Tests to monitor quality of deep‐frying fats and oils

There are dozens of tests an oil chemist has at his disposal for evaluating fresh and used frying oils. These include chemical tests, instrumental methods, physical methods and rapid tests. Not all are applicable to use when evaluating oils used for deep‐fat frying. Rather than run the gamut of all the tests available to the oil chemist or quality control technician, this presentation will focus on the different rapid tests that have been developed for the marketplace. These include physical tests, tests that measure physical parameters of the oil, and chemical tests. Tests may be quite simple or complex. The presenter will provide an overview on the different rapid test methods, but will emphasize that it is up to the researcher or the processor to evaluate for themselves whether the technology is something that they can use in their own operations.     

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.     

Factors affecting the concentration of acrylamide during deep‐fat frying of potatoes

The paper describes the effect of different factors influencing the concentration of acrylamide in deep‐fat fried potato products. In French fries the amount of acrylamide increased with the temperature as well as the frying time, especially at temperatures higher than 175 °C. The increase of acrylamide with the time followed a linear function, whereas a non‐linear relationship was given with the temperature of frying. As a result, a reduction of the processing temperature led to lower concentrations of acrylamide in the product. Both, oil type and silicon oil as antifoaming agents had no significant influence upon the acrylamide concentration in the food. The variety of potatoes had a strong effect on the acrylamide concentration in potato crisps and French fries. The investigation showed a significant correlation (r = 0.73) between the concentration of acrylamide and reducing sugars in raw potatoes, and no significant correlation with the asparagine concentration. The storage temperature of the raw material had an effect on the acrylamide concentration in the product. Lowering of the storage temperature from 8 to 4 °C resulted in an increase of the concentration of reducing sugars in the raw material, which led to a higher potential of acrylamide formation in the products. The experiments showed that the acrylamide concentration of French fries depended on the surface‐to‐volume ratio (SVR).     

Formation of short‐chain glycerol‐bound oxidation products and oxidised monomeric triacylglycerols during deep‐frying and occurrence in used frying fats

Heating fats and oils at high temperature in the presence of air, a common procedure in culinary practices such as frying, results in a complex mixture of oxidation products. These compounds may impair the nutritional value of the food. Among them, there is a growing interest in the group of oxidised triacylglycerol monomers because of their high absorbability. The main structures in this group include triacylglycerols (TG) containing short‐chain acyl groups formed by homolytic β‐scission of the alkoxy radicals coming from allylic hydroperoxides. In addition there are TG containing oxidised fatty acyl groups of molecular weight similar to that of their parent TG, i.e., epoxy, keto and hydroxy fatty acyl groups. In this review, the main routes of formation of oxidised TG monomers are detailed. Also, the most relevant advances in the analysis of intact TG molecules by high‐performance liquid chromatography coupled with mass spectrometry are discussed. Special attention is paid to the present analytical possibilities for accurate quantification of the most important oxidised compounds formed at high temperature. Both the need to convert fats and oils into simpler derivatives, thus concentrating the compounds bearing the oxidised structure, and the methylation procedure selected to avoid artefact formation are justified. Typical concentrations of short‐chain fatty acids, short‐chain aldehydic acids, short‐chain diacids, and monoepoxy fatty acids, ketoacids and hydroxyacids in frying oils from restaurants and fried‐food outlets, with polar lipids levels at the limit of rejection for human consumption, are given.     

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.     

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.     

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.     

Analysis of acrylamide and mechanisms of its formation in deep‐fried products

A reliable and sensitive gas chromatography‐mass spectrometry method was developed for the determination of acrylamide, a toxic compound recently discovered in baked, fried or grilled food. Satisfactory results for repeatability and recoveries were obtained by this method. The limit of detection for acrylamide was 15 μg/kg food and recoveries were between 95 to 103%. The improved method was then employed to study the influence of heat, heating time and type of frying oil on the formation of acrylamide during the deep frying of French fries. In this matrix acrylamide formation was promoted by heating in a time‐dependent manner. It appeared that acrylamide arose, when reducing sugars, dimethylpolysiloxane or partial glycerides were present. Three mechanisms of formation are discussed in this context. Although the mechanistic complexity increases dramatically in the presence of various food components, some recommendations can be given to minimize acrylamide levels in deep fried products.     

Correlation between physicochemical analysis and radical‐scavenging activity of vegetable oil blends as affected by frying of French fries

The main goal of the present work was to compare and correlate the results of physicochemical parameters and antiradical performance of some oil blends during deep‐frying, which will be an initial indicator for applying antiradical tests for monitoring deep‐frying oils. Two oil blends were prepared. The first blend was a mixture (1 : 1, wt/wt) of sunflower seed oil and palm olein (SO/PO) and the second was a mixture (1 : 1, wt/wt) of cottonseed oil and palm olein (CO/PO). The oil blends were evaluated during intermittent frying of French fries on two consecutive days for 16 h, with oil replenishing after 8 h. Changes in the fatty acid profile and some physicochemical parameters (peroxide value, color index, viscosity, total polar compounds and UV absorbance at 232 and 270 nm) were used to evaluate the alterations during frying. A quick spectrophotometric method was developed to assess deep‐frying oil quality. With the 2,2‐diphenyl‐1‐picrylhydrazyl (DPPH) method, the neutralization of the stable radical DPPH by antioxidants present in the oil during frying was measured. Radical‐scavenging activity (RSA) of both oil blends was recorded during frying, wherein the results showed that the SO/PO blend had the highest RSA. It was evident from the results that a proportional correlation and positive relationship existed between the levels of fatty acids and the physicochemical characteristics of the vegetable oil blends and their RSA. The initial results obtained allow us to suggest that antiradical measurements could be used to quantify the oxidative and hydrolytic deterioration of vegetable oils upon frying.     

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.     

Synthesis and characterization of novel copolymers with the trimethylsilyl group for deep‐UV photoresists

N‐(4‐Acetoxyphenyl) maleimide (APMI) and three kinds of comonomers bearing a trimethylsilyl group were copolymerized at 60°C in the presence of azobisisobutyronitrile (AIBN) as an initiator in 1,4‐dioxane to obtain the three IP, IIP, and IIIP copolymers. These copolymers were removed from the acetoxy group in a transesterification process into new IVP, VP, and VIP copolymers with a pendant hydroxyl group. Two modified processes were adopted to prepare photoresists using these copolymers. The first process involved mixing the dissolution inhibitor, o‐nitrobenzyl cholate, with the new copolymers. Second, o‐nitrobenzyl cholate was introduced into the copolymers using 1,8‐diazabicyclo[5.4.0]undec‐7‐ene (DBU) in dimethylformamide (DMF). The cyclic maleimide structure is responsible for the high thermal stability of these copolymers. After irradiation using deep–UV light and development with aqueous Na₂CO₃ (0.01 wt %), the developed patterns showed positive images and exhibited good adhesion to the silicon wafer without using any adhesion promoter. The resolution of these resists was at least 0.8 μm and an oxygen‐plasma etching rate was 1/5.3 to that of hard‐baked HPR‐204. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 83: 2791–2798, 2002; DOI 10.1002/app.10255