Synergistic effects of rosemary, sage, and citric acid on fatty acid retention of palm olein during deep-fat frying

A study to optimize the use of oleoresin rosemary extract, sage extract, and citric acid in refined, bleached, and deodorized (RBD) palm olein during deep-fat frying of potato chips was performed using response surface methodology. Results showed that the natural antioxidants used in this study retarded oil deterioration, as evidenced by retention of fatty acid profiles. The linoleic to palmitic (C18∶2/C16∶0) ratio was chosen as the parameter for optimizing the use of natural antioxidants in RBD palm olein during deep-fat frying. Linoleic (R ²=0.946) and palmitic (R ²=0.825) acids were found to be the most important dependent variables, giving highest R ² values to various antioxidant treatments after 25 h of frying. All three antioxidants had independent significant (P<0.05) effects on the C18∶2/C16∶0 ratio. In fact, significant effects on the C18∶2/C16∶0 ratio of RBD palm olein were also given by a second-order form. A combination of 0.076% oleoresin rosemary extract, 0.066% sage extract, and 0.037% citric acid produced the optimal retention of the essential fatty acid C18∶2. In addition, a synergistic effect among these antioxidants on the fatty acid ratio of RBD palm olein was found.     

Use optimization of natural antioxidants in refined, bleached, and deodorized palm olein during repeated deep-fat frying using response surface methodology

An optimization study on the use of oleoresin rosemary extract, sage extract, and citric acid added into refined, bleached, and deodorized (RBD) palm olein in deep-fat frying of potato chips was carried out using response surface methodology (RSM). Results showed that oleoresin rosemary extract was the most important factor affecting the sensory acceptability of potato chips. For taste and odor, its effects were highly significant (P<0.01), while for crispiness and overall acceptability, the effects were significant (P<0.05). As for sage extract, the level of this antioxidant had a highly significant (P<0.01) effect on appearance and taste and a significant effect (P<0.05) on odor and overall acceptability, but had no effect on crispiness. Although there was no significant synergistic correlation between citric acid and oleoresin rosemary extract or sage extract at the first order, its second order was significantly (P<0.05) related to taste, crispiness, and overall acceptability. An interaction between oleoresin rosemary and sage extracts also significantly (P<0.05) improved the score of overall acceptability of the potato chips. Contour maps of the sensory scores of potato chips indicated that the optimal points for appearance were achieved using 0.062% oleoresin rosemary extract, 0.066% sage extract, and 0.023% citric acid, while optimal task was achieved with 0.063% oleoresin rosemary extract, 0.075% sage extract, and 0.025% citric acid. With the same sequence of ingredients added into oil, the combinations required to achieve the optimal odor, crispiness, and overall acceptability scores were 0.058-0.046-0.026, 0.060-0.071-0.022, and 0.060-0.064-0.026%, respectively.     

Effectiveness of antioxidants in refined,bleached and deodorized palm olein

The addition of antioxidants butylated hydroxytoluene (BHT), propyl gallate (PG), tertiary butylhydroquinone (TBHQ), dilaurylthiodipropionate (DLTDP), and trihydroxybutyrophenone (THBP) at a level of 200 ppm to refined, bleached and deodorized (RBD) palm olein resulted in the retardation of the oxidative deterioration of the oil when stored at 60 C for a period of 10 weeks. The extent of oxidative deterioration was determined by measuring the peroxide and anisidine values and E _{1 cm} ^1% at 232 nm and 268 nm of the oil. Butylated hydroxyanisole (BHA) proved to be a relatively ineffective antioxidant, whereas TBHQ afforded the most protection for the RBD olein.     

Efficacy of the antioxidants BHA and BHT in palm olein during heating and frying

The effectiveness of butylated hydroxyanisole (BHA) and butylated hydroxytoluene (BHT) in retarding the deterioration of RBD palm olein during static heating (180 C) and frying operations was assessed by determining the peroxide, anisidine, acid and iodine values; absorbances at 232 and 268 nm; and the fatty acid composition of the oil. During static heating of the oil, BHA was found to be a more effective antioxidant than BHT whereas, during intermittent frying of potato chips, both the antioxidants were relatively ineffective in retarding the deterioration of the oil. The loss of BHT from the oil during static heating exceeded that of BHA. On the other hand, when potato chips were fried in the oil periodically, a higher loss of BHA was observed.     

A fourier transform infrared spectroscopic method for determining butylated hydroxytoluene in palm olein and palm oil

A simple, rapid, and direct FTIR spectroscopic method was developed for the determination of BHT content in refined, bleached, and deodorized (RBD) palm olein and RBD palm oil. The method used sodium chloride windows with a 50-mm transmission path. Fifty stripped oil samples of both RBD palm olein and RBD palm oil were spiked with known amounts of BHT concentrations up to 300 mg/kg (ppm). The data were separated into two sets for calibration and validation using partial least squares models. FTIR results for both oils correlated well with results obtained by the IUPAC HPLC-based method. For RBD palm olein, the coefficient of determination (R ²) was 0.9907 and the SE of calibration (SEC) was 8.47 ppm. For RBD palm oil, an R ² of 0.9848 and an SEC of 10.73 ppm were achieved. Because of the significant decrease in analysis time and reduction in solvent usage, this FTIR method for BHT is especially well suited for routine quality control applications in the palm oil industry.     

Optimization of physicochemical changes of palm olein with phytochemical antioxidants during deep-fat frying

Response surface methodology (RSM) was used to optimize the amounts of rosemary and sage extracts together with citric acid as synergist antioxidants in stabilizing refined, bleached, and deodorized palm olein during repeated deep-fat frying of potato chips. For all physicochemical properties studied, these phytochemical antioxidant treatments significantly (P<0.05) reduced the oxidation rate of the oil. During 5 d of frying, anisidine value, peroxide value, free fatty acid, polymer content, color units, viscosity, and absorbances at 232 and 268 nm gradually increased, whereas iodine value and ratio of 18∶2/16∶0 decreased. Further statistical analyses, including coefficient of determination (R ²) and probability of F values, indicated that mathematical models for each physicochemical parameter could be developed confidently in this study, with R ² for all parameters greater than 0.90. These results suggested that an optimal mixture of phytochemical antioxidants derived from rosemary and sage together with citric acid could be produced using RSM for stabilizing thermally processed oil. For many physicochemical parameters examined, the use of moderate levels of antioxidants could result in optimal responses.     

Use of rosemary extract in preventing oxidation during deep-fat frying of potato chips

The effect of using a rosemary extract on the stability of oil used for frying potato chips has been evaluated. Sliced potatoes were fried intermittently in soybean oil containing a natural extract from rosemary. The conditions used for frying were 185°C for 90 s. Two separate experiments, with and without replenishment of oil, were carried out. Oil samples were taken each day, not only from the frying pans but also by extraction with hexane from the chips. Changes in the induction period of the oil samples (Rancimat method) were determined. The induction period decreased as frying progressed. The reduction in the induction period was higher in the oil free of rosemary extract, and the chips were much darker in color. The oil containing the extract showed greater antioxidant activity, and reduced darkening and rancidity of the oil. Potato chips fried in the oil with added rosemary extract were more acceptable than chips fried in oil containing no extract until the last frying. The free radical scavenging activity of rosemary extract in comparison to other natural antioxidants was also determined by the reduction of O₂ ^.- in a hypoxanthine/xanthine oxidase system.     

Composition and thermal profile of crude palm oil and its products

Gas-liquid chromatography and high-performance liquid chromatography (HPLC) were used to determine fatty acids and triglyceride (TG) compositions of crude palm oil (CPO), refined, bleached, and deodorized (RBD) palm oil, RBD palm olein, and RBD palm stearin, while their thermal profiles were analyzed by differential scanning calorimeter (DSC). The HPLC chromatograms showed that the TG composition of CPO and RBD palm oil were quite similar. The results showed that CPO, RBD palm oil, RBD olein, and superolein consist mainly of monosaturated and disaturated TG while RBD palm stearin consists mainly of disaturated and trisaturated TG. In DSC cooling thermograms the peaks of triunsaturated, monosaturated and disaturated TG were found at the range of −48.62 to −60.36, −25.89 to −29.19, and −11.22 to −1.69°C, respectively, while trisaturated TG were found between 13.72 and 27.64°C. The heating thermograms of CPO indicated the presence of polymorphs β₂′, α, β₂′, and β₁. The peak of CPO was found at 4.78°C. However, after refining, the peak shifted to 6.25°C and became smaller but more apparent as indicated by RBD palm oil thermograms. The heating and cooling thermograms of the RBD palm stearin were characterized by a sharp, high-melting point (high-T) peak temperature and a short and wide low-melting point (low-T) peak temperature, indicating the presence of occluded olein. However, for RBD palm olein, there was only an exothermic low-T peak temperature. The DSC thermograms expressed the thermal behavior of various palm oil and its products quite well, and the profiles can be used as guidelines for fractionation of CPO or RBD palm oil.     

Chemical and Sensory Characteristics of Products Fried in High-Oleic,Low-Linolenic Rapeseed Oil

The effects of frying Berlin doughnuts and potato crisps in high-oleic, low-linolenic (HOLL) rapeseed oil were compared to other commonly used oils (i.e., palm olein, high-oleic sunflower oil, or partially hydrogenated oils). The chemical parameters characterizing the oxidative state of the products fried in HOLL were comparable to products being fried in other commonly used oils. The sensory characteristics of potato crisps fried in HOLL rapeseed oil were satisfactory and comparable to products fried in the other oils. Potato crisps were stable under nitrogen atmosphere for 20 weeks as measured by sensory quality scores. However, a storage time of 16 weeks was achieved for products stored under normal atmosphere. The suitability of HOLL rapeseed oil to improve the storage stability of Berlin doughnuts was limited. The sensory quality decreased during storage due to the development of abnormal taste and smell. Changes in the sensory quality were comparable to the results of the partially hydrogenated oils but worse for products fried in palm olein. Nevertheless, HOLL was a good alternative to partially hydrogenated oils as a frying medium.     

Colorimetric determination of total tocopherols in palm oil,olein and stearin

By using a preliminary heat-bleach at 250 C the Emmerie-Engel method has been adapted for the determination of total tocopherols (including tocotrienols) in crude as well as refined palm oil, olein and stearin. Total tocopherol contents found were: Crude palm oil, 794 ppm (n=10); RBD palm oil, 563 ppm (n=13); RBD palm olein, 643 ppm (n=40); RBD palm stearin, 261 ppm (n=19), where n is the number of samples analyzed. During the detergent fractionation no tocopherols were lost, but the tocopherols were concentrated in the olein fraction. The fate of the tocopherols during degumming, bleaching and steam refining/deodorizing of Crude palm olein containing 978 ppm total tocopherol was studied. Over the whole refining process only 8% of the tocopherols were lost, 62% of the original tocopherols were retained in the RBD palm olein, while the remaining 30% were concentrated in the fatty acid distillate which contained 7,040 ppm tocopherol.     

Studies on phytosterol oxides. I: Effect of storage on the content in potato chips prepared in different vegetable oils

Potato chips fried in palm oil, sunflower oil, and high-oleic sunflower oil were studied for the content of different phytosterol oxides during 0 to 25 weeks of storage in the dark. Oxidation products of sitosterol (24α-ethyl-5-cholesten-3β-ol) and campesterol (24α-methyl-t-cholesten-3β-ol) were synthesized to help identify the phytosterol oxides. The oxides of phytosterols were analyzed by preparative thin-layer chromatography, solid-phase extraction, capillary column gas chromatography (GC), and GC-mass spectrometry. Epimers of 7-hydroxysitosterol and 7-hydroxycampesterol; 7-ketositosterol and 7-ketocampesterol; epimers of 5,6-epoxy-sitosterol and 5,6-epoxy-campesterol; 24α-ethylcholestane-3β,5,6β-triol (dihydroxysitosterol) and 24α-methylcholestane-3β,5,6β-triol (dihydroxycampesterol) were detected and quantitated in the samples of chips fried in different vegetable oils. Potato chips fried in palm oil had the lowest level of total sterol oxides, ranging from 5 to ca. 9 ppm in the lipids from time 0 to 25 wk of storage. The level of total sterol oxides in chip samples fried in sunflower oil ranged from 46 to 47 ppm, and the lipids in samples fried in high-oleic sunflower oil ranged from 35 to 58 ppm from 0 time to 25 wk of storage. During 25 wk of storage no considerable increase in sterol oxides was observed in the samples of chips fried in palm oil and sunflower oil. The chip samples fried in high-oleic sunflower oil had slightly higher levels of sterol oxides after 10 and 25 weeks of storage. In addition to the levels of individual sterol oxides, a new method for enrichment of phytosterol oxides from the unsaponifiables and full-scan mass spectra of various oxidation products of sitosterol and campesterol are reported in this paper. Part of the results were presented at the 86th Annual Meeting of the AOCS, May 7–11, 1995, San Antonio, TX.     

Synergies between plant antioxidant blends in preventing peroxidation reactions in model and food oil systems

A study was conducted to investigate the oxidative behavior of various mixtures of rosemary, sage, and citric acid in a linoleic acid model system by oxygen consumption measurement and in a palm olein system by differential scanning calorimetry (DSC) analysis. Response surface methodology was used to optimize the use of the mixtures. Results showed that rosemary and sage were two important factors for the protective index (PI). The two antioxidants were highly significantly (P<0.001) in influencing PI values. There was a significant (P<0.01) synergistic effect between rosemary and sage on PI values. Citric acid was also found to be significant (P<0.05) for PI. With respect to onset time (T _o ), all three antioxidants were significant (P<0.05). However, no significant interaction among antioxidants was found for T _o . Mathematical models for both PI and T _o could be developed with confidence. The R ² values for PI and T _o were 0.992 and 0.926, respectively. A combination of 0.078% rosemary, 0.067% sage and 0.037% citric acid was the optimal combination for PI, whereas a combination of 0.068% rosemary, 0.075% sage, and 0.039% citric acid was required to reach the optimal T _o value.     

Addition of ferulic acid,ethyl ferulate,and feruloylated monoacyl- and diacylglycerols to salad oils and frying oils

To determine antioxidative effects of ferulic acid and esterified ferulic acids, these compounds were added to soybean oils (SBO), which were evaluated for oxidative stability and frying stability. Additives included feruloylated MAG and DAG (FMG/FDG), ferulic acid, ethyl ferulate, and TBHQ. After frying tests with potato chips, oils were analyzed for retention of additives and polar compounds. Chips were evaluated for hexanal and rancid odor. After 15 h frying, 71% of FMG/FDG was retained, whereas 55% of ethyl ferulate was retained. TBHQ and ferulic acid levels were 6% and <1%, respectively. Frying oils with ethyl ferulate or TBHQ produced significantly less polar compounds than SBO with no additives. Chips fried in SBO with TBHQ or ferulic acid had significantly lower amounts of hexanal and significantly less rancid odor after 8 d at 60°C than other samples. Oils were also aged at 60°C, and stability was analyzed by PV, hexanal, and rancid odor. Oils with TBHQ or FMG/FDG had significantly less peroxides and hexanal, and a lower rancid odor intensity than the control. FMG/FDG inhibited deterioration at 60°C, whereas ethyl ferulate inhibited the formation of polar compounds in frying oil. Ferulic acid acted as an antioxidant in aged fried food. TBHQ inhibited oil degradation at both temperatures. Presented at the 94th AOCS Meeting & Expo, Kansas City, MO, May 4–7, 2003.     

Determination of free fatty acids in crude palm oil and refined-bleached-deodorized palm olein using fourier transform infrared spectroscopy

A rapid direct Fourier transform infrared (FTIR) spectroscopic method using a 100 μ BaF₂ transmission cell was developed for the determination of free fatty acid (FFA) in crude palm oil (CPO) and refined-bleached-deodorized (RBD) palm olein, covering an analytical range of 3.0–6.5% and 0.07–0.6% FFA, respectively. The samples were prepared by hydrolyzing oil with enzyme in an incubator. The optimal calibration models were constructed based on partial least squares (PLS) analysis using the FTIR carboxyl region (C=O) from 1722 to 1690 cm⁻¹. The resulting PLS calibrations were linear over the range tested. The standard errors of calibration (SEC) obtained were 0.08% FFA for CPO with correlation coefficient (R ²) of 0.992 and 0.01% FFA for RBD palm olein with R ² of 0.994. The standard errors of performance (SEP) were 0.04% FFA for CPO with R ² of 0.998 and 0.006% FFA for RBD palm olein with R ² of 0.998, respectively. In terms of reproducibility (r) and accuracy (a), both FTIR and chemical methods showed comparable results. Because of its simpler and more rapid analysis, which is less than 2 min per sample, as well as the minimum use of solvents and labor, FTIR has an advantage over the wet chemical method.     

Effect of TBHQ on quality characteristics of RBD olein during frying

The changes in quality characteristics of refined, bleached and deodorized palm olein (RBD olein) during heating with intermittent frying for 5 hr/day for weight consecutive days in three systems were compared. The systems were (i) RBD olein without antioxidant (system 1); (ii) RBD olein to which 200 ppm of tertiary butylhydroquinone (TBHQ) had been added prior to frying on the first day (system 2), and (iii) RBD olein which had TBHQ added to a level of 200 ppm at the start of each day. The addition of TBHQ reduced the level of polar components and polymers in the oil, decreased the rates of change in iodine value and dielectric constant and decreased the rate of oxidation of C18:2. The reduction in the rates of these undesirable changes was more pronounced when the TBHQ was added to the system on each day of frying than when there was a single addition of TBHQ prior to frying on the first day. The undesirable effect of adding TBHQ was that it darkened the oil.     

Studies on Quality of Coconut Oil Blends after Frying Potato Chips

The quality (chemical and sensory) of oil blends prepared by blending equal proportions of coconut oil with sesame oil (blend 1), coconut olein with sesame oil (blend 2) and coconut olein with palmolein (blend 3) was evaluated after deep-fat frying of potato chips. After frying, the free fatty acid content did not change, however, the anisidine value increased. Blend 2 had the highest anisidine value (44.0). A marginal decrease in the iodine value and an increase in the diene values were observed in blends 1 and 2. The β-carotene content in blend 3 and tocols in all the three blends were found to decrease after frying. Sensory odor profiles of oil blends after frying showed a decrease in the characteristic coconut oil aroma. The earthy and seedy aroma associated with sesame oil was found to decrease on frying. The sensory profile of potato chips showed a slight bitter taste in the samples fried in blends 1 and 2. However, the intensity of bitterness decreased and the earthy note increased on storage. Blend 3 had the highest overall quality.     

Frying Quality Characteristics of French Fries Prepared in Refined Olive Oil and Palm Olein

The objective of this study was to compare two oils with different polyunsaturated/saturated (P/S) fatty acid ratios, refined olive oil (P/S 0.75) and palm olein (P/S 0.25), in frying French fries. The chemical qualities of the oil residues extracted from the French fries were assayed for five consecutive batches fried at 1-h intervals. The levels of total polar compounds, free fatty acids, p-anisidine value and phytosterol oxidation products (POPs) were elevated in French fries fried in both oils. The level of total polar compounds increased from 4.6 in fresh refined olive oil to 7.3% in final batches of French fries. The corresponding figures for palm olein were 9.8–13.8%. The level of free fatty acid in fresh refined olive oil increased from 0.06 to 0.11% in final products. These figures for palm olein were 0.04–0.13%. The p-anisidine value increased from 3.7 to 32.8 and 2.5 to 53.4 in fresh oils and in final batches of French fries in refined olive oil and palm olein, respectively. The total amount of POPs in fresh refined olive oil increased from 5.1 to 9.6 μg/g oil in final products. These figures were 1.9 to 5.3 μg/g oil for palm olein.     

Effect of natural antioxidants in virgin olive oil on oxidative stability of refined,bleached, and deodorized olive oil

The factors influencing the oxidative stability of different commercial olive oils were evaluated. Comparisons were made of (i) the oxidative stability of commercial olive oils with that of a refined, bleached, and deodorized (RBD) olive oil, and (ii) the antioxidant activity of a mixture of phenolic compounds extracted from virgin olive oil with that of pure compounds andα-tocopherol added to RBD olive oil. The progress of oxidation at 60°C was followed by measuring both the formation (peroxide value, PV) and the decomposition (hexanal and volatiles) of hydroperoxides. The trends in antioxidant activity were different according to whether PV or hexanal were measured. Although the virgin olive oils contained higher levels of phenolic compounds than did the refined and RBD oils, their oxidative stability was significantly decreased by their high initial PV. Phenolic compounds extracted from virgin olive oils increased the oxidative stability of RBD olive oil. On the basis of PV, the phenol extract had the best antioxidant activity at 50 ppm, as gallic acid equivalents, but on the basis of hexanal formation, better antioxidant activity was observed at 100 and 200 ppm.α-Tocopherol behaved as a prooxidant at high concentrations (>250 ppm) on the basis of PV, but was more effective than the other antioxidants in inhibiting hexanal formation in RBD olive oil.o-Diphenols (caffeic acid) and, to a lesser extent, substitutedo-diphenols (ferulic and vanillic acids), showed better antioxidant activity than monophenols (p- ando-coumaric), based on both PV and hexanal formation. This study emphasizes the need to measure at least two oxidation parameters to better evaluate antioxidants and the oxidative stability of olive oils. The antioxidant effectiveness of phenolic compounds in virgin olive oils can be significantly diminished in oils if their initial PV are too high.     

Review of stability measurements for frying oils and fried food flavor

Measurements of degradation in frying oils based on oil physical properties and volatile and nonvolatile decomposition products were reviewed. Rapid methods by means of test kits were also considered. Factors that affect the analysis of total polar components (TPC) in frying oils were examined. Relationships between TPC, free fatty acid (FFA) content, Food Oil Sensor readings (FOS), color change (ΔE), oil fry life and fried-food flavor were evaluated. Flavor scores for codfish, fried in fresh and discarded commercial frying oil blends, were dependent upon individuals in the consumer panel (n=77). Part (n=29) of the panel preferred the flavor of fresh fat; others (n=24) didn't; the rest (n=24) had no preference. FFA, FOS and TPC were analyzed in two soybean oils and in palm olein during a four-day period in which french fries were fried. Flavor score and volatiles of potatoes fried on days 1 and 4 in each oil were also determined. TPC, FFA and FOS significantly increased (P<0.05) in all oils during the frying period. TPC and FFA were highest in the used palm olein, and flavor of potatoes fried in palm olein on day 1 was less desirable than those fried in the soybean oils. Potatoes fried in day-1 oils had significantly higher concentrations (P<0.10) of several pyrazines and aldehydes than those fried in day-4 oils. Presented at the 84th Annual Meeting of the American Oil Chemists' Society, Anaheim, California, April 25–29, 1993.     

Frying Stability of Purified Mid-Oleic Sunflower Oil Triacylglycerols with Added Pure Tocopherols and Tocopherol Mixtures

To determine the effects of the addition of pure tocopherols to triacylglycerols, α, γ, and δ tocopherols were added singly and in various combinations to stripped mid-oleic sunflower oil (SMOSUN). Tortilla chips were fried in the treated oils and then aged at ambient temperature to determine storage stability of the fried food. Frying oils were evaluated for total polar compounds (TPC) as an indicator of oil deterioration, and they were also analyzed for retention of tocopherols. To determine effects of tocopherols on fried-food stability, chips were evaluated for hexanal as an indicator of oxidative stability and for odor characteristics by a trained, experienced analytical sensory panel. Oils extracted from the tortilla chips were also analyzed for residual tocopherols. TPC were highest in the SMOSUN control with no additives followed by the SMOSUN containing only α tocopherol. The SMOSUN oil containing γ tocopherol had the best fry life as indicated by the lowest TPC. Hexanal content and rancid odor intensity were highest in the chips fried in the SMOSUN control and in the SMOSUN containing only α tocopherol. The most stable tortilla chips were fried in SMOSUN containing all three (α, γ, and δ) tocopherols; however, the lowest hexanal levels were measured when γ and δ tocopherols were added at their highest concentrations.