In addition, the sausages with linseed oleogel also decreased the cholesterol content from 25.08 mg/100 g in control sausages to 20.12 and 17.23 mg/100 g in SF-25 and SF-50, respectively. It may therefore be concluded that these innovative meat products are a healthier alternative. However, sensory parameters should be improved in order to increase consumer acceptability, and further research is needed.

Hybrid gels: Influence of oleogel/hydrogel ratio on rheological and textural properties.

Hybrid gels can be used for controlled delivery of bioactives and for textural and rheological modification of foods. In this regard the hydrogel:oleogel ratio and gel development methodologies showed to be the aspects that influence most of their properties. The present study shows how different fractions of oleogel can influence the hydrogel matrix of an oleogel-in-hydrogel emulsified system in terms of polymorphic arrangement, microstructure, texture and rheology. The hydrogel was prepared by using an aqueous sodium alginate solution and the oleogel was prepared through the gelation of medium chain triglycerides with beeswax. Hybrid gels were prepared under constant shearing. Crystallinity was clearly changed as hydrogel and oleogel were combined. No polymorphism was observed in the X-Ray diffraction of hybrid gels, as these showed homogeneous results for all component ratios. The behaviour of samples with increasing oleogel-to-hydrogel ratio presented a decrease of both firmness and spreadability, and then, a decrease of gel adhesivity and cohesiveness. This textural response was a consequence of the disaggregated structure, stemming from the disruption of the hydrogel network, due to the inclusion of increasing amounts of oleogel. Rheological results showed that all hybrid gels presented a gel-like behaviour (G´â€¯> G´´). Oleogel's strength influenced the overall textural and rheological performance of hybrid gels. This work demonstrates the possibility of producing hybrid gels aiming to tailor texture on food systems.

Sterol-based oleogels' characterization envisioning food applications.

BACKGROUND: Phytosterols, in particular a mixture of pure γ-oryzanol and ß-sitosterol, develop a tubular system that is able to structure oil. In this study, different concentrations of a combination of γ-oryzanol and a commercial phytosterol mixture, Vitaesterol®, were used for the development of edible oil oleogels. RESULTS: Small-angle X-ray scattering (SAXS) and X-ray diffraction (XRD) were used to characterize at nano and molecular scale the aforementioned oleogels and confirm the formation of sterols-based hollow tubule structures. Increased hardness was observed with the increase of gelator content used in oleogel manufacturing. The produced oleogels showed promising features such as tailored mechanical strength and low opacity, which are important features when considering their incorporation into food products. CONCLUSION: Despite differences in gel strength, oleogels exhibited textural characteristics that make these structures suitable for incorporation in food products. The oil migration profile associated with these oleogels can provide a solution for the controlled release of lipophilic compounds as well as for the retention of oil in cooked food products. © 2018 Society of Chemical Industry.

Edible oleogels: an opportunity for fat replacement in foods.

The scientific and industrial communities have been giving great attention to the development of new bio-based materials with potential use in innovative technological applications. Among these materials are the structures with gel-like behavior that can be used in the cosmetic, pharmaceutical and food industries, aiming at controlling the physical properties of the final products. In the past ten years, words like oleogels and organogels have been increasingly used, the existing number of manuscripts and patents being proof of this tendency. In the food industry, oleogels can be used to control phase separation, and decrease the mobility and migration of the oil phase, providing solid-like properties without using high levels of saturated fatty acids as well as to be a carrier of bioactive compounds. In most cases, their main features are related to the reorganization process of gelators after an increase of the temperature, above the melting or glass transition temperature of the materials, known as the direct method, but it is also possible to develop oleogels by indirect methods, such as emulsification and the solvent exchange technique. In the direct methods, the reorganization is able to physically entrap oil leading to different physicochemical properties, the rheological behavior and texture properties being the frequently most studied ones. This review overviews the use of food grade and bio-based structurants to produce edible oleogels, aiming at fat replacement and structure-tailoring. Gelation mechanisms and oil phases used during oleogel production are discussed, as well as the current food applications and future trends for this kind of structure.

Fortified beeswax oleogels: effect of ß-carotene on the gel structure and oxidative stability.

This study was aimed at evaluating the physical conformation and oxidative stability of beeswax oleogels when fortified by the incorporation of ß-carotene (complex-beeswax oleogels). Rheological evaluation showed the presence of a strengthened structural conformation in the oleogels with ß-carotene in comparison with that in oleogels without ß-carotene; this was verified by the increase in rheological parameters. Small angle X-ray scattering data show that the lamellar crystal structure of the oleogels with ß-carotene exhibits similar d-spacings and lower radius of gyration (Rg) values for all concentrations due to the stronger oleogel network. X-ray diffraction measurements provide useful information on the crystal polymorphism type and arrangement of the internal lamellar phases of the crystals. Oil binding capacity is also affected by the incorporation of ß-carotene into the oleogel and proven to be higher for the complex-beeswax oleogels, which enhances the ability of the oleogels to retain an oil phase within their crystalline network. The oxidative profiles of the complex-beeswax oleogels were studied during storage, and beeswax at the concentrations of 4, 6, and 8% revealed higher oxidative stability than that at the concentration of 2%. In this study, the possibility of tailoring the properties of oleogels is demonstrated considering the foreseen applications of oleogels in food products, such as in texturizers, as well their capacity to deliver bioactives and thus add value to food products.

Structural and mechanical properties of organogels: Role of oil and gelator molecular structure.

This work aims at evaluating the influence of oil and gelator structure on organogels' properties through rheological measurements, polarized microscopy and small-angle X-ray scattering (SAXS). Four different food-grade gelators (glyceryl tristearate - GT; sorbitan tristearate - ST; sorbitan monostearate - SM and glyceryl monostearate - GM) were tested in medium-chain triglyceride and high oleic sunflower (MCT and LCT, respectively) oil phases. Organogels were prepared by mixing the oil phase and gelator at different concentrations (5, 10, 15, 20 and 25%) at 80°C during 30min. All organogels presented birefringence confirming the formation of a crystalline structure that changed with the increase of the gelator concentration. Through the evaluation of SAXS peaks it has been confirmed that all structures were organized as lamellas but with different d-spacing values. These particularities at micro- and nanoscale level lead to differences in rheological properties of organogels. Results showed that the oil type (i.e. medium- and long-chain triglyceride) and hydrophilic head of gelators (i.e. sorbitan versus glyceryl) exert influence on the organogels physical properties, but the presence of monostearate leads to the formation of stronger organogels. Moreover, gels produced with LCT were stronger and gelled at lower organogelator concentration than MCT.

Immobilization of bioactive compounds in Cassia grandis galactomannan-based films: Influence on physicochemical properties.

Galactomannan extracted from Cassia grandis seeds was used for the production of films containing different concentrations of the bioactive compounds lactoferrin (LF), bioactive peptides (BAPs), and phytosterols. SEM, FTIR, mechanical and thermal properties, colour, moisture content (MC), solubility, water vapour permeability (WVP), and contact angle (CA) were performed evaluating the effect of increasing concentrations of bioactive compounds on the films' physicochemical properties. The immobilization of bioactive compounds leads to films with roughness on their surface, as observed by SEM. The thermal events demonstrated that bioactive compounds avoided the establishment of more hydrogen bonds when compared to galactomannan control film; this behaviour was also confirmed by FTIR. All the studied films had a strong whiteness tendency as well as a yellowish appearance. The addition of Lf reduced MC and solubility values and leads to an increase of WVP and CA values, while the addition of BAPs and phytosterols did not changed the films solubility. The mechanical properties were affected by the addition of bioactive compounds, which improved the stiffness of the films. Galactomannan-based films from C. grandis showed to be a promising structure for the immobilization of biomolecules, pointing at a significant number of possible applications in food and pharmaceutical industries.

Lactoferrin-based nanoparticles as a vehicle for iron in food applications - Development and release profile.

This study aims at developing and characterizing bovine lactoferrin (bLf) nanoparticles as an iron carrier. bLf nanoparticles were characterized in terms of size, polydispersity index (PdI), electric charge (ζ-potential), morphology, structure and stability over time. Subsequently, iron release experiments were performed at different pH values (2.0 and 7.0) at 37°C, in order to understand the release mechanism. bLf (0.2%, w/v) nanoparticles were successfully produced by thermal gelation (75°C for 20min). bLf nanoparticles with 35mM FeCl3 showed an iron binding efficiency value of approximately 20%. The nanoparticles were stable (i.e. no significant variation of size and PdI of the nanoparticles) for 76days at 4°C and showed to be stable between 4 and 60°C and pH2 and 11. Release experiments at pH2 showed that iron release could be described by the linear superposition model (explained by Fick and relaxation phenomenon). On the contrary, the release mechanism at pH7 cannot be described by either Fick or polymer relaxation behaviour. In general, results suggested that bLf nanoparticles could be used as an iron delivery system for future food applications.

Antioxidant potential of two red seaweeds from the Brazilian coasts.

In this work, in vitro antioxidant activity of two Brazilian red seaweeds, Gracilaria birdiae and Gracilaria cornea, was characterized. The total phenolic content, the radical-scavenging activity and the antioxidant activity were determined in two solvent extracts of the algae. Liquid chromatography-mass spectrometry (LC-MS/MS) allowed identification of important antioxidant compounds. The ethanol extract of G. birdiae was found to have the highest value of total phenolic content: 1.13 mg of gallic acid equiv (GAE)/g of extract. The radical-scavenging activity of G. birdiae and G. cornea extracts has been evaluated at different extract concentrations; the IC(50) values of ethanolic extracts of G. cornea and G. birdiae were 0.77 and 0.76 mg mL(-1), respectively, while for methanolic extracts, the IC(50) values of G. cornea and G. birdiae were 0.86 and 0.76 mg mL(-1), respectively. The antioxidant activities of these two seaweeds' extracts as assessed by the ß-carotene-linoleic acid assay were equally high, achieving values of ß-carotene oxidation inhibition of up to 40%. Finally, in the methanolic extracts, LC-MS/MS allowed identification in both algae of two important antioxidants: apigenin and gallic acid.