Quantitative analysis of the main phenolics in rapeseed meal and oils processed differently using enzymatic hydrolysis and HPLC

Rapeseed meal is the dry residue of the rapeseed de-oiling process. It contains more phenolic compounds than any other oilseed meal. In analysis, rapeseed phenolic esters, mainly sinapine, are usually hydrolyzed to free phenolic acids, because sinapine is not available as a commercial standard. In this study, the efficiencies of different enzymes and enzyme preparations in hydrolyzing sinapine to sinapic acid were explored. The main phenolics in rapeseed meal were sinapine and sinapic acid. In rapeseed oil, the main phenolics were vinylsyringol, sinapine and sinapic acid. In hydrolyzing rapeseed meal, ferulic acid esterase and Ultraflo L were as effective in hydrolyzing sinapine as sodium hydroxide. Over 90% of sinapic acid derivatives were hydrolyzed to yield sinapic acid. Compared to base hydrolysis, enzyme treatment was not only as efficient but also less destructive to the liberated phenolics. Thus, enzymatic hydrolysis is a recommended procedure for optimal analysis of rapeseed phenolics. In rapeseed oils, hydrolysis was best applied in crude post-expelled rapeseed oils with high phenolic content.     

不同食用油氧化稳定性比较研究

为了比较不同食用油的氧化稳定性,选取紫苏油、亚麻籽油、核桃油、菜籽油和芝麻油5种食用油为原料,以烘箱法为对照,分别采用涂膜法和模拟法以过氧化值和酸值为考察指标对其氧化稳定性进行评价,并对其氧化过程中的脂肪酸组成变化进行探讨。结果表明:5种食用油氧化稳定性从高到低依次为:芝麻油菜籽油核桃油亚麻籽油紫苏油;在氧化初期,多不饱和脂肪酸含量减少,单不饱和脂肪酸含量和饱和脂肪酸含量有不同程度的增加,多不饱和脂肪酸含量对食用油氧化稳定性具有明显的影响,特别是亚麻酸含量;在评价氧化稳定性的方法中,烘箱法操作简便但无法反映氧化实际情况,涂膜法检测过程高效且实时,模拟法可反映食用油在使用中的实际氧化过程。     

New polyphenolic compounds in commercial deodistillate and rapeseed oils

Different phenolic compounds were identified in commercial rapeseed oils, as well as in a commercial by-product of oil refining, the deodistillate. Reversed-phase HPLC analysis and the successive fragmentation procedure by ESI-MSⁿ (electrospray ionisation mass spectrometry) showed a significant fragmentation pattern for new compounds, the cis- and trans-diastereomers of 4-vinylsyringol dimer [cis-4,6-dimethoxy-5-hydroxy-1-methyl-3-(3′,5′-dimethoxy-4′-hydroxyphenyl)indane and trans-4,6-dimethoxy-5-hydroxy-1-methyl-3-(3′,5′-dimethoxy-4′-hydroxyphenyl)indane] and the vinylsyringol trimer in trace amounts. The phenylindane were isolated by preparative HPLC and was clearly identified by nuclear magnetic resonance spectroscopy. Besides sinapic acid and its decarboxylated derivative, 4-vinylsyringol, this newly identified 4-vinylsyringol dimer was present in the deodistillate of processed rapeseed oil in significant amounts (sinapic acid, approx. 500 mg/kg, 4-vinylsyringol, approx. 200 mg/kg and 4-vinylsyringol dimer, approx. 3.50 g/kg). Additionally, the phenylindane was also detected in small amounts (6.4–63.0 mg/kg or trace amounts, respectively) in commercial rapeseed oils. The newly identified phenylindane compound had a high antioxidative potential (3.9 trolox-eq.) and might be an important phenolic compound in commercial deodistillate and rapeseed oils.     

Effect of refining on the nutritional value of rapeseed oils for the chick and rat

Experiments were conducted to examine the effect of refining upon the energy utilisation from high erucic acid rapeseed oil, low erucic acid rapeseed oil, maize oil, soya bean oil and herring oil. When fed to chicks and rats, refined high erucic acid rapeseed oils were markedly lower in m.e. and d.e. content and gave poorer growth and feed efficiency than the corresponding crude oils. Removal of the gums present in the crude oils was partially responsible for the reduction in the available energy of the oils. Alkali refining caused a further decrease while bleaching was the major step responsible for the reduced m.e. value for the chick. Low erucic acid rapeseed oil also showed a decrease in m.e. upon refining but the decrease was relatively small as compared with high erucic acid rapeseed oils. The refining of soya bean oil, maize oil and herring oil resulted in slight increases in m.e. and thus these oils responded quite differently to rapeseed oil upon refining.     

菜籽油中类胡萝卜素含量的影响因素及其抗氧化作用

类胡萝卜素为脂溶性化合物,在菜籽油中含量丰富。为提高菜籽油的营养价值和氧化稳定性,对菜籽油中类胡萝卜素含量的影响因素进行了分析,并对类胡萝卜素的抗氧化作用研究情况进行了综述。油菜籽品种以及加工工艺会影响菜籽油中的类胡萝卜素含量,而菜籽油中类胡萝卜素含量的提高,可以增强菜籽油的氧化稳定性。可通过转基因技术培育高类胡萝卜素含量的油菜籽品种,对油菜籽采用焙烤、微波等热处理和不脱皮的预处理方式,以及适度精炼等方法提高菜籽油中的类胡萝卜素含量。     

EFFECT OF PROCESSING ON CONSTITUENTS AND OXIDATIVE STABILITY OF MARINE OILS

Changes in the contents of neutral and polar lipids, α-tocopherol, free fatty acids and color of seal blubber oil (SBO) and cod liver oil (CLO) during different processing steps of alkali-refining, bleaching, and deodorization were monitored. Refined, bleached and deodorized (RBD) SBO and CLO contained approximately 39 and 71% less polar lipids than their crude counterparts, respectively. There was also a reduction of 98.5 and 97.4% in the corresponding free fatty acids content of RBD-SBO and RBD-CLO. The content of α-tocopherol in both oils decreased during processing, especially at the bleaching and deodorization steps. The oxidative stability of SBO and CLO following each processing step was determined by measuring peroxide and 2-thiobarbituric acid reactive substances values. Results so obtained indicated that crude oils were most stable while their refined-bleached counterparts were least stable, perhaps due to the removal of endogenous natural antioxidants such as α-tocopherol during processing of oils.     

Natural antioxidants from herbs and spices improve the oxidative stability and frying performance of vegetable oils

Lipid oxidation has been identified as the major deterioration process of vegetable oils. Undesirable effects are even more profound when food processing involves high temperatures in the presence of oxygen. Natural ground herbs (black pepper, ginger, turmeric, rosemary and oregano) were assessed for their antioxidant capacity, phenolic content and ability to improve the oxidative stability of vegetable oils. The most potent herb was incorporated in vegetable oils formulations which were subjected to consecutive frying cycles. The oxidative stability of the vegetable oils, the formation of conjugated dienes/trienes and the decimation of tocopherol levels after the frying process were assessed. Rosemary powder was the most effective antioxidant among the ones tested. The oxidative stability of tocopherol‐stripped corn oil with rosemary powder (1.53 ± 0.06 h) was significantly higher than the control (0.84 ± 0.02 h) and the oil with synthetic antioxidants (1.20 ± 0.03 h). Rosemary powder effectively improved the oxidative stability of sunflower (128.91%), olive (55.61%) and rapeseed (73.20%) oil during deep‐frying and prevented CD and CT formation in rapeseed oil.     

CORRELATION OF QUALITY OF FRYING OIL AND OIL EXTRACTED FROM POTATO FRITTERS FRIED IN LIQUID AND PARTIALLY HYDROGENATED RAPESEED OILS

The increase in consumption of food fried in the so-called 'deep-frying-oil'entails the necessity of knowledge of both thermooxidative transformation occuring in the frying medium and chemical composition of oil absorbed by the fried product. The aim of this study was to correlate the quality of frying medium and oil extracted from potato fritters fried under rigorously controlled laboratory conditions in liquid and partially hydrogenated rapeseed oils. Oxidation and polymerization reactions predominated during deep frying of potato fritters in both frying media, but hydrolysis occured only to a small degree. The peroxide value was not a suitable quality control indicator for monitoring the thermooxidative transformation during deep frying. The most suitable method for examining such transformations was to study the content and composition of the polar fraction. A correlation existed between the amount of polymers and oxidized triacylglycerols (TAGs) and the amount of polar fraction. Small differences existed in the content of thermooxidative transformation products in the frying medium and the oil extracted from potato fritters. By monitoring anisidine value (AnV), E^1%_1cm and the content and composition of the polar fraction in the frying medium, it was possible to evaluate the quality of the fat in the fritters. Thus, the use of partially hydrogenated compared to liquid rapeseed oil in deep frying process may be preferred because at the same content of polar fraction and its components partially hydrogenated rapeseed oil contained a lesser amount of secondary oxidation products.     

Oxidative and Antiradical Stabilities of Two Important Virgin Olive Oils from Ayvalik and Memecik Olive Cultivars in Turkey

Memecik and Ayvalik olive cultivars were harvested from Mugla province of Turkey and processed into oil using a three phase decanter. The oils of these cultivars were subjected to free fatty acid, peroxide value, ultra violet absorption, and fatty acid composition analysis. The results showed that all obtained values were very similar and within the limits of the International Olive Oil Council regulation for virgin olive oil. The oxidative stability in samples was assessed in terms of primary and secondary oxidation products using peroxide values and induction times, respectively. Total phenol and o-diphenol contents were determined by spectrophotometric assays. The antiradical capacity of phenolic fraction was determined by 1,1-diphenyl-2picrylhydrazyl method. These analyses showed that oxidative resistance, antiradical capacity, and the content of phenols and o-diphenols were higher for Memecik oil than Ayvalik oil.     

Influence of thermal treatment of rapeseed on the canolol content

4-Vinylsyringol, also referred to as canolol, is a highly active antioxidant and potent lipidperoxyl radical scavenger found in rapeseed. The canolol content of rapeseed can be increased through the decarboxylation of sinapic acid via roasting treatments. Different roasting conditions were tested and compared and an optimum for the canolol formation was found at 160 °C. The canolol content of the rapeseed samples with optimal roasting increased by a factor of 120 in relation to the unroasted sample. The rapeseed was ground, extracted and analysed by normal-phase HPLC/UV. The structure of canolol was confirmed by NMR and MS techniques. Several rapeseed oils were purchased in German food stores and analysed. No differences in canolol content were observed in both cold-pressed and rape kernel oil samples tested. Dehulled rapeseed samples demonstrated no significant difference in canolol content when compared to unpeeled rapeseed samples.     

不同抗氧化剂对菜籽油煎炸过程极性组分类别及含量的影响

向菜籽油中分别添加茶多酚、迷迭香、TBHQ做抗氧化剂,进行32 h连续煎炸油条实验,对不同煎炸时间所取油样的酸价、总极性组分(PC)含量及PC中分解产物和氧化聚合产物的含量进行测定,并与空白煎炸油样进行对比,研究不同抗氧化剂对菜籽油煎炸稳定性和品质的影响。结果显示,煎炸结束时,添加茶多酚、迷迭香、TBHQ及空白油样的酸价从煎炸初始的0.1 mg/g分别上升至1.4、2.2、2.9、4.5 mg/g,PC含量从3.90%分别上升至28.62%、46.01%、46.64%、25.8%,PC中分解产物总量从2.23%分别增加至2.69%、3.86%、4.81%、4.26%,氧化聚合产物总量从1.99%分别增加至28.50%、42.16%、41.94%、21.55%,其在PC中的占比由47.88%分别增加至91.44%、91.77%、89.91%、83.50%。添加抗氧化剂可以明显抑制菜籽煎炸油的酸价升高,但对PC升高没有抑制作用,甚至对PC中氧化聚合产物的形成具有促进作用。     

Loss of stability of “veiled” (cloudy) virgin olive oils in storage

Filtration of veiled virgin olive oil samples indicated a loss in stability that was assigned to a loss in total polyphenol content. Oil samples, after filtration, had quite similar peroxide values and absorbance in the UV region to the respective veiled ones. Nine months storage of veiled and filtered oils at ambient temperature, in the dark, revealed that gradual loss in stability, expressed as OSI values, was greater in the latter. This finding was reflected by the greater increase in peroxide values and also faster decrease in total polar phenol content in filtered samples. The RP-HPLC analysis of the phenolic fractions, at various stages of storage, indicated interesting differences in the evolution of individual phenols between the two types of samples. It is suggested that, not only the higher content, but also the forms of individual phenols liberated in veiled oils, due to hydrolytic processes, may be responsible for the unexpected high oxidative stability of this promising commercial category of virgin olive oil.     

不同加工工艺制取菜籽油理化性质的研究

本试验选取蒸炒-预榨-浸出工艺,膨化-预榨-浸出工艺,炒籽-压榨工艺制取的菜籽压榨毛油和浸出毛油样品,通过对酸值、过氧化值、生育酚、甾醇、反式脂肪酸、硫苷的测定,研究了菜籽油在不同工艺条件下油品的质量情况。研究表明：在质量品质和营养物质保留方面,采用膨化-预榨-浸出工艺生产的毛油质量优于蒸炒-预榨-浸出工艺和炒籽-压榨工艺,进一步验证了膨化-预榨-浸出工艺的优越性,即不需蒸炒,对胚片要求低,能耗低、精炼率高、产能可以提高,油脂和粕的质量可以得到改善,能够实现菜籽的高效加工,为油菜籽加工企业的发展提供了有力的技术保障。     

PHENOLIC COMPOUNDS, TOCOPHEROLS AND OTHER MINOR COMPONENTS IN VIRGIN OLIVE OILS OF SOME TUNISIAN VARIETIES

The phenols, α‐tocopherols, fatty acids and oxidative stability of six monovarietal virgin olive oils (VOOs) were determined. Fourteen phenolic compounds were detected and quantified by solid phase extraction and reversed phase‐high performance liquid chromatography. Dialdehydic form of elenolic acid linked to tyrosol and hydroxytyrosol, oleuropein and ligstroside aglycones were the main components in all samples. Pinoresinol was the most abundant component in lignan fraction. The total phenol content of these monovarietal oils varied from 66.82 mg/kg in “Neb Jmel” oil to 662.74 mg/kg in “El Hor” oil. A wide range of α‐tocopherol contents was also noticed; it varied from 141.94 mg/kg in “Semni” variety to 364.23 mg/kg in “Jdallou” variety. With regard to pigments, chlorophylls and carotenoids were found at variable concentrations: with median values of 11.33 and 3.10 mg/kg, respectively. Among the studied varieties, “Oueslati” and El Hor were characterized by the lowest levels of palmitic and linoleic acids and the highest values of oleic acid.     

Carbonaceous materials from seed hulls for bleaching of vegetable oils

Seed hulls, namely cottonseed, peanut, sunflower, soybean, faba bean and lupine were evaluated as carbonaceous materials for the bleaching of crude soybean oil. The six seed hulls were activated by carbonization, steam activation and acid activation. Two reference standards, Fullers earth and Tonsil clay, were used for comparison throughout the whole study. Bleaching of crude soybean oil under vacuum at 100 °C using the treated hulls was carried out. The effect of bleaching with the different hulls on the oil characteristics was evaluated by determining the % free fatty acid, % reduction in peroxide value, % removal of phospholipids, % bleachability and oxidative stability of the bleached oils. Results revealed that bleaching with carbonized hull yielded oils with least free fatty acid content and highest oxidative stability. Bleaching with acid activated hull carbons gave oils with least content of peroxides, phospholipids together with best color. Acid activation of the hulls resulted in highest increase in surface area, pore volume and least pore dimension.     

基于主成分分析的西式快餐条件下煎炸油品质评价

为了研究西式快餐条件下煎炸油的品质并建立其评价体系,考察了5种常见煎炸油(大豆油、菜籽油、葵花籽油、棕榈油及稻米油)在模拟西式快餐条件170℃连续7 d煎炸薯条过程中11个品质相关的理化指标,通过主成分分析法综合评价了5种煎炸油在煎炸过程中的煎炸性能,并建立煎炸油品质评价模型。结果表明,5种煎炸油煎炸周期结束后酸价、极性组分、羰基价、茴香胺值、全氧化值和色泽均显著升高(P<0.05),维生素E总量和氧化稳定指数均显著降低(P<0.05)。相关性分析显示茴香胺值、全氧化值、羰基价两两之间均显著性正相关(r=0.877～0.997,P<0.05),色泽与酸价呈极显著正相关(r=0.822,P<0.01),碘值与氧化稳定指数呈极显著负相关(r=-0.846,P<0.01),与亚油酸/棕榈酸比值呈极显著正相关(r=0.833,P<0.01)。主成分分析提取出3个综合性评价指标,累计贡献率达84.115%,反映了原指标的大部分信息,并进一步建立煎炸油煎炸性能的综合评价得分模型F=0.405F₁+0.295F₂+0.1...     

不同煎炸食材对高油酸菜籽油煎炸稳定性的影响

为研究高油酸菜籽油作为煎炸油的潜力,使用高油酸菜籽油煎炸土豆、鸡柳和豆腐3种不同食材18 h,分析煎炸过程中油样的总极性组分含量、酸值、过氧化值、碘值和脂肪酸组成的变化,并对煎炸食品进行了吸油率测定和感官评价,研究煎炸食材对高油酸菜籽油煎炸稳定性的影响。结果表明：3种食材对高油酸菜籽油总极性组分含量、酸值、过氧化值和碘值影响大小顺序均为土豆>鸡柳>豆腐;煎炸18 h时,3组高油酸菜籽油的单不饱和脂肪酸(MUFA)和多不饱和脂肪酸(PUFA)含量降低,而饱和脂肪酸(SFA)含量增加,其中煎炸土豆的高油酸菜籽油PUFA含量降幅最大,煎炸鸡柳的高油酸菜籽SFA含量增幅最大;煎炸3 h,3种食材感官评分分别达到了9.32、924分和9.12分,之后随着煎炸时间的延长感官评分降低,但豆腐的降幅最小。综上,结合豆腐水分含量高的特性,推测高油酸菜籽油更适合用于高水分含量食材的煎炸,且最佳煎炸时间应控制在3 h之内。     

Effects of Different Pretreatments to Fresh Fruit on Chemical and Thermal Characteristics of Crude Palm Oil

This study selected 5 methods, including boiling, hot air drying, high‐pressurized steam, freezing, and microwave radiation to pretreat fresh oil palm fruit before solvent extraction of the oil. Using fresh fruit as a control, the pretreatment methods were compared for the effects on the activity of the 2 main enzymes in the fruit and some physicochemical properties of the crude palm oil. The results indicated, although all the 5 pretreatments could inactivate lipase and peroxidase in the treated flesh significantly (P < 0.05), the high‐pressurized steam was the most effective. There were also differences in the unsaturated fatty acid contents of the 6 oils. The crude oil from frozen fruit contained significantly more vitamin E (37829.33 ppm) than previously reported. Microwave radiation was shown to significantly decrease the free fatty acid content and the peroxide value, while increasing the oxidative stability index. Thermal behaviors of the oils were significantly different to each other with the exception a few parameters (P < 0.05).     

油菜籽中多酚的分布及加工过程对菜籽多酚含量的影响

对油菜籽壳粕和脱壳后的菜籽肉粕中提取液的总酚含量、对DPPH 自由基清除能力以及FRAP 抗氧化能力进行比较,并采用液质联用法对提取液中的主要成分进行鉴定,对其中的芥子酸和芥子碱进行定量分析。结果表明：菜籽肉粕提取液中的总酚含量、对DPPH 自由基清除能力以及FRAP 抗氧化能力约为菜籽壳粕中的两倍,芥子酸和芥子碱的含量分别为菜籽壳粕中的约2.5 倍和1.5 倍。通过对实验室溶剂除油的菜籽粕与工业高温粕比较发现,高温榨油过程会使菜籽的总酚含量、抗氧化性、芥子酸和芥子碱含量有所下降,其中总酚含量下降了12.06%,DPPH 自由基和FRAP 抗氧化值分别降低10.0% 和5.6%,芥子酸和芥子碱含量分别下降了5.6% 和21.12%。     

Cornicabra virgin olive oil: a study of five crop seasons. Composition,quality and oxidative stability

The chemical composition of Cornicabra virgin olive oils (n=181) from five successive crop seasons (from 1994/95 to 1998/99) and its relationship with quality and oxidative stability is examined. The main characteristics of Cornicabra olive oils were: a high oleic acid (80.4±1.0%, as mean and standard deviation) and low linoleic acid content (4.5±0.6%); high campesterol level (4.2±0.2%), exceeding the EU Regulation upper limit of 4%; large total phenol content (ranging from 19 to 380 mg/kg as caffeic acid for the commercial oils, and from 180 to 614 mg/kg for the Abencor oils), and oxidative stability ranging from 9 to 143 h, by Rancimat, for the commercial oils and from 18 to 193 h for the Abencor oils. Sensory evaluation showed that the total score of 35% of commercial Cornicabra olive oil was lower than the limit of 6.5 established for the ‘extra-virgin’ category, whereas the minimum score observed for Abencor oils was 6.8. This means that, although the majority of the chemical parameters fell within the limits established for the maximum olive oil category, with a few exceptions, significantly more of these olive oils fail the sensory minimum requirements for the highest category.