Influence of interesterification on the oxidative stability of marine oil triacylglycerols

To understand the relationship between triacylglycerol structure of marine oils and their oxidative stability, peroxide values and absorbed oxygen levels of whale, sardine, cod liver and skipjack oils, interesterified by lipase and NaOCH₃, were compared with those of native oils during storage at 40°C. Triacylglycerol structures of marine oils were characterized by high-performance liquid chromatography and differential scanning calorimetry analyses. Enzymatically interesterified fish oils were more stable than native oils because the level of highly unsaturated triacylglycerols was decreased. However, the oxidative stability of interesterified whale oil was more susceptible to oxidation than the native oil.     

Chemiluminescence as a method for oxidative rancidity assessment in autoxidized marine oils

Chemiluminescence based on light emission from excited oxygen species,e.g. singlet oxygen and triplet carbonyls, has been used to measure the oxidative rencidity of fish oils. The luminescence was recorded after sodium hypochlorite addition to the oils dissolved intert-butanol. In addition to high sensitivity and ability to detect small changes in rancidity, the method is fast and may be used as a supplement to the standard chemical methods for quality assessment and antioxidant evaluation. However, care has to be taken in interpretation of the chemiluminescence data of different fish oils, as the light emission depends on both the composition and the rancidity level of the oil. The autoxidized oils were also characterized by peroxide value, thiobarbituric acid value, anisidine value, Kreis rancidity index, iodine value, ultraviolet measurements, capillary gas chromatography, size-exclusion chromatography and sensoric evaluation.     

Preparation of polyunsaturated phospholipids by lipase-catalyzed transesterification

Transesterifications were investigated to determine a means for preparing polyunsaturated phospholipids simply from soy phospholipid, sardine oil, and two kinds of microbial lipases originating fromCandida cylindracea andRhizopus delemar. The optimum reaction conditions forCandida cylindracea lipase were: 4 g of sardine oil, 10 mL of water, 0.7 g of lipase, 10 mL of hexane, 48 hr of reaction time at 37°C for 3 g of soy phospholipid, for which the transesterification ratio reached approximately 45%. Recovery of phospholipid was low, because hydrolysis also occurred under these reaction conditions. However, hydrolysis could be suppressed by using glycerine instead of water, and the recovery of phospholipid increased to 47%, although the transesterification ratio was reduced to 32%. Rhizopus delemar lipase has 1,3-specificity for triglycerides, and the transesterification ratio was approximately 37% in the 1-position of phospholipid. The resulting phospholipid was rich in polyunsaturated fatty acids and linoleic acid, while the total percentage of polyunsaturated fatty acids incorporated was 18.4%. Therefore, polyunsaturated phospholipids can be prepared easily by transesterification of soy phospholipid with fish oil by means of commercial lipases.     

Chitosan and marine phospholipids reduce matrix metalloproteinase activity in myeloma SP2 tumor‐bearing mice

An animal experiment was conducted to assess the antitumor effects of chitosan‐coated liposomes on myeloma SP2. The animal experimental groups designed for myeloma SP2 tumor‐bearing BALB/c mice were provided with five different drinks: (I) control (double‐distilled water); (II) squid phospholipid liposomes alone 1.0 mg/mL; (III) chitosan alone 5.0 mg/mL; (IV) squid phospholipid liposomes 1.0 mg/mL with chitosan 5.0 mg/mL in the form of a simple mixture; and (V) squid phospholipid liposomes 1.0 mg/mL coated with chitosan 5.0 mg/mL. At 20 days after implantation of the myeloma SP2 cells into mice, oral administration of the experimental drinks was provided for 35 days. There was significant suppression of tumor growth when chitosan and squid phospholipids were administered simultaneously in a simple mixture or as chitosan‐coated liposomes. Matrix metalloproteinase (MMP)‐2 and MMP‐9 activity was significantly less in the serum of mice that consumed chitosan‐coated liposomes than in control mice. We found that decreased tumor burden was related to MMP secretion. Therefore, chitosan‐coated marine phospholipid liposomes might be useful as potential agents for the treatment of myeloma SP2.     

Effect of ingredients on oxidative stability of fish oil‐enriched drinking yoghurt

The oxidative stabilities of fish oil‐enriched milk and fish oil‐enriched drinking yoghurt were compared by following the development of lipid oxidation in plain milk, plain yoghurt and yoghurt to which ingredients present in drinking yoghurt were added one by one. All samples were enriched with 1 wt‐% fish oil. After 3 weeks of storage, development of peroxide values, volatile secondary oxidation products and fishy off‐flavors were much more pronounced in the milk compared to any of the yoghurt samples, irrespective of any added ingredients used to prepare flavored drinking yoghurt. Thus, pectin, citric acid or glucono‐delta‐lactone did not affect the oxidative stability of fish oil‐enriched yoghurt emulsions. Furthermore, the fruit preparation and added sugar did not lead to increased antioxidative activity. It is concluded that yoghurt as the dairy component in the fish oil‐enriched emulsion was responsible for the remarkably high oxidative stability and was able to protect the n‐3 PUFA against oxidative deterioration. It should be considered that this strong antioxidative effect of yoghurt might mask potential antioxidative effects of the other ingredients in the drinking yoghurt.     

Comparison of two methods for extraction of volatiles from marine PL emulsions

The dynamic headspace (DHS) thermal desorption principle using Tenax GR tube, as well as the solid phase micro‐extraction (SPME) tool with carboxen/polydimethylsiloxane 50/30 µm CAR/PDMS SPME fiber, both coupled to GC/MS were implemented for the isolation and identification of both lipid and Strecker derived volatiles in marine phospholipids (PL) emulsions. Comparison of volatile extraction efficiency was made between the methods. For marine PL emulsions with a highly complex composition of volatiles headspace, a fiber saturation problem was encountered when using CAR/PDMS‐SPME for volatiles analysis. However, the CAR/PDMS‐SPME technique was efficient for lipid oxidation analysis in emulsions of less complex headspace. The SPME method extracted volatiles of lower molecular weights more efficient than the DHS method. On the other hand, DHS Tenax GR appeared to be more efficient in extracting volatiles of higher molecular weights and it provided a broader volatile spectrum for marine PL emulsion than the CAR/PDMS‐SPME method.     

Oxidative stability of hydrogenated menhaden oil shortening blends in cookies,crackers, and snacks

The oxidative stability of partially hydrogenated menhaden fish oil (PHMO) shortening/canola oil blends with added antioxidant tertiary butylhydroquinone (TBHQ) and various blended partially hydrogenated vegetable oil (PHVO) shortenings without antioxidant in aged cookies and crackers was analyzed by anisidine value (AV), peroxide value (PV), and Totox value. The results showed no significant differences (P<0.05) for PV, AV, or Totox value between the PHMO shortening containing TBHQ and the PHVO shortening in cookies, crackers, and deep-fried extruded snacks, except for the AV and Totox value of crackers.     

The antioxidant effects of phospholipids on perilla oil

Antioxidant effect of phospholipids on the oxidation of refined perilla oil (PO;α-18:3, 54.5%; 16:0, 7.2%; 18:0, 2.6%; 18:1, 18.6%; 18:2, 15.5%), tocopherol-free (POF) and tocopherol-enriched (POR) perilla oil were investigated by measuring weight-gains and by the oven test at 37°C. The oxidative stability of PO was especially increased by additions of phosphatidylethanolamine (PE) and phosphatidylserine (PS), but phosphatidylcholine (PC) scarcely showed an antioxidant effect. The oxidative stability of POF was markedly low, and none of the phospholipids (PC, PE, PS) showed an antioxidant effect on the oxidation of POF. The stability of POR was lower than that of PO regardless of its higher tocopherol contents. However, the oxidation of POR was significantly suppressed by additions of PE and PS, as was observed with PO. PC showed a small antioxidant effect on the oxidation of POR. Therefore, it seems that the antioxidant effects of phospholipids, especially of PE and PS, was due to the presence of tocopherols in the perilla oil.     

Tocopherol distribution and oxidative stability of oils prepared from the hypocotyl of soybeans roasted in a microwave oven

Whole soybeans (Glycin max L.) were roasted by exposure to microwaves at a frequency of 2,450 MHz, and their hypocotyls were separated from other tissues (seed coat and cotyledons). The quality characteristics and composition in the hypocotyl oils were studied in relation to their tocopherol distributions and were evaluated as compared to an unroasted oil sample. Only minor increases (P<0.05) in chemical and physical changes of the oils, such as carbonyl value, anisidine value and color development, occurred with increased roasting time. Significant decreases (P<0.05) were observed in the amounts of phospholipids in the oils after microwave roasting. Nevertheless, compared to the original level, more than 80% tocopherols still remained after 20 min of roasting. These results suggest that the exposure of soybeans to microwaves for 6 to 8 min caused no significant loss or changes in the content of tocopherols and polyunsaturated fatty acids in the hypocotyls. Therefore, a domestic microwave oven would be useful as a simple and quick means for preparing hypocotyl oil of good quality.     

Formation of oxidation compounds in sunflower and olive oils under oxidative stability index conditions

The objective of this work was to study the evolution of oxidation under oxidative stability index (OSI) conditions using the Rancimat apparatus. Sunflower oils with different degrees of unsaturation (conventional high‐linoleic sunflower oil, genetically modified high‐oleic sunflower oil, and a 1 : 1 mixture of both of them) and virgin olive oil were used. The sunflower oils were tested at 100 °C, while the olive oil was assayed at 100, 110 and 120 °C. Samples were analyzed at different time points and conductivity values, until the induction period (IP) was overpassed. A combination of adsorption and size‐exclusion chromatography was used for the quantification of oxidized triacylglycerol (TG) monomers, dimers and polymers. Additionally, peroxide values (PV) and ultraviolet absorption at 270 nm (K₂₇₀), as well as losses of tocopherols, were measured. The results showed that oxidized TG monomers were the only group of oxidation compounds that increased during the early oxidation stage. The end of the IP was marked by the initiation of polymerization after the exhaustion of tocopherols. In comparison with reported results obtained at room temperature, the main difference found was that the amounts of oxidation compounds at the end of the IP were much lower at OSI test temperatures. With the exception of the K₂₇₀ values, the results also showed that the IP endpoints provided by the OSI test were slightly higher than those obtained by quantification of oxidized TG monomers or by PV determination.     

Frying quality and oxidative stability of high-oleic corn oils

To determine the frying stability of corn oils that are genetically modified to contain 65% oleic acid, high-oleic corn oil was evaluated in room odor tests and by total polar compound analysis. Flavor characteristics of french-fried potatoes, prepared in the oil, were also evaluated by trained analytical sensory panelists. In comparison to normal corn oil, hydrogenated corn oil and high-oleic (80 and 90%) sunflower oils, high-oleic corn oil had significantly (P<0.05) lower total polar compound levels after 20 h of oil heating and frying at 190°C than the other oils. Fried-food flavor intensity was significantly higher in the normal corn oil during the early portion of the frying schedule than in any of the high-oleic or hydrogenated oils; however, after 17.5 h of frying, the potatoes fried in normal corn oil had the lowest intensity of fried-food flavor. Corn oil also had the highest intensities of off-odors, including acrid and burnt, in room odor tests. High-oleic corn oil also was evaluated as a salad oil for flavor characteristics and oxidative stability. Results showed that dry-milled high-oleic corn oil had good initial flavor quality and was significantly (P<0.05) more stable than dry-milled normal corn oil after oven storage tests at 60°C, as evaluated by flavor scores and peroxide values. Although the high-oleic corn oil had significantly (P<0.05) better flavor and oxidative stability than corn oil after aging at 60°C, even more pronounced effects were found in high-temperature frying tests, suggesting the advantages of high-oleic corn oil compared to normal or hydrogenated corn oils.     

Modification of the Ferrous Oxidation-Xylenol Orange Method for Determination of Peroxide Value in Highly Pigmented Sea Cucumber Viscera Lipid

A ferrous oxidation-xylenol orange (FOX) method was modified to measure the levels of hydroperoxides in highly pigmented sea cucumber (Cucumaria frondosa) viscera lipid. With the FOX method, oil hydroperoxides oxidize Fe(II) to Fe(III) ions, which in turn bind to xylenol orange (XO) to form a complex that has a maximum absorbance at 560 nm. When applied to lipid extracts containing high levels of carotenoid pigments, the carotenoids interfere in the absorbance measurement because the XO-complex and carotenoids absorb at the same wavelength. To avoid this, an approach was developed where carotenoids were removed from the solution containing the XO-complex before absorbance measurements were made. This was accomplished by aqueous extraction of the reaction solution, leaving an organic layer containing the carotenoid pigment. The absorbance of the aqueous layer was subsequently measured at 560 nm allowing for determination of the lipid hydroperoxide content (mmol kg⁻¹) using a cumene hydroperoxide calibration curve. The method was validated using oxidized, unpigmented fish oils. The modified FOX method described herein was linear, accurate, and precise, and was validated over a hydroperoxide concentration range of 5–35 meq kg⁻¹ lipid. This modified FOX method for hydroperoxide determination of highly pigmented lipids is a valuable alternative to the methods presently available for determination of peroxide values.     

Effect of vacuum frying on the oxidative stability of oils

The purpose of this study was to evaluate frying oil quality with different assessment methods during vacuum frying of carrot slices. In six consecutive days, palm oil, lard, and soybean oil were fried under vacuum at 105°C for 20 min each hour in an 8-h shift. Peroxide value, acid value, carbonyl value, total polar components, dielectric constant (Food Oil Sensor reading), viscosity, and fatty acid composition were used to evaluate the quality of these oils. Results showed that palm oil and lard possess greater thermal stability than soybean oil. The decrease in C_18:2/C_16:0 ratio was greater for soybean oil than the other two oils. Of the assessment methods used, peroxide value, carbonyl value, total polar components, and dielectric constant all showed good correlation with frying time and between each other. Viscosity was suitable to assess vacuum-fried lard and soybean oil, but not palm oil. The measurement of dielectric constant, on the other hand, appeared to be unsuitable to assess vacuum-fried soybean oil.     

Fatty acid composition of melon seed oil lipids and phospholipids

Fatty acid compositions of crude melon seed oil from two different sources were compared. Melon seeds fromCitrullus vulgaris (syn.C. lanatus) contained phosphatidylcholine (PC), lysophosphatidylcholine (LPC) and phosphatidylserine (PS), whereas melon seeds fromCitrullus colocynthis contained only PC and LPC, but not PS. Analysis of the total lipids revealed that the major fatty acid of the oils was 18:2n-6.Citrullus vulgaris seed oil contained 71.3% andC. colocynthis contained 63.4% of 18:2n-6. The predominant fatty acids in theC. vulgaris PC were 18:2n-6 (32.2%), 18:1n-9 (26.4%) and 16:0 (22.2%), whereas theC. colocynthis PC contained 44.6% of 18:1n-9 as the major fatty acid. The level of monoenes in theC. colocynthis variety (46.2%) was different from theC. vulgaris (27.3%). The major fatty acid in the LPC was 18:1n-9 for both varieties. Notably, theC. colocynthis variety did not contain any PS. The major fatty acids in theC. vulgaris PS were 18:1n-9 (37.9%) and 18:2n-6 (33.7%). Of all the phospholipids, LPC contained the greatest amount of monoenes, 48.6–52.4%.     

胡萝卜片真空油炸过程用油品质研究

主要探讨了真空油炸胡萝卜片后三种炸用油的稳定性，研究了三种炸用油的酸价、过氧化值、羰基价随油炸时间的变化规律，分析了它们之间的相关性。结果显示：与大豆色拉油相比，棕榈油和猪油有更高的油炸稳定性；三种油的酸价、过氧化值、羰基价与油炸时间存在着显著的相关性。     

Studies of chemical methods for assessing oxidative quality and storage stability of feeding oils

Peroxide value (PV), thiobarbituric acid number (TBA), anisidine value (AV), percent free fatty acids (FFA), and carbonyl value (CV) methods were compared in different experiments for their sensitivity and practicality in assessing the oxidative quality of four feeding oils: salmon oil, soybean oil, canola oil (oil from low erucic acid, low glucosinolate rapeseed), and canola soap stocks. In the first experiment, among the four methods (PV, AV, TBA and FFA) studied, PV appeared to be the most practical for its sensitivity, simplicity, and economy when the four oils were oxidized by bubbling air through at room temperature for 792 hr. In the second experiment, using herring oil, all four methods tested (PV, AV, TBA and FFA) were sufficiently sensitive once the oxidation of herring oil had passed the induction period and the oil was highly oxidized. In the third experiment, of the four methods (PV, AV, TBA and CV) compared, AV was the most sensitive for measuring the oxidative quality of canola oil aerated at 100 C for 240 hr. Results of further studies suggested that herring and canola oils stored under commercial conditions were stable for at least one year.