Utilization of green seed canola oil for in situ epoxidation

Green seed canola oil is underutilized for edible purposes due to its high chlorophyll content, which makes it more susceptible to photo‐oxidation and ultimately reduces the oxidation stability. The present work is an attempt to compare the kinetics of epoxidation of crude green seed canola oil (CGSCO) and treated green seed canola oil (TGSCO) with peroxyacids generated in situ in presence of an Amberlite IR‐120 acidic ion exchange resin (AIER) as catalyst. Among the two oxygen carrier studied, acetic acid was found to be a better carrier than the formic acid, as it gives 8% more conversion of double bond than the formic acid. A detailed process developmental study was then performed with the acetic acid/AIER combination. For the oils under investigation parameters optimized were temperature (55°C), hydrogen peroxide to double bond molar ratio (2.0), acetic acid to double bond molar ratio (0.5), and AIER loading (15%). An iodine conversion of 90.33, 90.20%, and a relative epoxide yield of 90, 88.8% were obtained at the optimum reaction conditions for CGSCO and TGSCO, respectively. The formation of the epoxide product of CGSCO and TGSCO was confirmed by Fourier Transform IR Spectroscopy (FTIR) and NMR (1H NMR) spectral analysis.     

Antioxidant Activities of Free and Liposome-Encapsulated Green tea extracts on canola oil oxidation stability

In the present study, green tea extract was encapsulated in liposomes based on the Mozafari method (with no organic solvents) and characterized for its physicochemical properties (encapsulation efficiency, particle size, and Z-potential). Encapsulation efficiency, particles size, and Z-potential were determined to be 51.34, 419 nm, and -57 mV, respectively. Total polyphenol content of the green tea by Folin-Ciocalteu's phenol reagent was measured as 164.2 mg gallic acid/g extract. Free radical scavenging activities of free and liposomal extracts were 90.6 and 93.4%, respectively, using the DPPH method. Antioxidant activity of the ethanolic extract of green tea in free and liposomal forms with concentrations of 200, 600, and 1000 mg L⁻¹ were assessed on oxidative stability of the canola oil at 60 °C for 0, 4, 8, 12, 16, 20, 24, 28, and 32 days. Results were compared to results of synthetic antioxidant butylated hydroxytoluene at 200 mg L⁻¹. To assess antioxidant activity on canola oil stability, peroxide, thiobarbitoric acid, and anisidine values were assessed as well as the total oxidation value and rancimat test. Results showed that the liposomal green tea extract was more effective than the free extract. Furthermore, a 600 mg L⁻¹ concentration of the green tea extract showed a significant antioxidant activity, compared to other extract concentrations. Increasing storage time and various concentrations of the ethanolic green tea extracts included significant effects on canola oil stability (P ≤ 0.05). Results demonstrated that the green tea extract could be used as an effective antioxidant. Free and liposomal extract (at 600 mg L⁻¹) resulted in stronger functionality than the synthetic antioxidant butylated hydroxytoluene.     

红茶、绿茶提取物联合应用的护肤功效研究

以红茶提取物、绿茶提取物为考察对象,考察了红茶提取物和绿茶提取物的单独及联合应用的防晒、保湿、抗氧化、美白、抗衰老等功能,测试了二者在以上功能联合应用是否具有协同增效作用。结果表明,红茶、绿茶提取物在保湿、抗氧化、美白、抗衰老等功能上,联合应用比二者单独应用效果更强,其中2 g/L红、绿茶提取物混合物在抑制酪氨酸酶、弹性蛋白酶方面的联合指数CI仅为0.29和0.054,协同增效效果显著。     

Utilization of green seed canola oil for biodiesel production

Increasing percentage of green canola seed every year is a serious problem for canola growers. Chlorophyll content of this oil is very high, which makes it more susceptible to photo‐oxidation and ultimately the oxidation stability of the oil is very reduced. Hence green seed canola oil is underutilized for edible purposes. The present work is an attempt to produce high‐quality biodiesel from green seed canola oil and methanol, ethanol and various mixtures of methanol and ethanol using KOH as a catalyst. A mixture of alcohols improved the rate of reaction. After transesterification of green seed canola oil using KOH, the chlorophyll content of the oil was decreased substantially (from 22.1 ppm to 10.3 ppm). Characteristics of the esters prepared from green seed canola oil were well within the limits of ASTM standards. Lubricity of the green seed oil esters was excellent (20% decrease in wear scar area) when added at 1 vol% to the base fuel. Oxidation stability is crucial for long‐term storage of the fuel. Oxidation stability index (OSI) of green seed esters was 4.9 h at 110 °C, which is much less than the European Standard (6 h at 100 °C). The low oxidation stability of green seed esters is attributed to its higher chlorophyll (10.3 ppm) content. An attempt was also made to reduce the chlorophyll content of the oil before transesterification using activated carbon treatment, and it was observed that chlorophyll content was reduced from 22.1 to 2.2 ppm. Copyright © 2006 Society of Chemical Industry     

Effect of baicalein and acetone extract of Scutellaria baicalensis on canola oil oxidation

There is an increasing interest in natural antioxidants present in traditional Chinese herbal medicines. The present study examined the antioxidant activity of heane, acetone, and methanol extracts, as well as baicalein purified from the dry roots of Scutellaria baicalensis Georgi (common name: Huangqin), in heated canola oil. Oxygen consumption and decreases in linoleic acid linolenic acid content were monitored in canola oil held at 90–93°C. Among the three extracts, the acetone extract was most effective against oxidation of canola oil, followed by the methanol extract of the dry roots. The antioxidant activity of these three extracts correlated well with their content of baicalein, which provided strong protection to canola oil from oxidation. The antioxidant activity of Huangqin acetone extract was dose-dependent. The acetone extract at 100 ppm or above was even more effective than butylated hydroxytoluene at 200 ppm in protecting canola oil from oxidation. The present results suggest that the acetone extract of these roots should be further explored as a potential source of natural antioxidants for use in the processed foods.     

Solvent effects on phase transition behavior of canola oil sediment

Differential scanning calorimetry (DSC) was used to study the melting and crystallization behavior of waxy sediment in canola oil and in mixtures (1:1, w/w) of oil and acetone or hexane under dynamic heating/cooling regimes. In the presence of a solvent, the DSC melting peak of sediment shifted to lower temperatures, suggesting that sediment was more soluble in the solvent/oil systems than in oil alone. This effect was greater with hexane than with acetone. The influence of a solvent on crystallization was more complex. With inclusion of hexane, the crystallization temperature of sediment was always lower than that in oil. With acetone, however, the crystallization temperature of sediment was slightly lower at high sediment content, but higher at low sediment content than in oil alone. The differences in melting and crystallization behavior of sediment in canola oil and the solvent/oil systems were attributed to solubility and viscosity effects. Variation in the crystalline solid structures of sediment was not evident from the melting enthalpies associated with the phase transformation.     

Possible causes for decreased stability of canola oil processed from green seed

Canola oil extracted from seeds with a high-chlorophyll content can contain chlorophyll derivatives in excess of 30 ppm. When processed, this oil has been observed to be less stable than oil (typically containing 5 to 25 ppm chlorophyll) processed from high-grade seed. Possible causes for this phenomenon were investigated in this study. The effect of initial pheophytin content was examined by mixing fully saturated oil (tricapryloylglycerol) with increasing amounts of pheophytin and then by subjecting the mixtures to processing conditions. When the processed oils were combined with an unsaturated oil (canola oil), the oxidative stabilities decreased as the pre-processing content of pheophytin increased. Examination of the effect of increased bleaching to remove excessive levels of pheophytin showed that oil stability decreased with increasing exposure to bleaching clay. Additionally, processing treatments did not remove secondary autoxidation products from oil that was abused prior to processing. Such a finding revealed the importance of initial oil quality on processed oil stability, i.e., the greater abuse of the crude oil (resulting in greater contents of secondary oxidation products), the lower the stability of the processed oil. Finally, previous reports by other researchers of pheophytin's pro-oxidative effect in oil stored in light were confirmed.     

Chlorophyllase biocatalysis in an aqueous/miscible organic solvent medium containing canola oil

Chlorophyllase catalyzes the bioconversion of chlorophyll into chlorophyllide by replacing the phytol group with a hydrogen atom. There is an increased interest in the biotechnological application of chlorophyllase for the removal of green pigments from edible oil and its potential as an alternative to the use of the conventional bleaching technique. Partially purified chlorophyllase, obtained from the alga Phaeodactylum tricornutum, was assayed for its hydrolytic activity in an aqueous/miscible organic solvent system containing refined-bleached-deodorized (RBD) canola oil, using chlorophyll and pheophytin as substrate models. The results indicated that chlorophyllase biocatalysis could be successfully carried out in an aqueous/miscible organic system containing RBD canola oil. The presence of 20% RBD canola oil decreased the hydrolytic activity of chlorophyllase by 2.2 and 6.7 times, using chlorophyll and pheophytin as substrates, respectively. In addition, acetone acted as an activator of chlorophyllase activity at low concentrations and an inhibitor at higher ones. The optimal reaction conditions for chlorophyllase biocatalysis in the aqueous/miscible organic system were determined to consist of 20% RBD oil and 10% acetone at a 200 rpm agitation speed and at a temperature and substrate concentration of 35°C and 12.6 μM for chlorophyll, and 30°C and 9.3 μM for pheophytin.     

Antioxidative activity of green tea catechin extract compared with that of rosemary extract

This study compared the antioxidative activity of green tea catechin (GTC) extract with that of rosemary extract in canola oil, pork lard, and chicken fat. The GTC extract was obtained from jasmine and longjing green teas and mainly consisted of four epicatechin isomers including (−)epigallocatechin gallate (EGCG), (−)epigallocatechin (EGC), (−)epicatechin (EC), and (−)epicatechin gallate (ECG). The oxidation was conducted at 100 ± 2°C by monitoring oxygen uptake. The oxygen consumption test demonstrated that GTC extract was much more effective than the rosemary extract against lipid oxidation in canola oil, pork lard, and chicken fat under the conditions of the present study. Together with our previous study which showed that GTC extract was more protective than butylated hydroxytoluene as an antioxidant, these results suggest that GTC as a mixture of EGCG, EGC, EC, and ECG may serve as an antioxidant in processed foods.     

Antioxidative activity of green tea catechin extract compared with that of rosemary extract

This study compared the antioxidative activity of green tea catechin (GTC) extract with that of rosemary extract in canola oil, pork lard, and chicken fat. The GTC extract was obtained from jasmine and longjing green teas and mainly consisted of four epicatechin isomers including (−)epigallocatechin gallate (EGCG), (−)epigallocatechin (EGC), (−)epicatechin (EC), and (−)epicatechin gallate (ECG). The oxidation was conducted at 100 ± 2°C by monitoring oxygen uptake. The oxygen consumption test demonstrated that GTC extract was much more effective than the rosemary extract against lipid oxidation in canola oil, pork lard, and chicken fat under the conditions of the present study. Together with our previous study which showed that GTC extract was more protective than butylated hydroxytoluene as an antioxidant, these results suggest that GTC as a mixture of EGCG, EGC, EC, and ECG may serve as an antioxidant in processed foods.     

A multistage hydrocyclone/stirred-tank system for countercurrent extraction of canola oil

Ground canola seed containing 46.9% oil (A) and partially extracted meal, similar to pre-pressed meal containing 13.7% oil (B), were ground in a methanol/ammonia/water solution, filtered to remove antinutrients and extracted countercurrently with hexane in a multistage hydrocyclone/stirred-tank extraction unit. An empirical model was developed for predicting the yield (i.e., oil recovery) from the process. Based on the model calculations, a six-stage unit operating at a hexane-to-meal ratio (R) of 6.2 L/kg was required for processing meal A. The calculated oil recovery was 98.3%, resulting in a meal containing 0.7% residual oil. Meal B required a five-stage unit operating at R=5.7 L/kg. The calculated oil recovery was 99.2% with 0.6% residual oil in the meal. The calculations were confirmed experimentally with two- and four-stage crosscurrent extraction processes.     

Formation and partial characterization of canola oil sediment

The occasional development of a haze in canola oil represents a problem to the quality and acceptability of this oil. The present study examined the formation of sediment in bottled canola oil during storage at 2, 6 and 12°C over a 4-d period. Oils stored at 2°C showed the highest rate of sediment formation, followed by storage at 6°C. Removal of sediment from canola oil prior to storage by cold precipitation and filtration did not eliminate this phenomenon, which still developed rapidly at 2°C. Chemical composition and thermal properties of canola oil sediment were compared to sediment obtained from commercial winterization of this oil. The thermal properties of the purified winterization sediment (melting temperature, 74.9°C) closely resembled those of the sediment from bottled canola oil. Saponification of both sediments yielded large amounts of long-chain fatty acids and alcohols, which were identified by gas chromatography-mass spectrometry. Sediment from commercial winterization contained higher amounts of fatty acids and alcohols with more than 24 carbon atoms in the chain. Presented in part at the AOCS meeting in Toronto, Ontario, May 1992.     

Enzymatic methylation of canola oil deodorizer distillate

Methylation of canola oil deodorizer distillate catalyzed by a nonspecific lipase was investigated. The conversion of fatty acids to methyl esters has been optimized by using a statistical design. Up to 96.5% conversion of fatty acids to their methyl esters has been achieved without the aid of vacuum or any water-removing agent. The effects of temperature, ratio of the reactants (methanol: fatty acids in the deodorizer distillate) and enzyme concentration on the equilibrium conversion were studied. The temperature and ratio of the reactants showed a significant effect on the conversion of fatty acids to methyl esters and they exhibited a strong interactive effect. Enzyme concentration in the range of 2.7% to 4.3% did not show a significant effect on the equilibrium conversion of fatty acids. Greater than 95% conversion of fatty acids to methyl esters was achieved at temperatures around 50°C and at a ratio of the reactants between 1.8 and 2.0. The inhibitory effect of hydrophilic methanol on the enzyme activity was largely reduced by working at the lower temperature range (around 50°C).     

Development of a method for chlorophyll removal from canola oil using mineral acids

Because of the high level of chlorophyll-type compounds found in canola oil, bleaching is an important and critical step in the canola oil refining process. In this study, a new method for reducing the chlorophyll-type impurities prior to the bleaching step was developed. This method is based on precipitating the chlorophyll compounds with mineral acids. Concentrations of chlorophyll-type compounds of up to 30 ppm could be reduced to amounts of less than 0.01 ppm by mixing the crude canola oil with a 0.4 wt% mixture of phosphoric and sulfuric acids (2:0.75, vol/vol) for 5 min at 50°C. Centrifugation and filtration also were examined as two main methods for separating the chlorophyll precipitates. The results showed that filtration by a precoated textural filter with filter-aid clay could separate the precipitates as well as the centrifugation method.     

Sensory stability of canola oil: Present status of shelf life studies

Sensory studies on autoxidation of canola oil, stored under several variations of Schaal Oven test conditions, suggest an induction period of 2–4 d at 60–65°C. Similar induction periods have been observed between canola and sunflower oils, whereas a longer induction period has been found for soybean oil. Canola oil seems to be more stable to storage in light than cottonseed and soybean oils but is less stable than sunflower oil. Storage stability of products fried in canola oil is similar to products fried in soybean oil. Storage stability of canola and cottonseed oils that had been used in the frying of potato chips showed that canola oil was more prone to autoxidation during storage at 40°C. The presence of light aggravated the oxidative effects and was similar for both oils. Advances in our knowledge about the shelf life of canola oil would be strengthened by standardization of Schaal Oven testing conditions and by specifying the testing protocol for photooxidation studies. Methods for training of panelists and for handling and evaluating oils and fried foods require definition. Rating scales used in the evaluation of oils need to be evaluated to ensure that reliable and valid measurements are achieved. Further progress is needed in the identification of chemical indicators that can be used to predict sensory quality of oils. Presented in part at AOCS Annual Meeting in Toronto, Ontario, Canada, May 1992.     

Chemical aspects of chlorophyll breakdown products and their relevance to canola oil stability

The production of prooxidant compounds brought about through subjecting chlorophyll a or pheophytin a to laboratory-scale processing in the presence of canola oil or tricapryloylglycerol was investigated. The addition of chlorophyll a (60 ppm) to canola oil prior to processing resulted in an oil of lowered stability. No large contribution to the produced instability by any one processing step was found when pheophytin a was added (60 ppm) to canola oil prior to processing. To isolate the effect of processing on the pigment, tricapryloylglycerol was used in the place of unsaturated canola oil as a carrier for pheophytin a (60 ppm). A control consisted of processed tricapryloylglycerol that had no added pheophytin prior to processing. The subsequent addition of pigment-treated processed tricapryloylglycerol to linseed oil (1:1, w/w) caused a decrease in the stability of the latter, when compared with the control. No differences were observed between the prooxidant tricapryloylglycerol and the control tricapryloylglycerol by methods involving ultraviolet spectroscopy and thin-layer or gas chromatography.     

Comparison of the composition and properties of canola and sunflower oil sediments with canola seed hull lipids

The phase transition behavior and chemical composition of sediments from Canadian and Australian canola oils, as well as from sunflower oil, were studied by differential scanning calorimetry, X-ray diffraction, polarized-light microscopy, and chromatographic techniques. Australian canola sediment was similar to Canadian canola sediment in both melting and crystallization behaviors and chemical composition. Compared to canola sediment, sunflower sediment underwent phase transformation (melting and crystallization) at lower temperatures, and the enthalpies associated with the phase changes were greater. The X-ray diffraction patterns for these materials were similar, indicating identical crystalline structures. Sunflower sediment contained mainly wax esters (99%), while canola sediment contained about 72–74% of waxes. Moreover, sunflower sediment consisted of shorter-chainlength fatty acids and alcohols than canola sediment. A hexane-insoluble fraction from Canadian canola hull lipids had fatty acid and alcohol profiles and X-ray diffraction pattern similar to the corresponding oil sediment.     

Effects of repeated frying on physicochemical characteristics,oxidative stress,and free radical scavenging potential of canola oil and ghee

The repeated use of cooking oils and ghee for the deep frying of food materials may affect their nutritional quality. The present study evaluated the effect of repeated frying on the physicochemical characteristics and antiradical potential of canola oil and ghee. The oil and ghee were used for frying of fish and chicken for 2, 4, 6, 8, and 10 frying cycles followed by the analysis of physicochemical, oxidative stress, and antiradical parameters. Regression analysis of the data showed a frying cycle-dependent significant linear increase in saponification (R² = 0.9507–0.9748), peroxide and acid values (R² = 0.956–0.9915), and malondialdehyde (MDA) production (R² = 0.9058–0.9557) of canola oil and ghee subjected to fish and chicken frying but exponential increase in saponification value (R² = 0.9778) and MDA production (R² = 0.7407) of canola oil and ghee used for fish frying. The increase in the number of frying cycles linearly decreased the iodine value (R² = 0.9781–0.9924), and 1, 1-diphenyl-2-picrylhydrazyl, hydroxyl, and 2, 2′-azino-bis(3-ethylbenzthiazoline-6-sulfonic acid) radical scavenging potential (R² = 0.9089–0.9979) of canola oil and ghee. Repeated frying in cooking oil and ghee increases oxidative stress and decreases their physicochemical and antioxidant qualities. Canola oil was comparatively more oxidative resistant than canola ghee. The regression equations derived from regression analysis will guide researchers to conduct similar types of univariate studies.     

Detection of olive oil adulteration with canola oil from triacylglycerol analysis by reversed-phase high-performance liquid chromatography

The objective of this study was to explore the use of reversed-phase high-performance liquid chromatography (RP-HPLC) as a means to detect adulteration of olive oil with less expensive canola oil. Previously this method has been shown to be useful in the detection of some other added seed oils; however, the detection of adulteration with canola oil might be more difficult due to similarities in fatty acid composition between canola oil and olive oil. Various mixtures of canola oil with olive oils were prepared, and RP-HPLC profiles were obtained. Adulteration of olive oil samples with less than 7.5% (w/w) canola oil could not be detected.     

Influence of solvent content on phase-transition temperatures of oil sedimen and solution viscosity in acetone/canola oil systems

The effect of acetone on phase transition behavior of sediment in canola oil was studied by differential scanning calorimetry under dynamic heating/cooling regimes. The melting temperature of sediment decreased with an increase in the solvent content of canola oil, suggesting an increase in the solubility of sediment in the oil solution. The crystallization of sediment in oil solution was facilitated by acetone, as indicated by the increase in the sediment crystallization temperature. Acetone dramatically reduced the viscosity of canola oil, particularly in the first 30% addition. The reduction of viscosity was far less with further addition of acetone. These results suggested that the optimum range of acetone content needed for sediment precipitation in canola oil would be in the range of 30–40%. A linear relationship was found between the density of canola oil and temperature. The influence of solvent on the density of canola oil/acetone solution can be accounted for by the mixing theory of ideal solutions, whereas the effect of temperature on the dynamic viscosity of oil solution is best described by a modified Arrhenius equation.