Performance of antioxidative compounds under frying conditions: A review.

Although much study has been done assessing activity of antioxidants at ambient and accelerated storage temperatures, the results cannot correctly depict their performance under frying conditions. Due to the stringent conditions imposed, most conventional antioxidative compounds failed under frying conditions, suggesting the need for a continuous modification to improve their effectiveness. Although syntheses and performance evaluation of over a hundred (semi)synthetic antioxidants have been reported in literature, only a small fraction have been specifically designed and/or evaluated under frying conditions. Here, the performance under frying conditions of major natural and synthetic antioxidants is reviewed. The recent trend in the designing of antioxidants for frying applications is also reviewed with the view of stimulating further study in this direction.

Performance of structured lipids incorporating selected phenolic and ascorbic acids.

Conditions applied during frying require antioxidant which is stable at these conditions and provides protection for frying oil and fried food. Novel structured lipids containing nutraceuticals and antioxidants were formed by enzymatic transesterification, exploring canola oil and naturally occurring antioxidants such as ascorbic and selected phenolic acids as substrates. Lipozyme RM IM lipase from Rhizomucor miehei was used as biocatalyst. Frying performance and oxidative stability of the final transesterification products were evaluated. The novel lipids showed significantly improved frying performance compared to canola oil. Oxidative stability assessment of the structured lipids showed significant improvement in resistance to oxidative deterioration compared to original canola oil. Interestingly, the presence of ascorbic acid in an acylglycerol structure protected α-tocopherol against thermal degradation, which was not observed for the phenolic acids. Developed structured lipids containing nutraceuticals and antioxidants may directly affect nutritional properties of lipids also offering nutraceutical ingredients for food formulation.

Monitoring of quality and stability characteristics and fatty acid compositions of refined olive and seed oils during repeated pan- and deep-frying using GC, FT-NIRS, and chemometrics.

Refined olive, corn, soybean, and sunflower oils were used as cooking oils for deep-frying at two different temperatures, 160 and 190 °C, and for pan-frying of potatoes at 180 °C for 10 successive sessions under the usual domestic practice. Several chemical parameters were assayed during frying operations to evaluate the status of the frying oils. Refined olive oil, as frying oil, was found to be more stable than the refined seed oils. In fact, this oil has proven the greatest resistance to oxidative deterioration, and its trans-fatty acid contents and percentages of total polar compounds were found to be lower at 160 °C during deep-frying. Finally, chemometric analysis has demonstrated that the lowest deterioration of the quality of all refined oils occurred in the refined olive oil during deep-frying at 160 °C and the highest deterioration occurred in the refined sunflower oil during pan-frying at 180 °C.

Phenolic extracts from Sorbus aucuparia (L.) and Malus baccata (L.) berries: antioxidant activity and performance in rapeseed oil during frying and storage.

In the present study, phenolic extracts and fractions from Canadian rowanberry (Sorbus aucuparia) and crabapple (Malus baccata) were screened for antioxidant activity using DPPH radical scavenging activity, and ß-carotene bleaching assays. Furthermore, rapeseed oil was supplemented with extracts/fractions and performance was assessed during accelerated storage at 65°C, under Rancimat at 120°C, and during frying at 180°C. A number of phenolic fractions showed significantly higher radical scavenging and antioxidant activity in the oil than the synthetic antioxidant, butylated hydroxytoluene (BHT). At the end of the 7-day storage, the peroxide value was reduced by up to 42% in the presence of extracts. The extent of thermooxidative degradation was significantly lower in oils fortified with the fruit extracts, with fractions from Sorbus species being more effective. Results from the present study suggested that polyphenolic extracts from these fruits can offer effective alternative to synthetic antioxidants during frying and storage of vegetable oils.

Spectroscopic characterisation of dimeric oxidation products of phytosterols.

Sterol dimers are the main oxidation products formed during sterols degradation at elevated temperatures. An investigation was carried out to decipher the structure of dimers differing in polarity, formed during ß-sitosterol thermo-oxidation. The oxidation products were fractionated using silica gel into non-polar (NP), mid-polar (MP) and polar fractions (P). Oligomers were further separated by size-exclusion chromatography (SEC). Tentative chemical structures of non-polar, mid-polar and polar dimers were identified using Ag(+)/CIS-MS and APCI-MS procedures after on-line RP-HPLC separation. Further structures were verified by NMR and FT-IR spectroscopies.

Phosphatidylcholine and dihydrocaffeic acid amide mixture enhanced the thermo-oxidative stability of canola oil.

Recently, we reported the synthesis of a series of dihydrocaffeic acid amides and evaluated their performance as antioxidants for frying applications using a model frying. In the present study, the possibility of a synergy between the amide, N-propyl-N-benzyl-3-(3,4 dihydroxyphenyl)propanamide (DCA) and phosphatidylcholine (PC) was explored in a 6-day actual frying operation. As measured by the amount of polar components (TPC), anisidine value (AnV), changes in fatty acid composition, residual tocopherol and hydroxynonenal (HNE), canola oil containing the formulated antioxidant was twice as stable compared to the regular unfortified oil. At the end of the frying period, the amount of HNE detected in regular canola oil and the fortified sample was at 5.7 and 2.5µg/g, respectively. Thus, the mixture containing phosphatidylcholine and dihydrocaffeic acid amide is a promising antioxidant for frying application.

γ-Oryzanols of North American Wild Rice (Zizania palustris).

γ-Oryzanol, a natural mixture of ferulic acid esters of triterpene alcohols and sterols, are an important bioactive components present in rice bran oil. In light of the recent increase in the popularity of wild rice among consumers, and the possibility of a direct relationship between γ-oryzanol composition and its bioactivity, the oryzanol profile of major wild rice (Zizania palustris) grown in North America was studied and compared to regular brown rice (Oryza sativa L.). A total of twenty-three γ-oryzanol components were separated, identified and quantified by HPLC coupled to an Orbitrap MS. The distribution of individual γ-oryzanols was similar for all the wild rice but significantly different from those of the regular brown rice. Unlike in the regular brown rice, a significant amount of steryl caffeate and cinnamate were found in the wild rice samples. Generally, the amounts of γ-oryzanol in the wild rice were higher compared to the regular brown rice, 1,352 vs. 688 µg/g. The results from this study showed that wild rice had a more diverse γ-oryzanol composition and the higher amounts compared to the regular brown rice.

Novel antioxidants are not toxic to normal tissues but effectively kill cancer cells.

Free radicals are formed as a result of cellular processes and play a key role in predisposition to and development of numerous diseases and of premature aging. Recently, we reported the syntheses of a number of novel phenolic antioxidants for possible application in food industry. In the present study, analyses of the cellular processes and molecular gene expression effects of some of the novel antioxidants in normal human tissues and in cancer cells were undertaken. Results indicated that whereas the examined antioxidants showed no effects on morphology and gene expression of normal human oral and gingival epithelial tissues, they exerted a profound cell killing effect on breast cancer cells, including on chemotherapy-resistant breast cancer cells and on oral squamous carcinoma cells. Among the tested antioxidants, N-decyl-N-(3-methoxy-4-hydroxybenzyl)-3-(3,4-dihydroxyphenyl) propanamide and N-decyl-N-(3,5-dimethoxy-4-hydroxybenzyl)-3-(3,4-dihydroxyphenyl) propanamide were the most promising, with excellent potential for cancer treatment. Moreover, our gene expression databases can be used as a roadmap for future analysis of mechanisms of antioxidant action.

Performance of Regular and Modified Canola and Soybean Oils in Rotational Frying.

Canola and soybean oils both regular and with modified fatty acid compositions by genetic modifications and hydrogenation were compared for frying performance. The frying was conducted at 185 ± 5 °C for up to 12 days where French fries, battered chicken and fish sticks were fried in succession. Modified canola oils, with reduced levels of linolenic acid, accumulated significantly lower amounts of polar components compared to the other tested oils. Canola oils generally displayed lower amounts of oligomers in their polar fraction. Higher rates of free fatty acids formation were observed for the hydrogenated oils compared to the other oils, with canola frying shortening showing the highest amount at the end of the frying period. The half-life of tocopherols for both regular and modified soybean oils was 1-2 days compared to 6 days observed for high-oleic low-linolenic canola oil. The highest anisidine values were observed for soybean oil with the maximum reached on the 10th day of frying. Canola and soybean frying shortenings exhibited a faster rate of color formation at any of the frying times. The high-oleic low-linolenic canola oil exhibited the greatest frying stability as assessed by polar components, oligomers and non-volatile carbonyl components formation. Moreover, food fried in the high-oleic low-linolenic canola oil obtained the best scores in the sensory acceptance assessment.

Frying stability of high oleic sunflower oils as affected by composition of tocopherol isomers and linoleic acid content.

The influence of linoleic acid content and tocopherol isomeric composition on the frying performance of high oleic sunflower oil was evaluated during a 14-day restaurant style frying operation. At equal linoleic acid content, no significant difference was observed between high oleic sunflower oil containing only α-tocopherol and the sample containing a mixture of α-, γ-, and δ-isomers as measured by the amount of total polar components, oligomers, anisidine value, and free fatty acids. On the contrary, at similar tocopherol isomeric composition, high oleic sunflower oil containing lower amount of linoleic acid showed superior frying stability compared to the sample with a higher content of linoleic acid, suggesting that the frying performance of high oleic sunflower oil is dictated primarily by the level of linoleic acid, with the tocopherol isomeric composition of the oil having no significant influence. In all oil samples, the loss of γ-tocopherol was higher than the corresponding loss of α-tocopherol.

Formation of trans fats during food preparation.

PURPOSE: An investigation was completed to determine how typical cooking procedures used in food preparation, such as baking and stir-frying, affect trans fats formation. METHODS: Canola oil was used as the main fat ingredient. Zucchini cake and gingersnap cookies were baked at 180o C and 200o C, while stir-fried chicken was prepared at 200o C and 275o C. The lipids from the food were extracted following the Folch procedure, and analyzed for trans fatty acids according to ISO official method 15304. RESULTS: Minimal changes were observed in the amount of trans fats during baking. Application of extreme temperatures during baking, which caused carbonization of the outer layer of products, yielded an insignificant increase in the amount of trans isomers. As with baking, stir-frying did not result in significant isomerization of the fatty acids, even when the oil was heated to 275o C and smoking heavily before the food was placed in it. Irrespective of the cooking procedure, linolenic acid was the most prone to isomerization with the highest amount of trans isomers formation. CONCLUSIONS: Baking and stir-frying at normal and/or extreme temperatures do not significantly affect the amounts of trans fats. Likewise, heating oil to the smoking point during stir-frying may decrease the amount of polyunsaturated fatty acids because of oxidative degradation.

Synthesis, radical scavenging activity, protection during storage, and frying by novel antioxidants.

Novel antioxidants, derivatives of trolox, and selected phenolic acids have been prepared in good yields and fully characterized by (1)H NMR, (13)C NMR, and MS. Their antioxidant activities have been assessed by DPPH and ORAC assays, and during frying and accelerated storage tests. Novel phenolic compounds exhibited higher radical scavenging activities than both trolox and α-tocopherol. Trolox hydroxybenzoate showed a significantly higher protection than α-tocopherol under storage conditions. All new antioxidants performed better than α-tocopherol under frying conditions. Moreover, their outstanding thermal stability makes them more valuable than α-tocopherol for frying applications.

Anti-inflammatory and antioxidant activities and constituents of Platostoma africanum P. Beauv.

Hexane and dichloromethane extracts of Platostoma africanum P. Beauv., a plant popularly employed in Nigeria in the treatment of rheumatic symptoms, were evaluated for anti-inflammatory and antioxidant activities. Acute inflammatory effects were studied in the egg-albumin-induced rat paw edema. Both extracts produced significant (p < 0.05) and dose-dependent inhibition of the egg-albumin-induced pedal edema with the 400 mg kg(-1) dose being markedly better than piroxicam. The hexane and dichloromethane extracts also showed significant antioxidant activity with the dichloromethane extract exhibiting an IC(50) comparable to that of BHT, a synthetic antioxidant. Phytochemical investigation of the extracts afforded eight acidic pentacyclic triterpenes, namely, ursolic acid, oleanolic acid, epimaslinic acid, maslinic acid, corosolic acid, hyptadienic, euscaphic acid and tomentic acid, and a mixture of beta-sitosterol and stigmasterol. These constituents are reported for the first time in the genus.

Sesquiterpenes from Culcasia scandens P. Beauv.

From Culcasia scandens P. Beauv., carota-4(5), 11(12)-diene (isodaucene), carota-3(4), 11(12)-dien-5-one, a new epoxide, 4,5-epoxy-carota-11(12)-ene (isodaucene epoxide) and beta-caryophyllene epoxide were isolated. The structures were established spectroscopically. Epoxidation of isodaucene with m-CPBA confirmed the structure and stereochemistry of the new epoxide.