超高效液相色谱法测定生物柴油中的11种脂肪酸及脂肪酸甲酯

建立了采用超高效液相色谱(UPLC)-蒸发光散射检测器(ELSD)测定生物柴油中11种常见的脂肪酸及脂肪酸甲酯含量的方法。这11种常见的脂肪酸及脂肪酸甲酯为豆蔻酸、亚油酸、棕榈酸、油酸、亚麻酸甲酯、硬脂酸、亚油酸甲酯、棕榈酸甲酯、油酸甲酯、芥酸和硬脂酸甲酯。样品经提取后用甲醇溶解,采用Acquity UPLC BEH Phenyl C18柱(100 mm×2.1 mm,1.7 μm)分离,乙腈-水（体积比为3∶1)混合液为流动相进行等度洗脱,采用的ELSD条件为增益80,漂移管温度为45 ℃,载气压力为172 kPa,雾化器为冷却模式,并用外标法进行定量分析。结果表明,在一定的质量浓度范围内,峰面积的对数和质量浓度的对数线性关系良好。与其他检测生物柴油成分的方法相比,该方法简单,分离效果好,速度快,特别是此方法可以同时实现脂肪酸及脂肪酸甲酯的分离,并进行定量分析,能有效测定反应的进行程度,从而满足生物柴油工艺研究的需要。     

气相色谱法测定生物柴油中脂肪酸甲酯含量

生物柴油是利用动植物油脂等可再生资源通过酯交换技术制造的可以替代石化柴油的新型清洁安全燃料[1-3]它的主要成分是脂肪酸甲酯。由于不同油脂原料所生产的生物柴油的脂肪酸甲脂组成不同因而测定时所需的气相色谱条件与方法也不尽相同[4-6]。本文采用HP-innowax毛细管色谱柱,     

Catalytic hydrogenation of fatty acid methyl esters

Catalytic hydrogenation of a mixture of fatty acid methyl esters, which are produced by re-esterification of vegetable (sunflower) oil and are contained in biodiesel fuel, was studied.     

Quantitative analysis of fatty acid methyl esters and dimethyl acetals on a polar (free fatty acid phase) capillary column

Separation of fatty acid methyl esters and dimethyl acetals from complex biological samples has been achieved by gas-liquid chromatography on a capillary column coated with free fatty acid phase. Response-correcting factors were determined, showing rather large variations with fatty acid length. Polyunsaturated fatty acid methyl esters were shown to have lower responses than saturated species, whereas dimethyl acetals and equivalent methyl esters were found to give similar responses. Total fatty acid and aldehyde compositions of human and simian erythrocytes were determined and compared, showing a somewhat higher level of linoleate and arachidonate, and a lower level of plasmalogens in simian erythrocytes.     

Evaluation of porous graphitic carbon as stationary phase for the analysis of fatty acid methyl esters by liquid chromatography

Summary Polyunsaturated fatty acids have been analysed as methyl esters by liquid chromatography on porous graphitic carbon and the results compared with those obtained on octadecyl bonded phases. Chromatographic behaviour on octadecyl bonded phases arises principally as a result of hydrophobic interactions with the bonded phase. Because the retention of analytes is greater on porous graphitic carbon than on octadecyl phases, organic mobile phases are required. When the number of double bonds is low (ca 1–3), the behaviour of porous graphitic carbon is similar to that of octadecyl bonded phases, but when this number increases stronger interactions with the flat surface of the graphite appear, resulting in new selectivity. These two ‘reversed-phase’ systems are considered complementary for separation of different fatty acid methyl esters. An additional advantage of porous graphitic carbon is that it enables isolation of hexadecartrienoic and hexadecadienoic acids, which are not available commercially.     

Determination of potassium in fatty acid methyl esters applying an ion-selective potassium electrode

An easy and inexpensive method of potassium determination in fatty acid methyl esters (FAME) applying an ion-selective potassium electrode (ISE-K) is presented. FAME are considered alternative fuel for diesel engines. Simple apparatus and procedure were developed to avoid contact of ester samples with the sensitive ISE-K membrane, which can damage the ISE membrane surface in long time operation. Using different FAME samples with a wide range of known potassium content a calibration curve was constructed. Among all samples, ISE-K satisfactory predicted potassium content in FAME as identified by the AAS reference method.     

Evaluation of a rapid method for preparation of fatty acid methyl esters for analysis by gas-liquid chromatography

The major limitation to fatty acid analysis by gas-liquid chromatography is associated with preparation of fatty acid methyl esters (FAME). In the present study, FAME preparations were made from plant oils (corn, olive, sunflower), sunflower oil margarine, lard and various animal tissue fats by a rapid transesterification involving tetramethylammonium hydroxide in methanol, and also by a longer conventional saponification-esterification method. Fats from animal (beef, mutton, pork) adipose tissues were extracted by a simpler modified procedure and also by the Folch method prior to the rapid and the conventional FAME preparations, respectively. FAME analysis on a gas-liquid chromatograph equipped with a Silar 10C glass capillary column indicated similar fatty acid composition of a given fat or oil, whether FAME was prepared by the rapid or the longer conventional method. The data obtained by both methods were very highly correlated for all the fats (r = 0.9895 - 0.9999). However, the rapid method showed a tendency for enhanced recoveries of lower chain fatty acids (e.g. 14:0), and also of unsaturated C18 isomers. Possibly, losses of fatty acids that occurred during the lengthy fat extraction, fatty acid esterification or ether-evaporation FAME concentration steps (conventional method) were minimised by the single transesterification step (rapid method). This rapid transesterification method appears to be an attractive alternative to FAME preparation from a wide variety of different fats for gas-liquid chromatographic analysis.     

Characterization of fatty acid methyl esters by thermal analysis

The thermal stability of selected straight-chain (C₆-C₁₄) esters of fatty acids has been studied by TG-DTG and DTA analysis. In DTG, a peak is detected between 84° and 125° C followed by a main effect in the range 105°–215°C, whereas in DTA only an exothermic peak appears in the range of 126.5° to 187°C (onset temperatures). The temperatures of these effects have been related with ignition points, molecular weights and boiling points. The characteristics of melting and recrystallization of the above fatty acid methyl esters and those with carbon numbers between C₁₄ and C₂₄ have been established by DSC along the melting range between ?83° and 50°C. Polymorphism appears in caproic, heptanoic, palmitic and stearic acid methyl esters.     

Assessment of ionic liquid stationary phases for the GC analysis of fatty acid methyl esters

The gas chromatographic separation of fatty acid methyl esters (FAMEs) on ionic liquid stationary phases was investigated. Seven commercially available ionic liquid columns were tested using a test mixture containing 37 fatty acid methyl esters. The influence of column temperature on the elution order was studied using five different temperature programs. Retention times were highly reproducible. Similar retention behavior was observed for the IL59, IL60, and IL61 columns. The peak pair C18:1 cis/trans was not baseline resolved on these columns, whose stationary phases are highly similar. C18:2 cis/trans, C18:3 n6/n3, and C20:3 n6/n3 were baseline separated on all columns. Baseline separation of the complete test mix was only obtained on the IL82 column using a heating rate of 5 K/min. In general, retention times decreased with increasing column polarity but unsaturated FAMEs were retained stronger compared to their saturated counterparts. Except for the IL59 column, retention crossover was observed when the temperature program was changed.     

Mass spectrometry of 3-methoxy fatty acid methyl esters

Fatty acids with a hydroxyl moiety at the C-3 position are found widely in bacterial lipids, but only rarely in mammalian lipids. The mass spectra of the methyl ether derivative of these hydroxy acids exhibit an intense ion at m/e 75, rather than the rearrangement ion at m/e 74 more typical of fatty acid methyl esters. The mass spectrometric behavior of several 3-methoxy fatty acid methyl esters were studied, and the origin of the unique ion at m/e 75 was established using ¹⁸O and ²H labeled analogs and metastable ion transitions. this ion was shown to arise from the loss of ketene from the 3,4 cleavage ion at m/e 117.     

Determination of azadirachtin and fatty acid methyl esters of Azadirachta indica seeds by HPLC and GLC

A simple and economical method has been developed to estimate the azadirachtin content and fatty acid composition of neem kernels. Neem kernels are crushed and soaked overnight in ethanol. The extract obtained is analysed by HPLC after filtering through a 0.22 micro m membrane. The peaks are separated using acetonitrile-water (40:60) 1 mL min(-1) as the mobile phase on an RP-18 column and monitored at 214 nm. For the determination of fatty acid composition, the fatty acids are directly transmethylated in the kernel powder by heating with methanol-acetyl chloride-benzene (20:1:4, v/v) for 1 h in a water bath. The fatty acid methyl esters (FAMEs) obtained are extracted in hexane and analysed using GLC. The separation of the FAMEs is achieved using an RH-Wax column using temperature programming, 170-200 degrees C at 2 degrees min(-1). The peaks are detected using an FID. Both the methods do not require any clean up or defatting of seeds. This results in faster, easier and more economical sample preparation.     

Extraction methods of fat from food samples and preparation of fatty acid methyl esters for gas chromatography: A review

Global trends moved towards fast food consumption due to the busy lifestyle of humans. Hence, the intake of fat-related food has exceeded the daily dietary reference intake (DRI) of fat, which caused multiple diseases. Analysis of the fatty acid profile plays a vital role in nutritional labelling and helps to understand the availability of diverse fatty acids among food commodities. This article reviews, general fatty acid extraction and derivatization techniques that have been developed in the past few decades due to the structural differences of fatty acids and briefed the steps involved in the complete process of fatty acid analysis using gas chromatography-mass spectrometry (GC–MS). Hence, the review mainly focused on conventional extraction methods, followed by microwave-assisted extraction (MAE), ultrasonic-assisted extraction (UAE), and supercritical fluid extraction (SFE) methods and widely used acid, base, and modified derivatization techniques. Importantly, this article compares the results of the previous studies in each section which assist to decide on the most appropriate pathway for the fatty acid analysis for different selected food types. Therefore, it is hoped that this review may help researchers to develop existing experimental methods and to improve ‘bad’ fatty acid level mitigation techniques in future.     

Reversed-phase high-performance liquid chromatography of fatty acid methyl esters with particular reference to cyclopropenoic and cyclopropanoic acids

High performance liquid chromatography of saturated, monounsaturated, diunsaturated, triunsaturated, cyclopropenoic (malvalic and sterculic) and cyclopropanoic (cis-8,9-methylenehexadecanoic and dihydrosterculic) fatty acids was performed with their methyl esters. All separations were carried out with two types of reversed phase columns, the eluent consisting of an acetonitrile/water mixture. The effect of water was studied in the range 0–15%. The best separation was obtained with acetonitrile/water (85:15 v/v). Quantitative results indicated that the detection limits depended upon ultraviolet wavelength and in the present study were 4 ng of methyl sterculate and 125 ng of methyl dihydrosterculate at 195 nm.     

Enantiomeric separation of various lipoxygenase derived monohydroxy polyunsaturated fatty acid methyl esters by high-performance liquid chromatography

Lipoxygenase derived monohydroxy polyunsaturated fatty acid methyl esters were separated by chiral high-performance liquid chromatography (HPLC) with a Chiralcel OD-H column in the normal-phase mode. Major lipoxygenase derivatives of linoleic, -linolenic and arachidonic acids are well resolved by this column, provided they have been individually purified. Our method allows an easy and rapid determination of lipoxygenases enantioselectivity. In all cases tested the R enantiomer is eluted first.     

Quantification of primary fatty acid amides in commercial tallow and tallow fatty acid methyl esters by HPLC-APCI-MS

Primary fatty acid amides are a group of biologically highly active compounds which were already identified in nature. Here, these substances were determined in tallow and tallow fatty acid methyl esters for the first time. As tallow is growing in importance as an oleochemical feedstock for the soap manufacturing, the surfactant as well as the biodiesel industry, the amounts of primary fatty acid amides have to be considered. As these compounds are insoluble in tallow as well as in the corresponding product e.g. tallow fatty acid methyl esters, filter plugging can occur. For the quantification in these matrices a purification step and a LC-APCI-MS method were developed. Although quantification of these compounds can be performed by GC-MS, the presented approach omitted any derivatization and increased the sensitivity by two orders of magnitude. Internal standard calibration using heptadecanoic acid amide and validation of the method yielded a limit of detection of 18.5 fmol and recoveries for the tallow and fatty acid methyl ester matrices of 93% and 95%, respectively. A group of commercially available samples were investigated for their content of fatty acid amides resulting in an amount of up to 0.54%m/m (g per 100 g) in tallow and up to 0.16%m/m (g per 100 g) in fatty acid methyl esters.     

Treatment of acidic palm oil for fatty acid methyl esters production

Acidic crude palm oil (ACPO) produced from palm oil mills with an acid value of 18 mg g⁻¹ was considered to be a possible feedstock for biodiesel production. Due to its high acidity, conventional transesterification cannot be applied directly for biodiesel production. Methane sulphonic acid (MSA, CH₃SO₃H) is used to reduce the acidity prior to the alkaline transesterification reaction. The laboratory-scale experiments involved an MSA to ACPO dosage of 0.25–3.5 %, a molar ratio (methanol to ACPO) from 4: 1 to 20: 1, reaction temperature of 40–80°C, reaction time of 3–150 min, and stirrer speed of 100–500 min⁻¹. The optimum esterification reaction conditions were 1 % of catalyst to ACPO, with a molar ratio of methanol to ACPO of 8: 1, a stirring speed of 300 min⁻¹, for 30 min and at 60°C. Under these conditions, the FFA content was reduced from 18 mg g⁻¹ to less than 1 mg g⁻¹ and with a yield of 96 %. The biodiesel produced met the EN14214 standard specifications. MSA was recycled for three times without losing its activity. The biodiesel produced in a two-stage process has a low acid value (0.14 mg g⁻¹).