近红外光谱分析法测定菜籽油中芥酸的含量

采用多通道PDA型近红外光谱仪,应用偏最小二乘法建立了菜籽油中芥酸含量与近红外透射光谱的校正模型,讨论多项式求导及平滑的窗口宽度和相关系数法筛选有效波长对校正模型的影响,并对10个预测集样品利用预测相关系数R_p和预测均方根误差RMSEP指标进行了预测精度分析,结果发现：在使用全谱数据进行偏最小二乘回归建模时,一阶7点求导及平滑的预处理方法结果最佳,此时建模效果为：R_p=0.739,RMSEP=1.659;在此基础上通过相关系数法筛选波长后的建模效果为：R_p=0.958,RMSEP=0.963。后者R_p提高29%,RMSEP减少42%。由此可得出多项式求导及平滑法和相关系数法相结合对校正模型稳健性,预测精度都有较大提高的结论。研究证明：多通道近红外光谱仪快速测测菜籽油中芥酸含量的方法是可行的。     

精炼工艺对亚麻籽油中反式酸含量的影响

本课题以含55%亚麻酸的压榨亚麻籽油为原料,研究亚麻籽油在精炼过程中油脂品质和反式酸含量的变化规律。结果表明,化学精炼和物理精炼工艺都能将亚麻籽毛油酸价由3.8mgKOH/g脱到0.3mgKOH/g以下;化学精炼过程亚麻籽油中反式酸含量变化由0.2%上升到0.4%;物理精炼过程亚麻油中反式酸含量变化比较明显,脱色后亚麻油反式酸含量为0.27%;在温度200℃,绝对压力10-50pa条件下亚麻油精炼脱酸,4h时亚麻油反式酸含量为0.91%,8h时反式酸含量为1.73%。另外研究表明,化学精炼过程亚麻油的过氧化值变化不大,经精炼后成品油过氧化值为4.1mmol/kg;物理脱酸过程中亚麻油的过氧化值缓慢增加,在200℃脱酸6h时,过氧化值为6mmol/kg以下。     

菜籽油皂脚中游离脂肪酸分子蒸馏分离模拟

该文利用分子蒸馏模型模拟分离皂脚中脂肪酸,进而为后续高效率制备生物柴油奠定基础.根据建立的分子蒸馏模型和物化参数的估算,对菜籽油皂脚中游离脂肪酸的分离进行模拟,并与实际试验数据进行了比较.研究结果表明:该模型在模拟分离菜籽油皂脚中游离脂肪酸时的结果与试验结果曲线趋势相近.随着蒸馏温度的增加,蒸馏量增大,蒸馏量模拟值与实验值的相对误差不超过16%.随着蒸馏温度的增加,重组分中游离脂肪酸含量不断降低,试验结果的脂肪酸浓度都大于模拟值,而相对误差随温度升高不断降低,蒸馏温度为453 K时较蒸馏温度为423 K时,相对误差降低近50%.     

Formation pathways of ethyl esters of branched short-chain fatty acids during wine aging

The particular behavior during wine aging of fermentative branched fatty acid ethyl esters, related to yeast nitrogen metabolism, compared that of their straight-chain analogues, related to yeast lipid metabolism, was first checked in 1-5 year aged Muscadet wines. Quantitative SIDA measurements showed that the levels of the former increased, whereas those of the latter decreased. Then, three hypothetical pathways suggested in the literature to explain these variations of branched esters were investigated. Two Muscadet and Sylvaner wines were spiked with levels of deuterated isobutanoic acid and its ethyl ester, similar to those of their natural analogues, then they were submitted to model aging. Quantitative SIDA measurements on the formation of these natural and labeled ethyl esters from the corresponding acids revealed that the behavior of the natural and labeled compounds were similar. The acid levels were much higher than the ester levels in the initial young wine, and a significant upward trend of their esterification ratios to those of the acid-ester equilibrium was observed with aging. Thus, this equilibrium proved to be the most effective in generating the branched fatty acid ethyl esters during wine aging. In contrast, the formation of these acids by Strecker-type degradation of wine amino acids in the conditions of the model aging or by hydrolysis of their glycoconjugates proved to be ineffective.     

Lipase-catalyzed acidolysis of tripalmitin with hazelnut oil fatty acids and stearic acid to produce human milk fat substitutes

Structured lipids (SLs) containing palmitic, oleic, stearic, and linoleic acids, resembling human milk fat (HMF), were synthesized by enzymatic acidolysis reactions between tripalmitin, hazelnut oil fatty acids, and stearic acid. Commercially immobilized sn-1,3-specific lipase, Lipozyme RM IM, obtained from Rhizomucor miehei was used as the biocatalyst for the enzymatic acidolysis reactions. The effects of substrate molar ratio, reaction temperature, and reaction time on the incorporation of stearic and oleic acids were investigated. The acidolysis reactions were performed by incubating 1:1.5:0.5, 1:3:0.75, 1:6:1, 1:9:1.25, and 1:12:1.5 substrate molar ratios of tripalmitin/hazelnut oil fatty acids/stearic acid in 3 mL of n-hexane at 55, 60, and 65 degrees C using 10% (total weight of substrates) of Lipozyme RM IM for 3, 6, 12, and 24 h. The fatty acid composition of reaction products was analyzed by gas-liquid chromatography (GLC). The fatty acids at the sn-2 position were identified after pancreatic lipase hydrolysis and GLC analysis. The results showed that the highest C18:1 incorporation (47.1%) and highest C18:1/C16:0 ratio were obtained at 65 degrees C and 24 h of incubation with the highest substrate molar ratio of 1:12:1.5. The highest incorporation of stearic acid was achieved at a 1:3:0.75 substrate molar ratio at 60 degrees C and 24 h. For both oleic and stearic acids, the incorporation level increased with reaction time. The SLs produced in this study have potential use in infant formulas.     

Determination of furan fatty acids in extra virgin olive oil

The presence of 4 different furan fatty acids (F-acids) was detected in 18 samples of transmethylated monovarietal extra virgin olive oil: methyl 10,13-epoxy-11,12-dimethyloctadeca-10,12-dienoate [diMeF(9,5)], methyl 12,15-epoxy-13,14-dimethyleicosa-12,14-dienoate [diMeF(11,5)] and both olefinic derivatives of diMeF(11,5) with one unsaturation on the side chains conjugated with the furan ring. Transmethylated oils were analyzed by normal phase high-performance liquid chromatography coupled on-line with capillary gas chromatography. After the gas chromatographic separation step, a more selective detection of F-acids was achieved by using a photoionization detector mounted in series with a flame ionization detector. The concentration of F-acids ranged between 50 ppb (detection limit of the method) and 2.1 ppm in the oil. The olefinic derivatives of diMeF(11,5) acids detected were not artifacts created during the sample preparation or during the chromatographic analysis.     

Genetically modified rapeseed oil containing cis-9,trans-11,cis-13-octadecatrienoic acid affects body fat mass and lipid metabolism in mice

Punicic acid, one of the conjugated linolenic acid (CLN) isomers, exerts a body-fat reducing effect. Although punicic acid is found in pomegranate and Tricosanthes kirilowii seeds, the amount of this fatty acid is very low in nature. The goal of this study was to produce a transgenic oil containing punicic acid. A cDNA encoding conjugase that converts linoleic acid to punicic acid was isolated from T. kirilowii, and the plant expression vector, pKN-TkFac, was generated. The pKN-TkFac was introduced into Brassica napus by Agrobacterium-mediated transformation. As a result, a genetically modified rapeseed oil (GMRO) containing punicic acid was obtained, although its proportion to the total fatty acids was very low (approximately 2.5%). The effects of feeding GMRO in ICR CD-1 male mice were then examined. Wild-type rapeseed (B. napus) oil (RSO) containing no CLN was used as a control oil. For reference oils, RSO-based blended oils were prepared by mixing with different levels of pomegranate oil (PO), either 2.5% (RSO + PO) or 5.0% (RSO + 2PO) punicic acid. Mice were fed purified diets containing 10% of either RSO, RSO + PO, RSO + 2PO, or GMRO for 4 weeks, and dietary PO dose-dependently reduced perirenal adipose tissue weight with a significant difference between the RSO group and the RSO + 2PO group. GMRO, as compared to RSO, lowered the adipose tissue weight to the levels observed with RSO + 2PO. The liver triglyceride level of the RSO + 2PO and GMRO groups but not that of the RSO + PO group was lower than that of the RSO group. The RSO + 2PO and GMRO groups, but not the RSO + PO group, had increased carnitine-palmitoyltransferase activity in the liver and brown adipose tissue. These results showed that dietary GMRO, even at a dietary punicic acid level as low as 0.25 wt % of diet, reduced body fat mass and altered liver lipid metabolism in mice and was more effective than an equal amount of punicic acid from PO.     

Rate of degradation of alpha-tocopherol,squalene, phenolics,and polyunsaturated fatty acids in olive oil during different storage conditions

Changes in the concentration of tocopherol, monophenols, o-diphenols, squalene, and polyunsaturated fatty acids in olive oil were evaluated during 1 year at various storage conditions. Samples of two different extra virgin olive oil (EOO), produced in Calabria (Italy), were stored in dark and in colorless bottles, filled up completely or to half, in order to simulate the domestic storage conditions. The extent of oxidation or photooxidation was monitored by periodic measurements of peroxide values and the rate of degradation of alpha-tocopherol, o-diphenols, squalene, and polyunsaturated fatty acids. The quantitative analysis of the constituents has been performed by HPLC-DAD, HPLC-MS, and GC-MS. The main changes in the concentrations of the analyzed compounds were associated with the major oxygen level in the half-empty glass bottles. alpha-Tocopherol was the first molecule to be oxidized (-20% after 2 months, -92% after 12 months). Squalene and o-diphenols were protected in the first months by the presence of alpha-tocopherol, and their content decreased significantly only after 6 and 8 months, respectively, in the half-empty bottles. The concentration of polyunsaturated fatty acids remained almost constant during 8 months for all four different storage conditions; their oxidation started when the level of the antioxidants decreased.     

分子蒸馏工艺参数对高碳脂肪醇提取物精制效果的研究

采用分子蒸馏技术进行高碳脂肪醇提取物的精制，试验结果表明，蒸馏压力66.7 Pa，蒸馏温度在160～230℃范围内，随着蒸馏温度升高，馏出物中的二十八烷醇和三十烷醇含量逐渐增加，并在190℃时出现峰值，之后下降；蒸馏温度190℃，蒸馏压力在26.7～266.7 Pa范围内，随着压力的下降，馏出物中的二十八烷醇和三十烷醇含量增加，到133.3 Pa处分别达到最大值。蒸馏温度和压力作为分子蒸馏的关键工艺参数对高碳脂肪醇的精制效果具有显著影响。     

Formation of conjugated linoleic acids in soybean oil during hydrogenation with a nickel catalyst as affected by sulfur addition

The effects of sulfur addition on the formation of conjugated linoleic acid (CLA) isomers were studied during the hydrogenation of soybean oil with a nonselective type nickel catalyst. Sulfur addition greatly promoted CLA formation in soybean oil during hydrogenation. As the amount of sulfur increased to a certain level, the maximal quantity of CLA in soybean oil during hydrogenation increased greatly. However, further increase in sulfur addition above the certain level decreased CLA formation. The optimal sulfur level for the promotion of CLA formation differed greatly with the amount of nickel used. It was of great interest to find that the optimal ratio of sulfur to nickel for the promotion of CLA formation was always 0.06:1, regardless of the nickel amount used. At the same ratio of sulfur to nickel, higher nickel content induced significantly higher production of CLA (p < 0.05). At the optimal sulfur to nickel ratio, an increase in the nickel amount from 0.05 to 0.15% produced approximately 1.5 times higher levels of CLA during hydrogenation under the tested conditions. The CLA isomer compositions were greatly affected by both sulfur addition and amounts of nickel used for treatment. This is the first report of the possibility that the total quantity of CLA and their isomer composition could be manipulated during hydrogenation by controlling the amounts of sulfur and nickel.     

Solubilization of selected free fatty acids in palm oil by biodegradable ethoxylated surfactants

The solubilization of three major components, viz., palmitic, oleic, and linoleic acids, in palm oil by ethoxylated surfactants was investigated. The results were analyzed in terms of the molecular properties of surfactants and free fatty acids (FFAs). It was found that the solubilities of these FFAs in various micellar solutions depend not only on their octanol-water partition coefficients (Kow), but also on their physicochemical properties. The study on the solubilization kinetics was conducted by choosing palmitic acid as a model solubilizate and Tergitol 15-S-7 as the model surfactant. A first-order film diffusion model, which accounts for the direct uptake of organic molecules at a solid surface into surfactant micelles, was adopted to analyze the effect of surfactant on dissolution of palmitic acid. It was observed that the presence of surfactant reduced the mass-transfer coefficient. Instead, the overall mass-transfer rate was enhanced because of the much higher driving force from the increased solubilization capacity.     

Formation of humic acids during plant residue humification and their nature

The process of humic acid formation during humification of plant residues (clover leaves and roots as well as timothy roots) was studied. According to some characteristics (elementary composition, IR-spectra, the content of COOH-groups) the newly-formed humic acids may be defined as “young forms”. The comparison of the new forms with more mature soil humic acids revealed the following specific features of the latter: (a) a higher degree of aromatic nuclei condensation; (b) a higher content of carboxyl groups; and (c) a more uniform structure.The authors discuss some defects of the methods used for extraction of humic acids from fresh and slightly humified plant residues by alkaline solutions. An artificial formation of humus-like substances and their extraction as admixtures together with true humic acids are inevitable with these methods. This should be taken into account in studying and systematizing such forms of humic acids.     

Antifeedant activity of some pentacyclic triterpene acids and their fatty acid ester analogues

The 3-O-fatty acid ester derivatives (C(12)-C(18)) of two pentacyclic triterpenic acids, ursolic acid and oleanolic acid, were synthesized under mild esterification conditions in excellent yields (80-85%) and screened for their antifeedant activity, together with the parent acids, against the agricultural pest tobacco caterpillar larvae (Spodoptera litura F) in a no-choice laboratory study. The Urs-12-ene-28-carboxy-3beta-octadecanoate and olean-12-ene-28-carboxy-3beta-hexadecanoate were found to exhibit exceptionally potent antifeedant activities at 50 microg/cm(2) concentration, even after 48 h.     

Correlation studies on oil content and fatty acid profile of some Cruciferous species

Mean individual fatty acid concentration among differentspecies of the family Cruciferae are not similar because of the presence ofdifferent kind of significant relationship among the individual fatty acids.Brassica napus L., Sinapis alba L.,Raphanus caudatus L.f. Raphanus sativusL. and B. nigra (L.) Koch arecomparatively low erucic acid (<40%) containing species. Crambeabyssinica Hochst. ex. R. E. Fries collections gave as high as 60%erucic acid. Low erucic acid concentration was found associated with thepresence of high level of palmitic and oleic acid concentrations. Erucic acidconcentrations were found varied within the range of 42 to 57% among thecollections of Brassica rapa L. and B.carinata A. Braun. All the collections ofB. nigra (L.) Koch were found to havehigher proportion of linoleic acid than the corresponding oleic acidconcentration. Linolenic acid concentrations of B.nigra (L.) Koch was also higher in comparison to otherspecies of the Cruciferae. Raphanus collections were foundto contain higher levels of total saturated fatty acids as well as eicosenoicacid. Oil content of the total collections under present study did not show anysignificant relationship either with linolenic acid or with erucic acidconcentration. But significant positive relationship was observed between totaloil and erucic acid level within the collections of B.juncea Czern. & Coss. Similarly significant negativecorrelation was observed between total oil and linolenic acid content inBrassica rapa L. ssp. trilocularis (Roxb.) Hanelt, yellow sarson.     

Enrichment of anhydrous milk fat in polyunsaturated fatty acid residues from linseed and rapeseed oils through enzymatic interesterification

Lipozyme TL IM was used in a solvent-free batch and microaqueous system for enzymatic interesterification of anhydrous milkfat (AMF) with linseed oil (LO) in binary blends and with rapeseed oil (RO) in one ternary blend. The aim was to obtain and characterize physicochemically fats enriched with unsaturated C 18 fatty acids (oleic, linoleic, and, especially, linolenic acids) from natural vegetable oils. Binary blends of AMF/LO 100/0, 90/10, 80/20, 70/30, and 60/40 (w/w) were interesterified. The change in triacylglycerol (TAG) profiles showed that quasi-equilibrium conditions were reached after 4-6 h of reaction. Free fatty acid contents <1%. The decrease in solid fat content and in dropping point temperature obtained with increasing content of LO and interesterification resulted in good plastic properties for the products originating from the blends 70/30 and 60/40. This was confirmed by textural measurements. Melting profiles determined by differential scanning calorimetry showed complete disappearance of low-melting TAGs from LO and the formation of intermediary species with a lower melting temperature. Oxidative stability of the interesterified products was diminished with increasing LO content, resulting in low oxidation induction times. A ternary blend composed of AMF/RO/LO 70/20/10 gave satisfactory rheological and oxidative properties, fulfilling the requirements for a marketable spread and, moreover, offering increased potential health benefits due to the enriched content in polyunsaturated fatty acid residues.     

Restoration of fillet n-3 long-chain polyunsaturated fatty acid is improved by a modified fish oil finishing diet strategy for atlantic salmon (Salmo salar L.) smolts fed palm fatty acid distillate

Reducing the lipid content in fish prior to feeding a fish oil finishing diet (FOFD) has the potential to improve n-3 long-chain (≥ C(20)) polyunsaturated fatty acid (LC-PUFA) restoration. This study had two main objectives: (1) determine whether feeding Atlantic salmon smolt a 75% palm fatty acid distillate diet (75PFAD) improves the apparent digestibility (AD) of saturated fatty acids (SFA) and (2) examine whether a food deprivation period after growth on 75PFAD leads to higher n-3 LC-PUFA restoration in the fillet when applying a FOFD. The AD of SFA was higher for 75PFAD compared to that of a fish oil (FO) diet. The relative level (as % total fatty acids (FA)) of n-3 LC-PUFA was higher in unfed fish compared to that in continuously fed fish after 21 and 28 day FOFD periods, respectively. Our results suggest that a food deprivation period prior to feeding a FOFD improves the efficiency of n-3 LC-PUFA restoration in the fillet of Atlantic salmon smolt.     

Effect of thermally oxidized oil and fasting status on the short-term digestibility of ketolinoleic acids and total oxidized fatty acids in rats

Western diets contain substantial amounts of lipid oxidation products. The effects of fasting status and oil oxidation on short-term digestibility of oxidized fatty acids (ox-FA) and ketolinoleic acids (keto-LA) of sunflower oils were evaluated. Twelve rats were fasted overnight for 3 days, whereas another 12 rats had free access to diet. From day 4, and for 4 days, two groups of rats, nonfasted (NFT) and fasted (FT), received 1 g/100 g body weight of sunflower oil reused from 40 deep-frying processes, and two control groups of rats, nonfasted (NFC) and fasted (FC), received the same amount of fresh oil. Ox-FA and keto-LA were determined 5 h after the last administration in the various gastrointestinal compartments together with the intraintestinal MDA. Oil digestibility was highest in NFC and lowest in FT rats. NFT and FT rats had higher (at least P < 0.05) intraintestinal MDA, ox-FA, and keto-LA than NFC and FC; MDA and keto-LA concentrations correlated with each other (P < 0.05). Ox-FA and keto-LA levels found in the gastric lumen suggest that digestion contributes to the formation of these compounds. Total ox-FA and keto-LA were efficiently absorbed during the first 5 h after test oil administration, but poorly absorbed in the case of fresh oils. Oil alteration influenced the digestibility of these compounds more than fasting, although the digestibility of oxidized oil was significantly affected by fasting.     

Hypolipidemic effect of oils with balanced amounts of fatty acids obtained by blending and interesterification of coconut oil with rice bran oil or sesame oil

Blended oils comprising coconut oil (CNO) and rice bran oil (RBO) or sesame oil (SESO) with saturated fatty acid/monounsaturated fatty acid/polyunsaturated fatty acid at a ratio of 1:1:1 and polyunsaturated/saturated ratio of 0.8-1 enriched with nutraceuticals were prepared. Blended oils (B) were subjected to interesterification reaction using sn-1,3 specific Lipase from Rhizomucor miehei. Fatty acid composition and nutraceutical contents of the blended oil were not affected by interesterification reaction. Male Wistar rats were fed with AIN-76 diet containing 10% fat from CNO, RBO, SESO, CNO+RBO blend (B), CNO+SESO(B), CNO+RBO interesterified (I), or CNO+SESO(I) for 60 days. Serum total cholesterol (TC), low-density lipoprotein cholesterol, and triacylglycerols (TAGs) were reduced by 23.8, 32.4, and 13.9%, respectively, in rats fed CNO+RBO(B) and by 20.5, 34.1, and 12.9%, respectively, in rats fed CNO+SESO(B) compared to rats given CNO. Rats fed interesterified oils showed a decrease in serum TC, low-density lipoprotein cholesterol (LDL-C), and TAGs in CNO+RBO(I) by 35, 49.1, and 23.2 and by 33.3, 47, and 19.8% in CNO+SESO(I), respectively, compared to rats given CNO. Compared to rats fed CNO+RBO blended oils, rats on CNO+RBO interesterified oil showed a further decrease of 14.6, 24.7, and 10% in TC, LDL-C, and TAG. Rats fed CNO+SESO interesterified oils showed a decrease in serum TC, LDL-C, and TAG by 16.2, 19.6, and 7.8%, respectively, compared to rats given blended oils of CNO+SESO (B). Liver lipid analysis also showed significant change in the TC and TAG concentration in rats fed blended and interesterified oils of CNO+RBO and CNO+SESO compared to the rats given CNO. The present study suggests that feeding fats containing blended oils with balanced fatty acids lowers serum and liver lipids. Interesterified oils prepared using Lipase have a further lowering effect on serum and liver lipids even though the fatty acid composition of blended and interesterified oils remained same. These studies indicated that the atherogenic potentials of a saturated fatty acid containing CNO can be significantly decreased by blending with an oil rich in unsaturated lipids in appropriate amounts and interesterification of blended oil.