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.     

Effects of natural and synthetic antioxidants on changes in refined, bleached, and deodorized palm olein during deep-fat frying of potato chips

The effects of antioxidants on the changes in quality characteristics of refined, bleached, and deodorized (RBD) palm olein during deep-fat frying (at 180°C) of potato chips for 3.5 h/d for seven consecutive days in five systems were compared in this study. The systems were RBD palm olein without antioxidant (control), with 200 ppm butylated hydroxytoluene (BHT), 200 ppm butylated hydroxyanisole (BHA), 200 ppm oleoresin rosemary, and 200 ppm sage extract. Fried oil samples were analyzed for peroxide value (PV), thiobarbituric acid (TBA) value, iodine value (IV), free fatty acid (FFA) content, polymer content, viscosity, E^1% _{1 cm} at 232 and 268 nm, color, fatty acid composition, and C_18:2/C_16:0 ratio. Sensory quality of the potato chips fried in these systems prior to storage was also evaluated. The storage stability of fried potato chips for 14 wk at ambient temperature was also determined by means of the TBA values and sensory evaluation for rancid odor. Generally, in the oil, oleoresin rosemary gave the lowest rate of increase of TBA value, polymer content, viscosity, E^1% _{1 cm} at 232 and 268 nm compared to control and three other antioxidants. The order of effectiveness (P<0.05) in inhibiting oil oxidation in RBD palm olein was oleoresin rosemary > BHA > sage extract > BHT > control. Prior to storage, the sensory evaluation of fried potato chips for each system showed that there was no significant (P>0.05) difference in terms of flavor, odor, texture, and overall acceptability. The same order of effectiveness (P<0.05) of antioxidants was observed for storage stability study of fried potato chips by TBA values. However, there was no significant (P > 0.05) difference in sensory evaluation for rancid odor during storage periods.     

Effectiveness of antioxidants in refined,bleached avocado oil

The addition of antioxidants propyl gallate (PG), α-tocopherol and ethoxyquin at a level of 250 ppm to refined, bleached avocado oil resulted in the retardation of the oxidative deterioration of the oil when it was stored in the dark at room temperature, exposed to daylight at room temperature (on the shelf) and at 60 C. The extent of oxidation was followed by measuring the peroxide and anisidine values and oil color. Ethoxyquin and α-tocopherol were relatively ineffective antioxidants, whereas PG greatly improved the stability of avocado oil stored in the dark at 60 C, but not in oil exposed to daylight.     

Effect of various packaging materials on storage stability of refined,bleached, deodorized palm oil

Refined, bleached, deodorized palm oil (RBD palm oil) was packaged in lacquered metal cans (LMC), green glass bottles (GGB), amber glass bottles (AGB), clear glass bottles (CGB), clear plastic bottles (CPB) and sealed polyethylene film (POLET), and stored in direct sunlight (40 ± 1°C) or in darkness (27 ± 1°C). Measurements of free fatty acid (FFA), peroxide value and anisidine value, at 14-day intervals for a period of 98 days, were used to assess the stability of the oil towards hydrolytic and oxidative deterioration. Total oxidation values for packaged oils stored in direct sunlight showed that LMC gave the greatest protection against oxidative deterioration, followed by GGB and AGB. POLET offered the least protection to the oil against oxidative deterioration, while CPB and CGB proved superior to POLET but inferior to GGB and AGB. For storage in the dark, LMC, AGB and GGB gave the greatest protection to RBD palm oil against oxidative deterioration, with no significant statistical differences between them, while CPB, CGB and POLET followed in that order, with significant differences between their respective abilities to protect the oil against oxidative deterioration. Oils packaged in CPB gave the highest FFA levels (statistically significant). The investigations clearly indicated that LMC is superior to all other tested packaging materials in offering maximum protection to RBD palm oil against hydrolytic and oxidative deterioration. Amber and green glass bottles could serve as viable alternatives to LMC, while CGB and CPB could be tolerated as suitable packaging systems for RBD palm oil. However, the study also clearly showed that POLET is unsatisfactory for use as packaging material for RBD palm oil.     

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.     

Effect of antioxidants on refined palm oil

Alkali refined palm oil and hydrogenated cotton-seed oil were stabilized with butylated hydroxytoluene, butylated hydroxyanisole, and tertiary butylhydroquinone. Under bulk storage temperatures significant reductions in the peroxide formation of palm oil were obtained only with tertiary butyl-hydroquinone. The reduction in peroxide formation with tertiary butylhydroquinone was much greater than anticipated from the active oxygen method results. The stability improvement of a snack product fried in palm oil stabilized with tertiary butylhydroquinone depended greatly on the frying conditions used. Under mild frying conditions tertiary butyl-hydroquinone had somewhat greater carry-through than butylated hydroxytoluene. Under more severe frying conditions tertiary butylhydroquinone provided less protection than butylated hydroxytoluene. Both palm oil and hydrogenated cottonseed oil stabilized with only butylated hydroanisole had higher active oxygen stabilities than the unstabilized controls; however, no reduction in peroxide formation of the butylated hydroxyanisole oils compared to the controls was found during storage of the oil or the snack product at 50–60 C.     

Stability of tapioca chips fried in RBD palm olein treated with antioxidants

The effectiveness of tertiarybutylhydroquinone (TBHQ), butylated hydroxyanisole (BHA) and butylated hydroxytoluene (BHT) in stabilizing tapioca chips was assessed by determining the peroxide andp-anisidine values, absorbances at 232 nm and 268 nm and the 18:2/16:0 ratios of oil extracted from tapioca chips. The order of effectiveness of the antioxidants in stabilizing the chips was found to be TBHQ > BHT > BHA. The order of effectiveness of antioxidants, TBHQ > BHT > BHA, was maintained for chips from corresponding 1st, 4th and 7th fryings. The loss of antioxidants during storage could not be directly related to oxidation parameters.     

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.     

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.     

Industrial trial to evaluate the effect of oxygen concentration on overall quality of refined, bleached, and deodorized soybean oil in PET bottles

Soybean oil, owing to its FA composition, is highly susceptible to deterioration by oxidation. The use of nitrogen gas permits the removal of dissolved oxygen and oxygen in the headspace of tanks and bottles. The objective of this work (an industrial trial) was to evaluate the shelf life of soybean oil packaged in polyethylene terephthalate (PET) bottles with different levels of oxygen in the headspace (<0.3, 5–6.5, 7–9, and >15%). The quality of the oil was evaluated during 6 mon. FFA and moisture increased and the smoke point decreased in all experimental conditions, even though the difference between the experiments was not significant. An increase was observed for peroxide value (PV), anisidine value (AV), and specific extinction, and higher increases in these parameters were observed in higher oxygen concentrations. After 180 d, the difference between the PV and AV was significant. According to sensory analysis, the shelf life of the oil increased from 60 to 90, 120, and 180 d as the initial concentration of oxygen was reduced from >15%, 7–9%, 5–6.5%, and 0–3%, respectively. The results demonstrated that shelf life of soybean oil packaged in PET bottles can be significantly increased by using nitrogen to reduce available oxygen in the headspace.     

Enzymatic interesterification of palm stearin and palm kernel olein

Palm stearin (POs) and palm kernel olein (PKOo) blends were modified by enzymatic interesterification (IE) to achieve the physical properties of margarine fats. POs and PKOo are both products of the palm oil industry that presently have limited use. Rhizomucor miehei lipase (Lipozyme IM 60) was used to catalyze the interesterification of oil blends at 60°C. The progress of interesterification was monitored by following changes in triacylglyceride composition. At 60°C interesterification can be completed in 5 h. Degrees of hydrolysis obtained through IE for all blends were decreased from 2.9 to 2.0 by use of dry molecular sieves. The solid fat contents of POs/PKOo 30:70 and 70:30 interesterified blends were 9.6 and 18.1 at 20°C, and 0 and 4.1 at 35°C, respectively. The slip melting point (SMP) of POs/PKOo 30:70 was 40.0°C before interesterification and 29.9°C after IE. For POs/PKOs 70:30, SMP was 47.7 before and 37.5°C after IE. These thermal characteristics of interesterified POs/PKOo blend ratios from 30:70 to 70:30 were comparable to those of commercial margarines. Results showed that IE was effective in producing solid fats with less than 0.5% trans.     

Trans-free vanaspati containing ternary blends of palm oil-palm stearin-palm olein and palm oil-palm stearin-palm kernel olein

Four samples of trans-free vanaspati were made using palm oil-palm stearin-palm olein (PO-POs-POo) blends (set A) and another four samples (set B) using palm oil-palm stearin-palm kernel olein (PO-POs-PKOo). Palm stearin iodine value [iodine value (IV), 30] and soft palm stearin (IV, 44) were used in this study. The products were evaluated for their physical and chemical properties. It was observed that most of the vanaspati were granular (grainy) and had a shiny appearance. Chemical analyses indicated that vanaspati consisting of PO-POs-POo had higher IV (47.7–52.4) than the PO-POs-PKOo vanaspati (37.5–47.3). The higher IV demonstrated by set A samples was due to their higher content of unsaturated fatty acids, 46.0–50.0% compared to 36.6–45.0% in set B. Decreasing the amount of palm oil while increasing palm stearin in the formulations resulted in higher slip melting points and higher yield values. Eutectic interaction was observed in PO-POs-PKOo blends. The β′ crystalline form was predominent in PO-POs-POo samples (set A). One formulation in set B exhibited β crystallinity. From the differential scanning calorimetry thermograms, samples in set B showed a high peak at the low-melting region as well as a high peak at the high-melting region. In set A, the peak at the low-melting region was relatively lower.     

Separation and characterization of pigments from bleached and deodorized canola oil

An analysis of pigments responsible for color formation during bleaching and deodorization of canola oils treated with activated bleaching earth (ABE) or novel mineral-acid/silica (AS) adsorbents is presented. The chromophores are trace glycerides and were concentrated by silica column chromatography. The concentrated color bodies were hydrolyzed and analyzed as free acids or methyl esters by reversed-phase high-performance liquid chromatography with photodiode array and mass spectrometry detection,¹H and¹³C nuclear magnetic resonance and infrared spectroscopies. Absorbance in deodorized oils is mostly from oxygenated C18 and C20 fatty acids with 1 to 4 double bonds. High-wavelength absorbance in AS-bleached oils is from conjugated pentane fatty acids that are not observed for ABE-bleached oils. Thus, both the bleaching agent and the deodorization treatment affect the distribution and concentration of such stable chromophores.     

Determination of mono- and diglycerides in palm oil,olein and stearin

Partial glycerides are important constituents of palm oil and can have significant effects on the physical properties of products containing palm oil or on the fractionation of palm oil. A method is described for their routine determination in palm oil. By analysis of 28 weekly composite samples of crude palm oil the following results were obtained: free fatty acids, mean=3.76%, range 2.4 to 4.5%; monoglycerides, mean=0.28%, range 0.21 to 0.34%; diglycerides, mean=6.30%, range 5.3 to 7.7%. During detergent fractionation of palm oil, diglycerides concentrate in the palm olein, but monoglycerides concentrate in the palm stearin. Palm fatty acid distillate was found to contain approximately 3% each of mono- and diglycerides. Because the refining and fractionation processes are continuous in the refinery, it is not possible to follow a single identifiable batch of crude palm oil through the refinery. To circumvent this problem, crude palm oil, stearin and olein from the refinery were bleached and steam refined in the laboratory and the partial glyceride contents determined at each stage of processing. Except for fractionation, the content of glycerides did not change during processing. For oil, olein and stearin, monoglycerides were reduced significantly both after bleaching and after steam refining.     

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.     

Hydrolysis of palm olein catalyzed by solid heteropolyacids

The hydrolysis activity of superacids on palm olein, including tungstophosphoric acid and molybdophosphoric acid and their partially ion-exchanged cesium (Cs) salt, were investigated and compared with macroporous cation-exchanged resin and aluminum-incorporated mesoporous molecular sieve. The activities of the superacids supported on the resin and silica were also determined. The reactions were carried out in a stirred batch reactor with continuous steam injection at temperatures from 140 to 180°C. The reaction kinetics, obtained by regression, are first order with respect to TG of the superacids and Cs salts. Of the catalysts studied, the superacids loaded onto cation-exchanged resins were the most active on a weight basis. However, in terms of the turnover number per acid site, the Cs salt of tungstophosphoric acid had 13 times the activity of the cation-exchanged resin. The original superacids had lower activities than the Cs salts in terms of their turnover number. The observations are qualitatively in line with the higher acid strengths of the catalysts, as confirmed by the low activity of the aluminum silicate mesoporous molecular sieve, which is known to have a high concentration of low-to moderate-strength acid sites. The activation energy of the reaction with the Cs salts was ∼49 kJ mol⁻¹. This is rather low as compared to that catalyzed by the cation-exchanged resin.     

Transesterification kinetics of palm olein oil using supercritical methanol

Continuous transesterification of palm olein oil using supercritical methanol was investigated in the absence of a catalyst. The variables studied were reaction temperature (270–350 °C), pressure (20–40 MPa), and residence time (5–25 min), with a methanol-to-oil molar ratio of 40. Preheating at 245 °C was used to form a homogeneous phase in the absence of thermal decomposition of palm olein oil. The activation energies and reaction activation volumes of the fatty acid methyl ester (FAME), and those of the individual components (C16:0, C18:0, C18:1, and C18:2 methyl esters), were calculated. The entropies of activation (ΔS^‡) of the transesterification reactions were also obtained. As the transesterification of vegetable oil in supercritical methanol included a strongly negative (−175 J/mol K) entropy of activation, transesterification required harsh conditions.     

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.     

Enzymatic transesterification of palm olein with nonspecific and 1,3-specific lipases

The enzymatic transesterification of palm olein was conducted in a low-moisture medium with nonspecific and 1,3-specific lipases from microbial sources. The enzymes were first immobilized on Celite, lyophilized for 4 h and then added to a reaction medium that consisted of 10% (wt/vol) palm olein in water-saturated hexane. The catalytic performance of the enzymes was evaluated by determining the changes in triglyceride (TG) composition and concentrations by reverse-phase high-performance liquid chromatography (HPLC) and the formation of free fatty acids by titration. Studies with lipase fromCandida rugosa showed that the degree of hydrolysis was reduced by drying the immobilized preparation and that the best drying time was 4 h. In all cases, the transesterification process resulted in the formation of PPP, a TG initially undetected in the oil, and increases in the concentrations of OOO (1.3–2.1-fold), OOL (1.7–4.5-fold), and OLL (1.7–4.3-fold), where P, O, and L are palmitic, oleic, and linoleic acids, respectively. SOS (where S is stearic acid), another TG not detected in the oil, was synthesized byRhizomucor miehei andPseudomonas lipases, with the latter producing more of this TG. There was a corresponding decrease in the concentrations of POP, PLP, POO, and POL. PPP concentration ranged from 1.9% (w/w) forMucor javanicus lipase to 6.2% (w/w) forPseudomonas lipase after 24 h. The greatest degree and fastest rate of change were caused byPseudomonas lipase, followed by the enzymes fromR. miehei andAspergillus niger. The effects of transesterification and hydrolysis of palm olein by the various lipases resulted in changes in the overall degree of saturation of the triglyceride components. There seems to be no clear correlation between the enzyme positional specificity and the products formed. Possible mechanisms for the formation of PPP, OOL, OLL, OOO, and SOS are discussed.