Formation and distribution of oxidized fatty acids during deep‐ and pan‐frying of potatoes

The formation of cis‐9,10‐epoxystearate, trans‐9,10‐epoxystearate, cis‐9,10‐epoxyoleate, cis‐12,13‐epoxyoleate, trans‐9,10‐epoxyoleate, trans‐12,13‐epoxyoleate and the co‐eluting 9‐ and 10‐ketostearates during eight successive pan‐ and deep‐frying sessions of pre‐fried potatoes in five different types of vegetable oils – namely cottonseed oil, sunflower oil, vegetable shortening, palm oil and virgin olive oil – was followed and quantified both in fried oils and in fried potatoes by GC/MS after derivatization to methyl esters. These oxidized fatty acids were present at relatively low concentrations in the fresh oils and pre‐fried potatoes while they increased linearly with frying time, reaching up to 1140.8 µg/g in virgin olive oil (VOO) and 186.9 µg/g in potatoes pan‐fried in VOO after eight pan‐frying sessions, with trans‐9,10‐epoxystearate predominating in all cases. The formation of polymerized triacylglycerols (PTG) was also quantified in frying oils by size exclusion HPLC. Pan‐frying caused higher oxidized fatty acid and PTG formation compared to deep‐frying. Epoxyoleates and PTG concentrations were increased after frying in polyunsaturated oils, while epoxystearate and 9‐ and 10‐ketostearate concentrations were increased after frying in monounsaturated oils. No specific absorption of the oxidized fatty acids by the fried potatoes seems to occur. The dietary intake of oxidized fatty acids and PTG by the consumption of fried potatoes was discussed.     

Content of trans,trans‐2,4‐decadienal in deep‐fried and pan‐fried potatoes

Trans,trans‐2,4‐decadienal is a by‐product of frying oil that is also transferred to fried food. This aldehyde has been found and quantified both in frying oils and fumes generated during frying. Furthermore, it has been reported that 2,4‐decadienal has cytotoxic and genotoxic effects and promotes LDL oxidation. In the present work trans,trans‐2,4‐decadienal was detected directly in fried potatoes (french‐fries). Moreover, the influence of frying conditions (deep‐frying, pan‐frying), the oil type (olive oil, sunflower oil, cottonseed oil, palm oil and a vegetable shortening) and the degree of thermal deterioration (eight successive frying sessions without replenishment) on the production of 2,4‐decadienal in oil and potatoes was studied. The isolation of the aldehyde was performed by methanol extraction, while the identification and quantification was performed by RP‐HPLC. The quantity of trans,trans‐2,4‐decadienal produced during successive pan‐frying demonstrated a peak at the third and fourth frying session. The highest concentration of trans,trans‐2,4‐decadienal was detected in potatoes fried in sunflower oil, and the lowest in olive oil. The quantity of trans,trans‐2,4‐decadienal in fried potatoes decreased during successive deep‐frying at the seventh frying session or remained stable, except for cottonseed oil. The quantity of trans,trans‐2,4‐decadienal in fried potatoes was considered to be dependent on the oil used, on the frying process and, to a lesser extent, on the oil deterioration. In all cases tested, the highest concentration of trans,trans‐2,4‐decadienal was detected during deep‐frying. The unsaturation degree of the frying oil was considered to promote the formation of trans,trans‐2,4‐decadienal. Considering the quantity of 2,4‐decadienal found in french‐fries and in the respective frying medium, direct quantification of 2,4‐decadienal is required in order to make an estimation of intake from french‐fries.     

Plasma Modified Membrane for Daily Recovery of Oil from Repeated Frying Operation with Frequent Oil Replenishment

Sunflower oil was used for deep frying of potatoes at 170 ± 5 °C and for 8 h per day for 5 days in a fryer with an automatic oil filtration system. Three different frying operations were performed: operation (OP)-1, OP-2 and OP-3; that correspond to the oil unfiltered at the end of each frying day, the oil filtered through the fryer's own filter (passive filtration) and the oil firstly subjected to passive filtration and then filtered through a polyethersulfone membrane modified with hexamethyldisiloxane via radio frequency plasma (75 W-5 min, discharge power–time), respectively. The performance of each operation was investigated in terms of free fatty acids (FFA), conjugated dienoic acids (CD), TOTOX value, total polar content (TPC), Hunter color, viscosity, fatty acid composition, and tocopherol content. The results showed that OP-3 could decrease FFA, CD, TOTOX, TPC, L*a*b* value, viscosity and linoleic acid (18:2)/palmitic acid (16:0) ratio in 29.6, 11.7, 25, 30.8, 6.1*11.3*20.8*, 7.8, 12.2 %, respectively, compared to the unfiltered oil (OP-1). Regenerated oil from OP-3 had a frying life approximately 17 h more than oils from both OP-1 and OP-2.     

Oxidative Stability and Changes in Chemical Composition of Extra Virgin Olive Oils After Short‐Term Deep‐Frying of French Fries

We aimed at investigating oxidative stability and changes in fatty acid and tocopherol composition of extra virgin olive oil (EVOO) in comparison with refined seed oils during short‐term deep‐frying of French fries, and changes in the composition of the French fries deep‐fried in EVOO. EVOO samples from Spain, Brazil, and Portugal, and refined seed oils of soybean and sunflower were studied. Oil samples were used for deep‐frying of French fries at 180 °C, for up to 75 min of successive frying. Tocopherol and fatty acid composition were determined in fresh and spent vegetable oils. Tocopherol, fatty acid, and volatile composition (by SPME–GC–MS) were also determined in French fries deep‐fried in EVOO. Oil oxidation was monitored by peroxide, acid, and p‐anisidine values, and by Rancimat after deep‐frying. Differential scanning calorimetry (DSC) analysis was used as a proxy of the quality of the spent oils. EVOOs presented the lowest degree of oleic and linoleic acids losses, low formation of free fatty acids and carbonyl compounds, and were highly stable after deep‐frying. In addition, oleic acid, tocopherols, and flavor compounds were transferred from EVOO into the French fries. In conclusion, EVOOs were more stable than refined seed oils during short‐term deep‐frying of French fries and also contributed to enhance the nutritional value, and possibly improve the flavor, of the fries prepared in EVOO.     

Utilization of high‐oleic rapeseed oil for deep‐fat frying of French fries compared to other commonly used edible oils

Changes in chemical, physical and sensory parameters of high‐oleic rapeseed oil (HORO) (NATREON?) during 72 h of deep‐fat frying of potatoes were compared with those of commonly used frying oils, palm olein (PO), high‐oleic sunflower oil (HOSO) and partially hydrogenated rapeseed oil (PHRO). In addition to the sensory evaluation of the oils and the potatoes, the content of polar compounds, oligomer triacylglycerols and free fatty acids, the oxidative stability by Rancimat, the smoke point and the anisidine value were determined. French fries obtained with HORO, PO and HOSO were still suitable for human consumption after 66 h of deep‐fat frying, while French fries fried in PHRO were inedible after 30 h. During the frying period, none of the oils exceeded the limit for the amount of polar compounds, oligomer triacylglycerols and free fatty acids recommended by the German Society of Fat Science (DGF) as criteria for rejection of used frying oils. After 72 h, the smoke point of all oils was below 150 °C, and the amount of tocopherols was reduced to 5 mg/100 g for PHRO and 15 mg/100 g for HORO and HOSO. Remarkable was the decrease of the oxidative stability of HOSO measured by Rancimat. During frying, the oxidative stability of this oil was reduced from 32 h for the fresh oil to below 1 h after 72 h of frying. Only HORO showed still an oxidative stability of more than 2 h. From the results, it can be concluded that the use of HORO for deep‐fat frying is comparable to other commonly used oils.     

Seed roasting improves the oxidative stability of canola (B. napus) and mustard (B. juncea) seed oils

Animal fats and partially hydrogenated vegetable oils (PHVO) have preferentially been used for deep‐frying of food because of their relatively high oxidative stability compared to natural vegetable oils. However, animal fats and PHVO are abundant sources of saturated fatty acids and trans fatty acids, respectively, both of which are detrimental to human health. Canola (Brassica napus) is the primary oilseed crop currently grown in Australia. Canola quality Indian mustard (Brassica juncea) is also being developed for cultivation in hot and low‐rainfall areas of the country where canola does not perform well. A major impediment to using these oils for deep‐frying is their relatively high susceptibility to oxidation, and so any processing interventions that would improve the oxidative stability would increase their prospects of use in commercial deep‐frying. The oxidative stability of both B. napus and B. juncea crude oils can be improved dramatically by roasting the seeds (165 °C, 5 min) prior to oil extraction. Roasting did not alter the fatty acid composition or the tocopherol content of the oils. The enhanced oxidative stability of the oil, solvent‐extracted from roasted seeds, is probably due to 2,6‐dimethoxy‐4‐vinylphenol produced by thermal decarboxylation of the sinapic acid naturally occurring in the canola seed.     

Stability of Essential Fatty Acids and Formation of Nutritionally Undesirable Compounds in Baking and Shallow Frying

During cooking oils and fats are exposed to high temperatures that may affect the nutritional quality of foods that are prepared in this way. Concerns have been raised about the degradation of polyunsaturated fatty acids and the formation of potentially harmful compounds during deep frying, but relatively little is known about these changes in other cooking processes. In the present study sponge cakes and fried potatoes were prepared via standardised baking and shallow frying procedures by using different oils and fats (sunflower oil, rapeseed oil, various margarines or butter). The effect of cooking on the retention of two essential fatty acids (linoleic acid and α-linolenic acid) and the formation of trans fatty acids (TFA) and polymerised triacylglycerols (PTG) was evaluated by analyzing fat extracted from the cooked food. It was found that over 95 % of essential fatty acids were retained upon completion of both cooking techniques. The formation of TFA was not significant. Polymerisation was noticeable only in shallow frying, although the final levels of PTG were negligible (<1.3 %). Overall, in contrast to deep frying, oil-based media high in polyunsaturated fatty acids seem to be a good alternative for domestic cooking techniques as they increase the nutritional value of the prepared food.     

Sunflower Oil–Beeswax Oleogels Are Promising Frying Medium for Potato Strips

Sunflower oil–beeswax oleogels at 3% (BWO-3) and 8% (BWO-8) organogelator concentration are prepared to evaluate oleogels as frying medium for potato strip frying against commercial sunflower oil (SO). Rheological and thermal analyses of oleogels prove that the samples are fully solid (20±3 °C) and totally liquid (180 °C), and thermoreversible. Fresh and used (after frying) fat analyses show that free fatty acidity (FFA), peroxide value (PV) and total polar materials (TPM) are enhanced in all samples at the 7th h, but the relative enhancement levels are lower in oleogel samples. Potato strips fried in oleogels absorb significantly less oil (11.97% and 12.07%) than the control sample (15.20%). Potatoes fried in oleogels are also more bright and yellower than the control sample. Textural profile of the fried potatoes indicates that the samples fried in oleogels are harder, springier, and gummier than that of the control sample. Sensory analysis shows that oleogel fried potatoes get higher sensory scores. Also, overall acceptability of potatoes fried in BWO-8 sample is the highest (8.50) among all. The prepared oleogels are found quite promising frying medium in this study. Further studies with other types of oleogels in extended period frying of various foods are suggested. Practical applications: The development of innovative frying techniques to produce healthier products with lower fat and calorie values are still a remarkable research area. Oleogelation is an emerging strategy used for solid-like oil designing and based on the formation of 3D networks by the addition of organogelators. Oleogelation is accepted as a healthy strategy to structure liquid oils into solid consistency, and oleogels have great edible applications in processed foods, and can be used as a frying medium. This work can guide the use of sunflower oil–beeswax oleogels as a frying medium and allow the development of more healthy fried snacks.     

Carbon dioxide blanketing impedes the formation of 4‐hydroxynonenal and acrylamide during frying. A novel procedure for HNE quantification

Acrylamide and 4‐hydroxynonenal (HNE) are among the most detrimental compounds formed during high temperature processing of food. The effect of carbon dioxide blanketing (CDB) on the formation and accumulation in food of these compounds during deep‐fat frying was investigated. French fries were fried for 7 h daily and for 7 days in canola oil at 185 ± 5°C without and with CO₂ protection. The amount of acrylamide and HNE accumulated in the French fries were analyzed. Compared to standard frying conditions (SFC), frying under CDB reduced the amount of HNE by 62%. On the 3rd day of frying, the amount of acrylamide in fries fried under SFC was 3.3 times higher compared to frying with CO₂ protection. Frying with carbon dioxide protection is an effective and practical way to impede formation of toxic components during deep‐fat frying. To assess formation of HNE a simple, sensitive and reliable procedure for HNE analysis in frying oils and fried products was developed and evaluated. Practical applications : The toxicity of HNE and acrylamide, coupled with the increasing consumption of fried foods necessitates that measures be taken to reduce their formation and subsequent accumulation in fried foods. The frying method proposed in this study is very effective and requires only a simple modification to the fryer. Developed rapid and simple procedure for HNE analysis allows more accurate quantification.     

Hydrolysis of used frying palm olein and sunflower oil catalyzed by porcine pancreatic lipase

The enzymatic hydrolysis of frying used vegetable oils with different degrees of alteration were measured using porcine pancreatic lipase (acylglycerol acylhydrolase EC 3.1.1.3). Successive frying of potatoes significantly increased the level of total polar lipid content in the palm olein from 9.3±0.1 mg/100 mg oil to 26.4±0.3 mg/100 mg oil after 90 fryings, and from 4.0±0.1 mg/100 mg oil to 27.7±0.3 mg/100 mg oil in sunflower oil after 60 fryings. Triacylglycerol polymers, triacylglycerol dimers, and oxidized triacylglycerols also increased 37-, 7.9-, and 7.5-times in palm olein, respectively, and 56-, 22-, and 4.7-times in sunflower oil, respectively. However, diacylglycerols and free fatty acid levels related to hydrolytic alteration did not increase with the number of fryings in both oils. The substrate concentration in the reactor was determined by calculating the molecular weight of each oil showing a different degree of alteration. We compared the methodology used by us and that used by other authors. The results show that the methods are reproducible and that the values obtained are in concordance with theoretical values. The kinetic parameters apparent Michaelis-Menten constant (K _M ^app ) and apparent maximum velocity of hydrolysis (V _max ^app ) were different in unused palm olein (5.1±0.7 and 166±7.6, respectively) than in sunflower oil (2.2±0.3 and 62±2.2, respectively). However, changes inK _M ^app andV _max ^app were not related to the degree of alteration of the oils.     

Effects of frying on the trans‐fatty acid formation in soybean oils

To evaluate the effects of repeated deep‐frying on the trans‐fatty acid (TFA) formation in soybean oils, simultaneous frying experiments were carried out. French fries were prepared using three different types of soybean oil (pressed soybean oil, PSBO; first‐grade solvent extracted soybean oil, FG‐SESBO; and third‐grade solvent extracted soybean oil, TG‐SESBO). French fries were fried intermittently at 180–185°C for a total frying time of 32 h and at an interval time of 30 min. It was found that the initial amount of total TFAs was 0.29 g/100 g, 0.31 g/100 g, and 0.90 g/100 g in PSBO, TG‐SESBO, and FG‐SESBO, respectively. Before the frying started, the C18:1,t‐9, trans‐linoleic acid (TLA), trans‐linolenic acid (TLNA), and total TFA content of the PSBO and TG‐SESBO were significantly lower than in the FG‐SESBO (p<0.05). However, in the frying oil samples, the final concentration of total TFA in the PSBO, TG‐SESBO, and FG‐SESBO were 1.79 ± 0.17 g/100 g, 1.12 ± 0.10 g/100 g, and 1.70 ± 0.07 g/100 g, which was 6.17‐, 3.61‐, and 1.89‐fold higher that in fresh oil, respectively. The highest increasing slopes of C18:1,t‐9, TLA, TLNA, and total TFA were observed in the PSBO. Practical applications : A high intake of TFAs has been shown to lead to an increased risk of coronary heart disease. Plant oils, particularly soybean oil, have been widely used in the food industry in China. Frying is one of the most common methods to cook food. The formation of TFAs during frying has been shown to be closely related to the temperature and duration of the frying process. However, the effects of frying on the formation of TFAs in different soybean oils have not been well studied. In the present study, we demonstrated that increasing the number of frying cycles can cause an intensive increase in the concentration of TFAs in different types of soybean oil, but especially in PSBO.     

Untersuchungen zur Charakterisierung von Fritierfetten aus der Praxis

Investigations for Characterising Frying Fats According to A. Mankel the simultaneous consideration of the acid value, the content of petroleum ether insoluble oxidised fatty acids and the smoke point is suitable to evaluate the quality of used frying fats and oils. At present this combination is generally considered as the best method of evaluation. Quick tests, which can be carried out adjacent to the fryer and whereby only the content of free fatty acids is measured, have only a limited significance. A novel quick test, the ?Fritest®”? of Messrs. Merck, is supposed to assess the oxidation products – as the saponification colour number does. But the ?Fritest®”? does not take the colour of the fat in account which would partially eliminate the influence of the inherent colour of the fat as also the influence of the frying goods. We carried out this test with soyabean, sunflower and hardened groundnut oil used for frying. In the case of sunflower oil samples from three fryers with different frying goods the ?Fritest®”? indicated the necessity of oil renewal and deterioration of the oil resp. although there was no deterioration recognizable according to the criteria of Mankel. Producers and publications recommend the use of hardened groundnut oil for frying. One such oil which had been used under conditions similar to commercial practice was found by ?Fritest®”? to be not satisfying the specifications of food regulations. In the case of soyabean oil used for fish frying the ?Fritest®”? as well as Mankel's criteria indicated deterioration. K. Lang and coworkers could, however, not observe any detrimental physiological properties on rats as a result of feeding trials with these oils over many years.     

The content of tocopherols and oxidative quality of oils prepared from sunflower (Helianthus annuus L.) seeds roasted in a microwave oven

Sunflower seeds ((Helianthus annuus were roasted for 6, 12, 20 or 30 min at a frequency of 2450 MHz using a domestic microwave oven. After the kernels were separated from the sunflower seeds, the quality characteristics and the compositions of the oils were investigated in relation to their tocopherol distributions, and they were further evaluated as compared with an unroasted oil sample. Only minor increases (p < 0.05) in chemical and physical changes of the oils, such as the carbonyl value, the p‐anisidine value and the color development, occurred at a prolonged roasting period. Significant decrease (p < 0.05) was observed in the amounts of phospholipids in the oils after microwave roasting. Nevertheless, compared to the original level, more than 92 wt‐% tocopherols still remained after 30 min of roasting. With a few exceptions, these results indicate that the exposure of sunflower seeds to microwaves for 12 min caused no significant (p < 0.05) loss or change in the content of tocopherols and polyunsaturated fatty acids in the kernels.     

The Effects of Microwave Frying on Physicochemical Properties of Frying and Sunflower Oils

Deep fat frying is a method of food preparation which has been popular for quite a number of years. During deep frying, the quality of oil and the finished product decreases as the result of heat treatment of the oil exposed to air at high temperature. Application of heat by microwave as an alternative to the conventional method of frying has become popular in recent years. In this research, the effects of microwave frying on the changes in the quality indices of used oil have been investigated. To achieve this, potato slices were fried in both frying and sunflower oils by application of medium power microwave (550 W) for 20 min, three times a day, for five consecutive days, and oils were sampled for analysis. The results obtained from the chemical tests demonstrated that used frying oil had lower polar compounds, a higher induction period, and more saturated fatty acids than sunflower oil. The interesting point observed was that peroxides formed as the result of oxidation chain reactions were not broken down and were built up due to the lower temperature and shorter period of frying. Therefore microwave frying might be considered as a suitable alternative to the conventional frying due to less degradation of the oil and consequently a lower production of artifacts.     

Cyclic fatty acids in sunflower oils during frying of frozen foods with oil replenishment

Frying of frozen foods has become popular because it considerably reduces cooking time. Polymers and cyclic fatty acid monomers (CFAM) formed during frying are potentially toxic and therefore their production should be minimized. Twenty discontinuous fryings of different frozen foods were carried out over ten consecutive days, in sunflower oil (SO) and in high‐oleic acid sunflower oil (HOSO), by adding fresh oil after each frying to bring the volume of the fryer oil back to 3 L. CFAM methyl ester derivates were hydrogenated, isolated, concentrated and quantified by HPLC using a reverse‐phase column, followed by gas chromatography. After 20 fryings, significantly higher contents of polar material, polymers and CFAM (all p <0.001) were found in SO than in HOSO. Bicyclic compound formation was four times higher in SO (p <0.001). The fat from the fried potatoes presented a polymer content very similar to that of their corresponding oils. The 100‐g rations of the SO‐fried potatoes from the 20^th frying supply 49 or 15%, respectively, more polymers and CFAM and 1 mg more bicyclic fatty acids than the 100‐g rations of HOSO‐fried potatoes. Because digestion and absorption of polar material, polymers and CFAM occur, the data clearly show the advantageousness and advisability of frying with HOSO rather than SO.     

Monitoring of 2,4‐decadienal in oils and fats used for frying in restaurants in Athens,Greece

Some frying by‐products of medium polarity, so‐called medium‐polarity materials (MPM), produced during domestic deep‐frying of French‐fried potatoes in edible vegetable oils, have recently been isolated and linearly correlated to % total polar materials and % polymerized triglycerides. The in vitro oxidation of low‐density lipoproteins in a dose‐dependent manner by MPM has also been reported. In the present study, the MPM constituents were identified after extraction of MPM from the oils, subsequent purification by RP‐HPLC, and GC‐MS analysis. The main constituent of MPM was trans,trans‐2,4‐decadienal, a compound that has previously been reported to be formed during peroxidation of linoleic and arachidonic acid. 2,4‐Decadienal was also quantified in oils and fats used for frying in restaurants in Athens, Greece, by direct injection of oil sample solutions in HPLC. For the most commonly used frying oils, 2,4‐decadienal concentration ranges were 0.3–119.7 mg/kg for sunflower oil, 13.3–92.7 mg/kg for cottonseed oil, 4.1–44.9 mg/kg for palm oil, and 2.0–11.3 mg/kg for vegetable cooking fats. Considering the common catering practices of frying, 2,4‐decadienal was more likely to be found in sunflower oil after deep‐frying of potatoes. Comparing the amounts of this aldehyde found in oils from restaurants to the amounts previously found for domestic frying (up to 30 mg/kg after the 8^th successive frying session in sunflower oil), the probability of consuming a level of 2,4‐decadienal in restaurant‐prepared food that is higher than the level in home‐fried food was determined to be approximately one third.     

<Emphasis Type="Italic">cis</Emphasis>-, <Emphasis Type="Italic">trans</Emphasis>- and Saturated Fatty Acids in Selected Hydrogenated and Refined Vegetable Oils in the Indian Market

The fatty acid composition of 27 samples of commercial hydrogenated vegetable oils and 23 samples of refined oils such as sunflower oil, rice bran oil, soybean oil and RBD palmolein marketed in India were analyzed. Total cis, trans unsaturated fatty acids (TFA) and saturated fatty acids (SFA) were determined. Out of the 27 hydrogenated fats, 11 % had TFA about 1 % where as 11 % had more than 5 % TFA with an average value of about 13.1 %. The 18:1 trans isomers, elaidic acid was the major trans contributor found to have an average value of about 10.8 % among the fats. The unsaturated fatty acids like cis-oleic acid, linoleic acid and α-linolenic acid were in the range of 21.8–40.2, 1.9–12.2, 0.0–0.7 % respectively. Out of the samples, eight fats had fatty acid profiles of low TFA (less than 10 %) and high polyunsaturated fatty acids (PUFA) such as linoleic and α-linolenic acid. They had a maximum TFA content of 7.3 % and PUFA of 11.7 %. Among the samples of refined oils, rice bran oil (5.8 %) and sunflower oil (4.4 %) had the maximum TFA content. RBD palmolein and rice bran oils had maximum saturated fatty acids content of 45.1 and 24.4 % respectively. RBD palmolein had a high monounsaturated fatty acids (MUFA) content of about 43.4 %, sunflower oil had a high linoleic acid content of about 56.1 % and soybean oil had a high α-linolenic acid content of about 5.3 %.     

Formation of 4‐Hydroxy‐2‐Trans‐Nonenal,a Toxic Aldehyde,in Thermally Treated Olive and Sunflower Oils

4‐Hydroxy‐2‐trans‐nonenal (HNE) is a toxic aldehyde produced mostly in oils containing polyunsaturated fatty acid due to heat‐induced lipid peroxidation. The present study examined the effects of the heating time, the degree of unsaturation, and the antioxidant potential on the formation of HNE in two light olive oils (LOO) and two sunflower oils (one high oleic and one regular) at frying temperature. HNE concentrations in these oil samples heated for 0, 1, 3, and 5 hours at 185 °C were measured using high‐performance liquid chromatography. The fatty‐acid distribution and the antioxidant capacity of these four oils were also analyzed. The results showed that all oils had very low HNE concentrations (<0.5 μg g^?1 oil) before heating. After 5 hours of heating at 185 °C, HNE concentrations were increased to 17.98, 25.00, 12.51, and 40.00 μg g^?1 in the two LOO, high‐oleic sunflower oil (HOSO), and regular sunflower oil (RSO), respectively. Extending the heating time increased HNE formation in all oils tested. It is related to their fatty‐acid distributions and antioxidant capacities. RSO, which contained high levels of linoleic acid (59.60%), a precursor for HNE, was more susceptible to degradation and HNE formation than HOSO and LOO, which contained only 6–8% linoleic acid.     

Synthesis of fatty acid esters from acid oils using lipase B from Candida antarctica

Esterification of corn and sunflower acid oils with straight‐ and branched‐chain alcohols were conducted using lipase B from Candida antarctica (Novozym 435) in n‐hexane. Sunflower acid oil consisted of 55.6% free fatty acids and 24.7% triacylglycerols, while the free fatty acids and triacylglycerols contents of corn acid oil were 75.3% and 8.6%, respectively. After 1.5 h of methanolysis of sunflower acid oil, the highest fatty acid methyl ester content (63.6%) was obtained at 40 °C and the total fatty acid/methanol molar ratio was 1/1, using 15% enzyme based on acid oil weight. The conversion of both acid oils with straight‐ and branched‐chain alcohols was not significantly affected by the chain length of the alcohols. However, the lowest fatty acid methyl ester content (50%) was obtained in the reaction of corn acid oil with methanol. Sunflower acid oil was converted to fatty acid esters using primer alcohols such as n‐propanol, i‐ and n‐butanol, n‐amylalcohols, n‐octanol, and a mixture of amylalcohol isomers, resulting in a fatty acid ester content of about 70% at 40 °C.     

Heat treatment of vegetable oils III. GC-MS characterization of cyclic fatty acid monomers in heated sunflower and linseed oils after total hydrogenation

Fractions of cyclic fatty acid monomers (CFAM) were isolated from linseed oil heated at 275°C for 12 hr under nitrogen, at 240°C for 10 hr under nitrogen and at 240°C for 10 hr under air. Cyclic fatty acid monomers fractions were also isolated from a sunflower oil heated at 275°C for 12 hr under nitrogen and at 200°C for 48 hr in a commercial fryer. The CFAM fractions were hydrogenated and their composition studied by gas liquid chromatography coupled with mass spectrometry (GC-MS). The CFAM in the fraction isolated from heated linseed oil samples were a mixture (1:1) ofcis andtrans cyclopentyl and cyclohexyl isomers, while the CFAM in the fractions isolated from heated sunflower oils were mostly cyclopentyl isomers. The major cyclopentyl isomers weretrans andcis methyl 7-(2′-hexylcyclopentyl) -heptanoate, methyl 9-(2′-butyl-cyclopentyl)-nonanoate and methyl 10-(2′-propylcyclo-pentyl)-decanoate. The major cyclohexyl isomers were thetrans andcis methyl 9-(2′-propylcyclohexyl)-nonanoate which represented about 50% of the CFAM isomers isolated from heated linseed oil samples. For part II in this series see Ref. 1.