The quest for novel vegetable oil structuring strategies has been progressing since the discovery of the deleterious impacts of trans fats. Although oleogelation using bioderived molecular gelators has been proven to be successful as an alternative to traditional hydrogenation methods, efforts are needed to meet the industrial requirements. A major constraint during the fabrication of oleogels is to achieve consistency in physical properties during scale-up. Experiments showed that gelation fails to occur when larger volumes were prepared based on the minimum gelation concentration (MGC) of gelators, determined using the smallest oil volume (1 mL), a general laboratory practice. This observation was consistent with all the molecular gelators used in this study; sorbitol dioctanoate, mannitol dioctanoate, and 12-hydroxystearic acid. To understand this behavior, a mathematical model was developed since gelator network propagation is governed by the cooling rate. The model indicates that maintenance of a minimal thermal gradient via uniform heat dissipation and gelation time is necessary to achieve homogeneous gel propagation across the vial. With these predictions, we hypothesized and confirmed that oleogels with constant surface area-to-volume ratio could result in identical gelation times and consistent physical properties (MGC, melting temperature, melting enthalpy, yield stress, solid phase content, and oil binding capacity) during scale-up.

Rice bran oil (RBO) has been a popular choice of cooking oil in several Asian countries for decades, and the interest in RBO is fast growing in Western countries due to the high levels of hearty unsaturated fats and other components beneficial to health. Further knowledge of unsaturated fatty acid content and composition in rice lines will assist in improving the quality of rice bran processing by allowing robust extraction of rice bran for oil production. The studies focused on the RBO composition of rice lines with beneficial genotypes are scarce. Accordingly, we investigated the total bran lipid content and composition of three of the most abundant, healthy, unsaturated fatty acids that freely exist in RBO: oleic, linoleic, and α-linolenic acids in nine parental lines (two male sterile lines and seven male lines) and seven hybrid rice lines, by utilizing an efficacious organic extraction to collect RBO and by developing a user-friendly reverse-phase high-performance liquid chromatography (HPLC) methodology. Our results showed that the hybrid lines had the highest oil content ( ratio = 7.2017, value = 0.0019), while the male lines had the highest levels of two of the three free unsaturated fatty acids analyzed (linoleic acid, mg and oleic acid, mg). Oil weight was negatively correlated with α-linolenic acid ( = -0.6535, value <0.0001). All three free unsaturated fatty acids were positively correlated. Our samples' natural variation in lipid content suggests that some rice lines are more suitable for oil production.

Oleogels based on sterols such as β-sitosterol blended with the sterol ester γ-oryzanol are a very interesting class of systems, but there are aspects of their formation and structure that remain elusive. It has previously been shown that a methyl group on the C30 position of the sterol-ester plays an important role in gelation. This work explored the effect that having C30 methyl groups on both the sterol and the sterol-ester had on the gelation process and subsequent gel structure. Lanosterol and saponified γ-oryzanol (which was synthesized as part of this study) were identified as materials of interest, as both feature a methyl group on the C30 position of their steroidal cores. It was observed that both sterols formed gels when blended with γ-oryzanol, and also that lanosterol gelled sunflower oil without the addition of γ-oryzanol. All of these gels were significantly weaker than that formed by β-sitosterol blended with γ-oryzanol. To explore why, molecular docking simulations along with AFM and SAXS were used to examine these gels on a broad range of length scales. The results suggest that saponified γ-oryzanol-γ-oryzanol gels have a very similar structure to that of β-sitosterol-γ-oryzanol gels. Lanosterol-γ-oryzanol gels and pure lanosterol gel, however, form with a totally different structure facilitated by the head-to-tail stacking motif exhibited by lanosterol. These results give further evidence that relatively slight changes to the molecular structure of gelators can result in significant differences in subsequent gel properties.

Vitamin E refers to a family of eight tocopherols (T) and tocotrienol (T3) isomers. Due to the unique pharmacological and anticancer activity of the individual isomers, there is a need to extract and separate the individual T3 isomers from T/T3 rich fractions of palm oil. The objective of the present study was to present a detailed protocol for the extraction of gram quantities of vitamin E isomers from a T3 rich fraction (Tocotrol™) that was obtained from palm oil, by column chromatography using a binary hexane:EtOAc (1-12%) phase system. The chemical integrity and identity of the extracted isomers was confirmed by TLC, HPLC, H-NMR, and Raman analysis. To evaluate their anticancer activity, vitamin E isomers were first entrapped into nanoemulsions and then tested against a panel of breast and pancreatic cancer cell lines. Nanoemulsions were prepared by the solvent evaporation technique. They had an average droplet size between 156-200 nm. In confirmation to what has been reported in the literature, γ-T3 and δ-T3 isomers were found to be significantly more active against tumor cells than the α-T and α-T3 isomers. The current study has demonstrated the feasibility of extracting the individual vitamin E isomers at high yields from natural sources while maintaining their chemical integrity and pharmacological activity.

The phase behavior of binary mixtures of γ-oryzanol and β-sitosterol and ternary mixtures of γ-oryzanol and β-sitosterol in sunflower oil was studied. Binary mixtures of γ-oryzanol and β-sitosterol show double-eutectic behavior. Complex phase behavior with two intermediate mixed solid phases was derived from differential scanning calorimetry (DSC) and small-angle X-ray scattering (SAXS) data, in which a compound that consists of γ-oryzanol and β-sitosterol molecules at a specific ratio can be formed. SAXS shows that the organization of γ-oryzanol and β-sitosterol in the mixed phases is different from the structure of tubules in ternary systems. Ternary mixtures including sunflower oil do not show a sudden structural transition from the compound to a tubule, but a gradual transition occurs as γ-oryzanol and β-sitosterol are diluted in edible oil. The same behavior is observed when melting binary mixtures of γ-oryzanol and β-sitosterol at higher temperatures. This indicates the feasibility of having an organogelling agent in dynamic exchange between solid and liquid phase, which is an essential feature of triglyceride networks.

The effect of specific oil surface (SOS) during pan frying of rapeseed oil on its thermal stability and antioxidant capacity (AC) was evaluated. Rapeseed oils with different oil layer heights (OLH = 0.5, 1.0, 1.5, 2.0, and 2.5 cm) were heated on an electric frying pan coated with Teflon at 180 ± 10 °C until a selected end point of 25 % total polar compounds (TPC) was reached. The changes of chemical parameters of oil samples such as peroxide value, -anisidine value, Totox value, free fatty acids, TPC and AC using the 2,2-diphenyl-1-picrylhydrazyl assay were determined. Irrespective of the applied methods, the highest changes in oil with OLH = 0.5 cm were observed. Heating in low OLH also led to the fastest time of TPC formation in rapeseed oil; the 0.5-cm layer reached 25 % TPC in a relatively short time (71.5 min) compared to the highest OLH = 2.5 cm ( = 315.1 min). The SOS and the rate of change in the heated oils decreased with increasing OLH. Crucial effects of SOS on physicochemical oil changes were observed. The present study demonstrated the protective effect of increasing the OLH on the quality of the heated rapeseed oils.

Studies on the synthesis of esters of natural origin fatty acids (oleic acid) and a branched synthetic isostearic acid derived from oleic acid with commercially available selected higher polyols in the presence of homogeneous metallic catalysts have been carried out. The effects of the synthesis temperature, molar ratio and the catalysts amount have also been studied. It was shown that higher fatty acid conversion and selectivity to tri- and tetraesters were obtained for organotin catalyst Fascat 2003, which was used as the esterification catalyst. Anti-wear test confirmed good tribological properties of the obtained esters.

Extruded cereal snacks are usually deficient in protein, mineral ingredients, valuable fatty acids. With the rise of health awareness among consumers, food manufacturers and scientists are pressed to take measures in order to develop new functional/health-beneficial foods. The aim of this work was to manufacture extruded crisps enriched with α-linolenic acid (obtained from linseed oil) and to observe whether storage of the product for the period of 6 months would cause its disqualification, primarily due to its sensory properties and secondarily due to its chemical properties. The research demonstrated that the addition of linseed oil to corn crisps at the amount of 5 % enables to obtain functional corn crisps containing over 2 g of ALA in a portion of 100 g even after 6 months of storage at room temperature. ALA-enriched crisps maintain the original sensory profile after 6 months of storage and their sensory profile is similar to the profile of crisps without the addition of linseed oil if they are packed in barrier packaging filled 100 % with argon. Therefore, they may be a healthier alternative to typical corn crisps.

Ultrasound-assisted extraction (UAE) and conventional solid-liquid extraction were applied to extract total antioxidants from two rapeseed varieties. The antioxidant capacities (AC) of winter and spring rapeseed cultivars were determined by four different analytical methods: ferric reducing antioxidant power (FRAP), cupric reducing antioxidant capacity (CUPRAC), 2,2'-diphenyl-1-picrylhydrazyl (DPPH), 2,2'-azino-bis-3-ethylbenzothiazoline-6-sulfonic acid (ABTS). The average AC of the studied rapeseed cultivars ranged between 4.21-10.03 mmol Trolox (TE)/100 g, 7.82-10.61 mmol TE/100 g, 8.11-51.59 mmol TE/100 g, 22.48-43.13 mmol TE/100 g for FRAP, CUPRAC, DPPH and ABTS methods, respectively. There are positive correlations between total phenolics (TPC = 804-1625 mg sinapic acid (SA)/100 g) and AC of the studied rapeseed extracts ( = 0.2650-0.9931). Results of the principal component analysis (PCA) indicate that there are differences between the total amounts of antioxidants in rapeseed samples extracted by different extraction techniques. Rapeseed extracts obtained after 18 min of ultrasonication revealed the highest content of total antioxidants. The UAE is a very useful, efficient and rapid technique of oilseed samples preparation for determination of AC by different analytical methods.

A supercritical fluid extraction (SFE) method has been developed for the extraction of lipids in bilberry. Experimental design was used to optimize pressure, temperature and extraction time using CO as solvent. Best SFE condition for total lipids was 450 bar, 60 °C and 45 min. The SFE method was compared to conventional Bligh & Dyer (B&D) extraction. The amount of fatty acid methyl esters (FAME) was found to be 4.84 ± 0.06 mg and 4.564 ± 0.003 mg per g of the freeze-dried bilberry sample for the developed SFE and B&D methods, respectively, while the amount of total lipids was found to be 54.40 ± 6.06 mg and 65.70 ± 0.67 mg per g of sample for SFE and B&D, respectively. This discrepancy between FAME and total lipids could be explained by the presence of wax esters, sterol esters, carotenoids and phospholipids, as determined by supercritical fluid chromatography.

This study was aimed at evaluating the capability of W29 for the synthesis of lipolytic enzymes in a medium containing plant oils from non-conventional sources with some components displaying bioactivity. Oils from almond, hazelnut, and coriander seeds were obtained by using -hexane (Soxhlet method) and a chloroform/methanol mixture of solvents (Folch method), and their effect on the growth and lipolytic activity of was compared. A comparison of these two extraction methods showed that the extraction with -hexane was less effective regarding the oil extraction yields than the extraction conducted according to Folch's procedure. The lipolytic activity of the studied yeast was higher in the culture media containing oils extracted with the Soxhlet method than the Folch method but it was lower compared to olive oil medium. Among all oils tested, almond oil extracted with -hexane was the best inducer of extracellular lipases synthesized by . Its lipolytic activity achieved the maximum value of 2.33 U/mL after 48 h of culture. After 24 h of culture, it was close to the value obtained for the medium containing olive oil. Almond oil was a source of oleic and linoleic acids, which may determine differences in the lipolytic activity. The linoleic acid content in almond oil was higher than that found in other oils. When n-hexane was used for extraction, the resultant oils were characterized by lower contents of polyphenols and poorer antioxidative activity.

This study examined the thermo-oxidative degradation of stigmasterol fatty acids esters. Stigmasterol stearate, oleate, linoleate and linolenate were synthesized by chemical esterification and their purity evaluated by H-NMR and GC-MS. The degradation of stigmasterol esters was examined after heating them at 60 and 180 °C for 1, 2, 4, 8 and 12 h. It was established that stigmasterol esters were prone to thermo-oxidative degradation, with time and temperature affecting the degree of degradation. The unsaturation of fatty acids affected the rate of stigmasteryl ester degradation. The kinetics of StS and StO degradation were similar and the additional double bonds in StL and StLn resulted in their faster decomposition. The esters degraded faster at 180 than at 60 °C. The sterol and fatty acid molecules degraded at different rates, such that the fatty acid moiety deteriorated faster than the sterol at both temperatures, independent of the time of heating and the level of unsaturation.

Two samples of triacylglycerols i.e., olive oil and triolein, and one sample of diacylglycerol were investigated. In the course of compression, the density of the samples was determined by measurements of the change of piston position in a pressure chamber and volume correction due to chamber expansion under pressure. The speed of sound was evaluated from the time of flight of an ultrasonic impulse between emitting and receiving transducers placed in the high pressure chamber. The adiabatic compressibility, the intermolecular free length, the molar volume, the van der Waals' constant and the surface tension were evaluated from the density, the speed of sound and the average molecular mass. All tested liquids undergo a high-pressure phase transition. Discontinuities in the measured isotherms of the physicochemical parameters of the investigated oils indicate the presence of high-pressure phase transitions. Moreover the time dependent change of pressure at constant volume during the phase transition was measured. The fundamental difference in the molecular structure of these acylglycerols influences their behavior significantly under high pressure.

AOCS Official Method Ce 6-86 "Antioxidants, Liquid Chromatographic Method" was originally developed to confirm the correct antioxidant was added at the specified concentration to refined oils. Today, this method is increasingly utilized to validate that antioxidants are absent from oil products. False positive results can have a significant impact on the ability to sell products in specific markets and can impart additional business expenditures for conclusive secondary analyses. In the current work, quantification of -butylhydroquinone (TBHQ) in crude canola/rapeseed oil using liquid chromatography (LC) with ultraviolet (UV) detection was compromised by an interfering peak. Analyses using liquid chromatography-mass spectrometry (GC-MS) and high-resolution accurate mass LC-MS identified the interferent as 2,6-dimethoxy-4-vinylphenol (canolol), an endogenous compound present in crude canola/rapeseed oil. Resolution of canolol and TBHQ using LC-UV can be achieved via minor modification of the chromatographic conditions.

The aim of the study was to determine the effect of oil degradation on the content of glycidyl esters (GEs) in oils used for the frying of French fries. As frying media, refined oils such as rapeseed, palm, palm olein and blend were used. French fries were fried for 40 h in oils heated to 180 °C in 30-min cycles. After every 8 h of frying, fresh oil and samples were analyzed for acid and anisidine values, color, refractive index, fatty acid composition, and content and composition of the polar fraction. GEs were determined by LC-MS. Hydrolysis and polymerization occurred most intensively in palm olein, while oxidation was reported for rapeseed oil. The degradation of oil caused increased changes in the RI of frying oils. Losses of mono- and polyunsaturated fatty acids were observed in all samples, with the largest share in blend. The highest content of GE found in fresh oil was in palm olein (25 mg kg) and the lowest content of GE was found in rapeseed oil (0.8 mg kg). The palm oil, palm olein and blend were dominated by GEs of palmitic and oleic acids, while rapeseed oil was dominated by GE of oleic acid. With increasing frying time, the content of GEs decreased with losses from 47 % in rapeseed oil to 78 % in palm oil after finishing frying.

The application of flaxseed extracts as food ingredients is a subject of interest to food technologists and nutritionists. Therefore, the influence of the extraction method on the content and composition of beneficial compounds as well as anti-nutrients is important. In the study, the effects of two solvent extraction methods, aqueous and 60 % ethanolic, on phenolic and cyanogenic glucoside profiles of flaxseed extract were determined and compared. The impact of extracted phenolic compounds on the antioxidant capacity of the extracts was also investigated. Defatted meals from brown and golden flax varieties were used as extraction material. The ethanolic extraction was more selective for phenolics (100.8-131.7 mg g) than the aqueous one (11.5-15.7 mg g). However, the contribution of particular phenolic compounds to total phenolics was much more dependent on flax variety than extraction method. A strong relationship was observed between both radical scavenging and ferric reducing activity and the content of phenolics (particularly secoisolariciresinol diglucoside). The correlation between extract chelating ability and phenolics was moderate suggesting that other flaxseed compounds are involved in this activity. The extraction method strongly affected cyanogenic glucoside content of flaxseed extracts; the aqueous extraction caused 96 % reduction in cyanogenic glucoside content (0.56-0.62 mmol g) when compared to the content in defatted meal (9.1-11.6 mmol g). On the contrary, ethanolic extraction resulted in the high cyanogenic glucoside content in the extracts (71-89 mmol g). The results reveals that ethanolic extraction gives extracts rich in antioxidant lignans; aqueous extracts have lower antioxidant activity than ethanolic but cyanogenic glucosides are significantly reduced.

Thermal damage to proteins can reduce their nutritional value. The effects of toasting time on the kinetics of hydrolysis, the resulting molecular weight distribution of 00-rapeseed meal (RSM) and the soluble and insoluble protein fractions separated from the RSM were studied. Hydrolysis was performed with pancreatic proteases to represent protein digestibility. Increasing the toasting time of RSM linearly decreased the rate of protein hydrolysis of RSM and the insoluble protein fractions. The extent of hydrolysis was, on average, 44% higher for the insoluble compared with the soluble protein fraction. In contrast, the rate of protein hydrolysis of the soluble protein fraction was 3-9-fold higher than that of the insoluble protein fraction. The rate of hydrolysis of the insoluble protein fraction linearly decreased by more than 60% when comparing the untoasted to the 120 min toasted RSM. Increasing the toasting time elicited the formation of Maillard reaction products (furosine, -carboxymethyl-lysine and -carboxyethyl-lysine) and disulfide bonds in the insoluble protein fraction, which is proposed to explain the reduction in the hydrolysis rate of this fraction. Overall, longer toasting times increased the size of the peptides resulting after hydrolysis of the RSM and the insoluble protein fraction. The hydrolysis kinetics of the soluble and insoluble protein fractions and the proportion of soluble:insoluble proteins in the RSM explain the reduction in the rate of protein hydrolysis observed in the RSM with increasing toasting time.

Transesterification of palm olein with glycerol can increase the functionality by introducing additional hydroxyl groups to the triglyceride structure, an advantage compared to using palm olein directly as feedstock for producing palm-based polyol. The objective of this study was to synthesize transesterified palm olein-based polyol via a three-step reaction: (1) transesterification of palm olein, (2) epoxidation and (3) epoxide ring opening. Transesterification of palm olein yielded approximately 78 % monoglyceride and has an hydroxyl value of approximately 164 mg KOH g. The effect of formic acid and hydrogen peroxide concentrations on the epoxidation reaction was studied. The relationships between epoxide ring-opening reaction time and residual oxirane oxygen content and hydroxyl value were monitored. The synthesized transesterified palm olein-based polyol has hydroxyl value between 300 and 330 mg KOH g and average molecular weight between 1,000 and 1,100 Da. On the basis of the hydroxyl value and average molecular weight of the polyol, the transesterified palm olein-based polyol is suitable for producing rigid polyurethane foam, which can be designed to exhibit desirable properties. Rigid polyurethane foams were synthesized by substituting a portion of petroleum-based polyol with the transesterified palm olein-based polyol. It was observed that by increasing the amount of transesterified palm olein-based polyol, the core density and compressive strength were reduced but at the same time the insulation properties of the rigid polyurethane foam were improved.

In this study, the effect of temperature (140, 160, 180 °C) and roasting time (5, 10, 15 min) on the bioactive compound content (canolol, tocopherol and plastochromanol-8) of cold-pressed oil from yellow-seeded rapeseed lines of different colors was investigated. Roasting increased the peroxide value in the seed oils compared to the oils from the control samples. However, roasting did not affect the acid values of the oils, which were 1.15-1.47 and 1.30-1.40 mg KOH/g, for line PN1 03/1i/14 (yellow seeds) and line PN1 563/1i/14 (brown seeds), respectively. In this study, the seeds of line PN1 03/1i/14 were characterized by different changes in canolol content during roasting than the seeds of PN1 563/1i/14. There was a 90-fold increase in canolol for the line PN1 03/1i/14 (768.26 µg/g) and a 46-fold increase for the line PN1 563/1i/14 (576.43 µg/g). Changes in tocopherol and PC-8 contents were also observed. There was an increase in the contents of γ-T and PC-8 in the oils obtained from the seeds roasted at 180 °C for 10 and 15 min. γ-T content increased by 17-18% after 15 min of roasting, whereas the PC-8 content increased twofold.

In our study, we characterized the antioxidant activity and oxidative stability of cold-pressed macadamia, avocado, sesame, safflower, pumpkin, rose hip, Linola, flaxseed, walnut, hempseed, poppy, and milk thistle oils. The radical scavenging activity of the non-fractionated fresh oil, as well as the lipophilic and hydrophilic fractions of the oil was determined using a 1,1-diphenyl-2-picrylhydrazyl (DPPH) assay. The fatty acid composition of the fresh and stored oils was analyzed by gas chromatography. The acid value, peroxide value, -anisidine value and conjugated diene and triene contents in the fresh oils, as well as in those stored throughout the whole period of their shelf life, were measured by CEN ISO methods. The antioxidant activity of the oils expressed as Trolox equivalent antioxidant capacity (TEAC), ranged from 0.17 to 2.32 mM. The lipophilic fractions of the oils were characterized by much higher antioxidant activity than the hydrophilic ones. There were no significant changes in fatty acid composition and only slight changes in the oxidative stability parameters of the oils during their shelf life. Through the assessment of the relationship between antiradical activity and the oxidative stability of oils, it is proposed that a DPPH assay predicts the formation of oxidation products in cold-pressed oils-however, the correlations differ in fractionated and nonfractionated oils.

Tiger nut oil is a novel oil that requires more research data on its characteristics. In this study, the oil was extracted using both enzyme-aided pressing (EAP) and aqueous enzymatic extraction (AEE) methods. Using enzymes as a pre-treatment prior to mechanical pressing increased the concentration of some phenolic acids and tocopherols present in extracted oils compared to controls. High pressure processing as a pre-treatment before aqueous enzymatic extraction also enhanced tocopherols and total polyphenolic content in oils. The percentage free fatty acid and peroxide values indicated that under the initial extraction parameters, the oils were stable and they all met the standards for virgin olive oil set by the International Olive Oil Council. Residual meals from both extraction processes contained low protein contents ranging from 2.4 to 4.6 %. Additionally, EAP and AEE meals contained low DP (degree of polymerisation) sugars that appeared as 1-kestose (DP3) and nystose (DP4). EAP had the highest total DP3 and DP4 sugar content of 82.5 mg/g. These sugars would need further assessment to verify their identity and determine their suitability as a potential food.