The application of nanostructured lipid carrier (NLC) in UV filters encapsulation was found to enhance its safe use. In this work, kenaf seed oil-NLC (KSO-NLC) co-loaded with UV filters encapsulated was used as an active ingredient in α-tocopherol cream to develop a photoprotective prototype. It was then subjected to further analysis to determine the physical properties storage stability and cytotoxicity. The ratio of KSO-NLC to α-tocopherol cream was optimised based on the SPF value using UV transmittance analyser. The physical properties of the samples were analysed and the amount of α-tocopherol was quantified by ultra-high performance liquid chromatography (UHPLC). The optimised sample was then evaluated for in vitro antioxidant activities using DPPH and ABTS assays. Meanwhile, in vitro cytotoxicity was studied on normal human dermal fibroblast (NHDF) cell line using MTT and CCK-8 assays. The sample produced by KSO-NLC to α-tocopherol cream in ratio 1:2 (N3) showed SPF value > 50. Besides, the samples showed microbial stability and sustainable α-tocopherol content upon 12 weeks of storage. The cytotoxicity evaluation of N3 and α-tocopherol cream (N5) showed > 100 % cell proliferation indicated there is no side effect on the cell growth, yet it triggered the cell proliferation with the presence of bioactive compounds. Overall, the results herein gathered are very promising towards the development of new green cosmetic formulations with the utilisation of KSO-NLC and palm-based α-tocopherol cream.

Epoxidized methyl esters (EMO) with their high oxirane ring reactivity, acts as a raw material in the synthesis of various industrial chemicals including polymers, stabilizers, plasticizers, glycols, polyols, carbonyl compounds, biolubricants etc. EMO has been generally quantified by the gas chromatography (GC) and high performance liquid chromatography (HPLC) techniques. Taking into the account of the limitations of these techniques, two qHNMR based equations have been proposed for the quantification of EMO in the mixture of EMO and methyl esters (MO). The validity of the proposed method was determined using standard mixtures of MO and EMO having different molar concentrations. The developed equations have been applied on the samples of EMO prepared from oleic acid in two step process viz., esterification followed by epoxidation. The qHNMR based EMO quantification showed acceptable agreement with the results obtained from HPLC analysis.

Enriching foods with long-chain (LC) n-3 polyunsaturated fatty acids (PUFAs) requires a delivery emulsion system, which is both thermodynamically and oxidatively stable. The antioxidant and stabilizing properties of three types of polysaccharide extracts from brown algae Saccharina latissima with mixed composition of polysaccharides (SA: 98% Sodium alginate, SF: 90% alginate and 9% fucoidan, SL: 14.5% fucoidan, 9.5% laminarin and co-extracted non-polysaccharides) were evaluated. SA, SF, SL and REF (added commercial sodium alginate) all showed in vitro ferrous ion chelating ability in the order: SA(99%)>SL(78%)>REF(31%)>SF(16%). The difference in antioxidant activity between SA, REF and SF appeared related to structural differences of alginate (M/G ratio). A storage trial was conducted using 70% (w/w) fish oil-in-water delivery emulsions added sodium caseinate (NaCas) (0.23 wt%) as emulsifier in combination with SA, SF, SL or commercial NaAlg (REF) in different concentrations (C1=0.1, C2=0.2 C3=0.3 and C4=0.4 wt%). A control with only NaCas were included (CON). The physical (e.g. creaming and droplet-size distribution) and oxidative (peroxide value and volatiles) stability of the emulsions, were evaluated (12 days, dark at 20˚C). Acceptable physical stability (creaming index, CI) was found for, REF (all concentrations), SF=0.2 wt% (C2), SL and SA=0.3 wt% (C3) and 0.4 wt% (C4). In general, the oxidative stability decreased by adding REF, SA and SF (except for REF at C1), as prooxidant activity was observed. However, SA showed antioxidant activity against formation of 2-ethylfuran. SL showed antioxidant activity in decreasing formation of volatile compounds in emulsions when added in concentrations above 0.2 wt%.

Consumers are becoming aware of the relevance of eating low levels of trans and saturated fats in processed foods. In addition, many countries are adopting regulatory measures on the use of these ingredients. For this reason, the exploration of new technologies capable of producing structures that trap liquid oil (composed of unsaturated fatty acids, considered healthier) has been widely investigated in order to replace saturated and trans fats in food products. One of the most promising technologies is the so-called oleogels, which present a great challenge to mimic sensory attributes related to the texture of processed foods based on saturated fats. In this review, we discuss how the different approaches used in the production of oleogels, direct or indirect methods, as well as compositional variables, such as oleogelators and mixing ratio, can directly influence the mechanical properties of these structures. An overview of the parameters that can interfere with these properties contributes to a better understanding of the building of the oleogels and their possible applications.

Monoacylglycerol (MAG) and diacylglycerol (DAG) are two natural components found in most edible oils and fats. Conventional synthesis of MAG and DAG is usually conducted by glycerolysis of triacylglycerol (TAG) at high temperatures (above 200 °C) in the presence of an alkaline catalyst. In this work, the synthesis of MAG and DAG using enzymatic glycerolysis of olive oil was investigated using Tween 80 as surfactant, n-butanol as co-surfactant and the novel lipase in free/liquid formulation Lipozyme TL 100L as catalyst. Experimental design was used to evaluate the effect of enzyme load and reaction temperature on the feedstock conversion. Enzyme load and system temperature were significant variables in the statistical design and the best condition was found at 35 °C, 7.5 vol% of Lipozyme TL 100 and glycerol to oil molar ratio of 2:1 with conversion of TAG at approximately 98 % after 2 h of process. A mathematical model based on the Ping-Pong Bi-Bi mechanism was used to describe the reaction kinetics. The model adequately described the behavior of the system and can be a useful tool for the design of reactors in larger scales.

Glycerol monooleate (GMO)-stabilized liquid water-in-vegetable oil (W/VO) emulsions are difficult to stabilize due to the desorption of GMO from the W-VO interface towards the oil phase. This work improved the stability of GMO-stabilized liquid 20 wt% water-in-canola oil (W/CO) emulsion by modifying the dispersed aqueous phase composition with hydrogen bond-forming agents. As a control, 20 wt% water-in-mineral oil (W/MO) emulsion was also utilized. Different concentrations of hydrogen bond-forming agents (citric acid (CA), ascorbic acid (AA), low methoxyl pectin (LMP)) with and without salts (sodium chloride (S) or calcium chloride (Ca)) was added to the aqueous phase before emulsification, which enhanced emulsifier binding to the water-oil interface. The emulsions were characterized by phase separation, stability against accelerated gravitation, microstructure and rheology. W/CO emulsion without any aqueous phase additive destabilized instantly, whereas W/MO emulsion stayed stable. The addition of hydrogen bond-forming agents and salts significantly improved emulsion stability. LMP, with many hydrogen bond-forming groups, was able to provide the highest emulsion stability after 7 days in both oils compared to AA, CA and their mixtures with S. Emulsions with both oils formed weak gels with viscous and elastic characteristics due to the formation of an extensive network of water droplet aggregates. Overall, the hydrogen bond-forming agents interacted with GMO at the interface, thereby improving their presence at the water droplet surface, allowing significantly improved stability of GMO-stabilized liquid W/CO emulsions. The knowledge developed in this research can be useful in applying GMO in stabilizing liquid water-in-oil emulsion without using any crystal network.

Current research on wax-based oleogels indicates wax esters to be the key component in many natural waxes. This necessitates understanding the properties of pure wax esters to unravel the gelling mechanism in wax-based oleogels. Therefore, wax esters with different carbon numbers and symmetries were studied and characterized regarding their thermal (DSC) and viscoelastic (oscillatory rheology) behavior. Pure wax esters and binary mixtures of wax esters were studied as such and in oleogels formed in combination with medium chained triglyceride oil at WE-inclusion levels of 10 % (w/w). Interpretation of the observations was based on detailed analysis of pre-existing data on crystallographic (SAXS) and thermal properties. It is found that all observations concerning single pure WE’s obey a systematic framework linking molecular make up, crystal structure and behavior. The study on the gelling of four different binary mixtures of wax esters revealed that substantial chain length differences do have the expected consequence of separate crystallization. Mixtures of wax esters with only limited chain length difference reconfirmed earlier speculations on mixing and crystal structure. Applying mixtures of wax esters only differing in their position of the ester bond indicated ideal mixing behavior in the solid phase of the gels. Actually, the data revealed that despite these expected observations in both systems, additional thermal events occur at specific mixing ratios. Their supposed relation to compound formation certainly needs further confirmation. Rheological analysis confirmed that sequential crystallization results in highest firmness values for the systems studied.

The crystallization behavior of mango kernel fat (MKF) at 25 °C with and without the application of high-intensity ultrasound (HIU) (20 kHz, 125 W) was studied as a function of ultrasound amplitude level (30%, 50% and 70% of the maximum amplitude of 180 μm). The irradiation time was fixed at 5 s. It was found that HIU induced MKF crystallization. The crystallization induction time decreased with a decrease in crystal size and an increase in the number of crystals as the HIU amplitude increased. The β′→β transformation was also accelerated with HIU application. This work has shown that there is a great potential for the use of HIU in the food industry to achieve a shorter and more controllable crystallization process. In particular, HIU could be used as an efficient tool for controlling the polymorphic transition of fats.

Cannabinoids biosynthesis in phytoplankton has attracted much attention due to the rapid development of genetic tools and the optimization of genetic transformation methods in microalgae. To monitor the biosynthesis process, proper sample preparation and practical instrumental methods are needed to measure the various precursors, intermediates, cannabinoids, and their degradation products. The objective of this study was to develop a sample preparation procedure for the quantification of olivetolic acid (OA), cannabigerolic acid (CBGA), cannabidiolic acid (CBDA), tetrahydrocannabinolic acid (THCA), olivetol (OL), cannabidiol (CBD), and tetrahydrocannabinol (THC) using single-quadrupole gas chromatography-mass spectrometry (GC-MS). Isochrysis galbana was used as the model matrix. After methanol extraction, samples were purified using solid phase extraction (SPE), silylated with N-methyl-N-(trimethylsilyl)trifluoroacetamide, and analyzed using GC-MS in electron ionization mode. A strong anion-exchange SPE efficiently recovered OA, CBGA, CBDA, and THCA. A graphitized carbon black SPE was necessary to purify OL, CBD, and THC. Both columns removed amino acids, sugars, polyols, and pigments from the algae extract and prepared samples that are suitable for silylation and GC-MS analysis. The total protocol, including solvent extraction, SPE, silylation, and GC-MS analysis, was validated in accordance with the ICH guidelines. Performance characteristics of our method are superior to existing protocols with similar complexity in the literature.

Oleogelation offers the possibility to reduce the saturated fatty acid (SAFA) content while maintaining the desired organoleptic properties. Hereby, SAFA are replaced by other structurants which can create a three-dimensional network that immobilizes the liquid oil. Depending on the type of structurants, different structuring routes are identified. The use of monoglycerides (MAGs) as structurants is a promising approach thanks to their great self-assembling properties. However, implementation into the food industry is still hampered due to insufficient characterization. This research includes a multiscale analysis of two dynamically produced MAG-based oleogels as a function of the storage time (up to 8 weeks). Slight differences in the production process resulted in differences in techno-functional properties between the MAG-based oleogels MO1 and MO2. MO1 consisted of larger crystals, which resulted in a lower rigidity, lower stability and lower oil binding capacity compared to the other oleogel (MO2). On the nanoscale, it was found that the crystal nanoplatelets (CNPs) of MO1 contained a higher number of lamellae compared to the MO2. Additionally, the results obtained with ultra-small angle X-ray scattering indicated a larger equivalent diameter for the CNPs of MO1. As a function of the storage time, both oleogels did not show major structural changes up to 8 weeks of storage.

Oleogelation is an efficient way to structure oil and reduce saturated fatty acids of lipid products. Multi-component gels are of particularly interest attributed to the ability to tune gel properties by alteration of the component proportions. In this study, monoacylglycerol (MAG) and diacylglycerol (DAG) are used as gelator mixture and the influence of the ratio of these two crystalline particles on the characteristics of oleogels was investigated. The crystallization and melting behavior, solid fat content (SFC), crystal morphology, polymorphism and mechanical properties of the oleogels were characterized. The oleogels with higher gelator level displayed higher oil binding ability and shorter crystal formation time. The oleogels with higher MAG ratio exhibited more blade-like crystals, and the mixed oleogels with MAG: DAG of 3:7 and 5:5 showed altered crystal morphology with finer crystal size and reduced crystallization enthalpies possibly due to the increased nucleation seeds promoted by MAG. The oleogels with high MAG level showed lower equilibrium SFC during isothermal crystallization but faster crystallization rate, higher hardness and elasticity. Therefore, by changing the ratio of DAG with MAG, the crystallization profile and rheological properties of oleogels can be tailored and used as traditional solid fat substitutes in lipid-based products.

The first part of this study showed that the triglyceride composition of purified oils has little impact on sterol/sterol ester oleogels. Hence, changes in the gels’ properties observed in previous studies must arise from minor polar components, particularly by changing the interactions within the fibrillar network. Selected molecules (oleic acid, tocopheryl acetate, monoglycerides, and water) were added to three purified oils to unravel the individual contributions introduced by different functional groups. While all additives retarded the molecular self-assembly of sitosterol with oryzanol, distinct effects were found for gel hardness, transition temperatures and enthalpies, strain sweep responses, and microstructure. It was discovered that the maximum storage modulus in the linear viscoelastic region does not necessarily relate to the gels’ compression firmness. In samples comprising oleic acid and tocopheryl acetate, discrete interaction mechanisms with the scaffolding elements were suggested since results between the two additives developed differently and were dose-dependent. A network supporting effect was suggested at low concentrations, in line with previous results for oils comprising low levels of thermal deterioration products. The microstructure of oleogels was considerably modified with additives. Unfortunately, effects are difficult to quantify due to the packed surface observed in AFM micrographs.

To date no single gas chromatographic method can simultaneously measure all fatty acids (FA), including trans FA (TFA), that are contained in dairy products, partially hydrogenated oils (PHO), and refined vegetable oils. Using 100% poly(biscyanopropyl siloxane) capillary columns, ruminant and dairy fats are preferentially analyzed by applying temperature programs that separate short chain FA, but not trans-18:3 from 20:1. Refined vegetable oils and PHO are preferentially analyzed by applying isothermal elutions that provide quantification of all 18 carbon TFA including trans-18:3 FA, but not of all short chain FA. In this short communication, we propose a temperature program method capable of simultaneously measuring short chain FA and all 18 carbon TFA including trans-18:3 by applying a negative temperature gradient after the elution of trans-18:1. A simplified version of the method is also described for equipment not able to perform negative temperature gradients.

The role of solvent composition, in particular, minor oil components on sterol/sterol ester oleogels, has been studied recently [1]. Reportedly, deterioration products hamper network formation and modify the gel’s macroscopic properties, probably due to alterations of the scaffolding elements’ interactions. However, the role of the FA composition of TAGs has not yet been addressed. In this study, minor oil components of three vegetable oils with varying degrees of unsaturation (iodine values) were removed, and the oils were chemically and physically characterized before and after the treatment. Consequently, β sitostero/γ-oryzanol oleogels were produced, and the gel-sol (DSC) and sol-gel (rheology) transitions were monitored. Moreover, large and small deformation tests were performed, and the results were linked to oil parameters. In contrast to minor oil components, the FA composition has little impact on oleogel properties. The decline in gel hardness with IV is possibly linked to a lower solvent viscosity. However, a considerable drop in gel-sol transition temperature was observed with increasing IV indicating fewer elements of scaffolding. That was linked to the rapid formation of primary oxidation products in purified flaxseed oil during oleogel preparation, impairing tube formation. Similar to previous results on deterioration products, these minor components seem to aid network strength at low concentrations resulting in similar transition enthalpies and G’. That might be due to shifted network interactions in the presence of molecular species with functional groups. In the second part of this study, these modified interactions in the presence of selected minor components will be discussed.

Oleosins are mandatory to avoid coalescence of oil bodies (OBs), so commercial proteases are used to efficiently demulsify OBs into food oil. However, the commercial proteases and pH regulators (acid and alkali) greatly restrict this method in industry. In this study, aspartic endopeptidases, subtilisin-like proteases, metalloendopeptidase, and serine carboxypeptidases were identified in isolated sesame OBs by liquid chromatography tandem mass spectrometry (LC–MS/MS). Tricine–sodium dodecyl sulfate–polyacrylamide gel electrophoresis and protease inhibitor assay revealed that aspartic endopeptidases exerted high activity against oleosins in a pH range of 3−6 and a temperature range of 40−70 °C, while subtilisin-like proteases exhibited sharp optimum at pH 5. Metalloendopeptidase contributed to the low activity against oleosins at pH 7−9. Trichloroacetic acid–nitrogen soluble index and free amino acid analyses quantitatively revealed that the activity of serine carboxypeptidases was high at pH 3−5, and optimal at pH 4; the combined activity of aspartic endopeptidases and subtilisin-like proteases was optimal at pH 5. By incubating the isolated sesame OBs at pH 5 and 60 °C for 2 h, approximately 97% of total lipids were recovered as free oil. At last, LC−MS/MS analysis gave deep insight into the intrinsic proteins of sesame OBs: three kinds of oleosins with molecular weights around 17 kDa, and four kinds around 15 kDa; besides 27 kDa caleosin, four kinds of oil body-associated proteins and one kind of peroxygenase-like protein also around 27 kDa; in addition to 39 kDa steroleosin, 11-beta-hydroxysteroid dehydrogenase-like 6 also around 39 kDa.

The utilization and popularization of biodiesel are always limited by its poor cold flow properties. Both bio-based alcohol and diesel from direct coal liquefaction (DDCL) has potential to enhance the cold flow properties of biodiesel. Ternary blends of waste cooking oil biodiesel (BWCO) with DDCL and bio-based ethanol (ET) or 1-butanol (BT) for improving the cold flow properties of biodiesel. The pour point (PP), cold filter plugging point (CFPP), and cloud point (CP) of BWCO-ET, BWCO-BT, and BWCO-DDCL binary blends, and BWCO-ET-DDCL and BWCO-BT-DDCL ternary blends were comparatively assessed. Ternary phase diagrams were also applied into analyze the blending effect of the three components on the cold flow properties of biodiesel. Results showed that both DDCL, ET and BT can remarkably enhance the cold flow properties of BWCO. BT and DDCL presented a better synergistic depression effect. For ternary blends in 20:10:70 blending ratio, BWCO-BT-DDCL exhibited the lowest PP, CFPP, and CP of −23 °C, −19 °C, and −17 °C, respectively. The crystallization behavior and crystal morphology of blended fuels are also observed via a polarizing optical microscope, and find that DDCL together with BT in biodiesel can effectively retard the aggregation of large crystals and inhibit crystals growth.

The upgrading of oleyl alcohol synthesis via methyl oleate reduction using NaBH4 without H2 supply was investigated. It was possible to synthesize selectively the valuable unsaturated fatty alcohol with high yields. Non-catalytic and catalytic experiments were developed trying to improve the low final oleyl alcohol yield previously obtained. The effect of reaction temperature, methyl oleate/NaBH4 molar ratio and properties of different catalysts on final oleyl alcohol yield was analyzed. Thus, alumina-supported metal (M) catalysts (M = Fe, Ce, Mo) were synthesized by impregnation at incipient wetness. The M/Al2O3 catalysts were characterized in their chemical, textural, structural and acid-base properties using ICP, N2 physisorption, XRD and NH3 and CO2 TPD. During non-catalytic methyl oleate reduction final methyl oleate conversion and oleyl alcohol yield of 94% were obtained using a methyl oleate/NaBH4 molar ratio of 0.11 at 333 K. Catalytic activity of M/Al2O3 solids did not correlate with basic site number but increased as acid site number and ionic potential of M cations increase. This suggests that cations with high acid site number and polarizing power are the ones that promote the polarization of the ester C=O and anion [BH4]- bonds favoring de methyl oleate conversion. In addition, the reaction mechanism for fatty acid methyl ester reduction was investigated from a theoretical approach using Density Functional Theory method at B3LYP/6-31++G(d,p) computational level. Results obtained during theoretical calculations confirmed that the formation of reducing alcoxyborohydride species is energetically favored and allowed to understand the events at microscopic level involved in the reaction mechanism.

Plant-based high internal phase oil-in-water emulsions (HIPEs) are promising fat replacers. However, producing stable HIPES with improved viscoelastic properties is a challenge for the food industry. Conjugation of plant proteins, such as lupin protein isolate, with phenolic compounds, such as proanthocyanidins from grape seed extract, associated (or not) with moderate heat treatment arise as potential methods to tune the surface properties of proteins and, consequently, the droplet-droplet interactions that drive the viscoelastic properties of HIPEs. In this way, unheated (UHC) and heated (85°C, 15 min) (HC) lupin protein (LPI)-grape seed extract (GSE) conjugates were produced and used to stabilize high internal phase oil-in-water emulsions. Evaluation of stability by Turbiscan and oil loss by centrifugation over 56 days of storage did not reflect the kinetic stability of HIPEs against process conditions. Under shearing, UHC-stabilized emulsions at high GSE concentrations showed oil release, whereas all HC-stabilized HIPEs released oil. However, the increase in GSE concentration and heat treatment improved the viscosity and storage modulus (G’) of HIPEs, possibly due to the droplet-droplet interaction originating from hydrophilic and hydrophobic interactions in UHC and HC-stabilized HIPEs, respectively. This pivotal study confirmed that conjugation of a plant protein with GSE and heat treatment could improve the viscoelastic properties of high internal phase oil-in-water emulsions and produce HIPEs with superior texture (higher G’).