气相色谱/质谱法测定植物油中脂肪酸氯丙醇酯

采用苯基硼酸(PBA)衍生化-气相色谱/质谱(GC-MS)联用技术,建立了同时检测植物油中脂肪酸3-氯-1,2-丙二醇酯和脂肪酸2-氯-1,3-丙二醇酯(MCPD酯)的方法.对样品前处理过程中各因素进行了优化,获得了最佳条件,即称取0.1 g左右的食用油样品,加入内标后,经0.5 mL甲醇钠/甲醇(0.5 mol/L)水解1 min,中和后用3.0 mL正己烷脱脂净化两次;以0.25 mL PBA液衍生净化液后,用2.0 mL乙酸乙酯萃取衍生物3次,萃取液经氮气吹干后,用0.5 mL异辛烷溶解,离心后取上清液用GC-MS测定,内标法定量.在此条件下,样品中MCPD酯响应是德国DGF法响应的15～33倍;杂质相对去除率高达99.1％;有关方法学指标均较为理想.在MCPD酯为25～500 ng(以MCPD计)范围内,MCPD与内标峰面积的比值和浓度呈线性相关,相关系数大于0.9990.以花生油为加标基质,在250～1000 μg/kg范围内,进行3个水平的重复加标回收实验(n=6),3-MCPD酯和2-MCPD酯的加标回收率分别为81.1％～92.3％和103％～120％;相对标准偏差(RSD)分别为6.3％～12.4％和4.9％～9.4％;检出限分别为76.0和65.0 μg/kg.利用本方法测定2011年FAPAS考核样品(棕榈油)中3-MCPD酯的含量,测定值为4.01 mg/kg.结果表明,本方法灵敏度高,定量结果准确可靠,从根本上解决了仪器系统容易被污染的问题.     

Determination of Cu,Cd, Ni,Pb and Zn in Edible Oils Using Reversed-Phase Ultrasonic Assisted Liquid–Liquid Microextraction and Flame Atomic Absorption Spectrometry

A simple and green reversed-phase ultrasonic assisted liquid?liquid microextraction method for determination of Cu, Cd, Ni, Pb and Zn in edible oils was developed. Detection was carried out by flame atomic absorption spectrometry. The influence of main parameters including ultrasonic time and temperature, disperser solvent, volume of extracting solvent and centrifuging time on the extraction efficiency of target analytes were investigated and optimized. In the proposed method, a few microliters of water (containing 3%, v/v, nitric acid) as extracting solvent was injected into the oil sample and mixture transferred to ultrasonic bath. Then, the mixture was centrifuged in order to accelerate in phase separation. Finally, the aqueous phase was removed and delivered to flame atomic absorption spectrometer. Calibration curves for all metals were linear in the range of 5?100 ng/mL. The limit of detections for Cu, Cd, Ni, Pb and Zn were 0.8, 0.3, 0.5, 1.5 and 0.5 ng/mL, respectively. Relative standard deviation (RSD) values were in the range of 0.6?1.9%. The recoveries were in the range of 95.2–101.2% with RSD values ranging from 0.8 to 1.9%. The proposed method was applied successfully for the determination of interested metals in commercial edible oils.     

Glycidyl fatty acid esters in food by LC-MS/MS: method development

An improved method based on liquid chromatography-tandem mass spectrometry (LC-MS/MS) for the analysis of glycidyl fatty acid esters in oils was developed. The method incorporates stable isotope dilution analysis (SIDA) for quantifying the five target analytes: glycidyl esters of palmitic (C16:0), stearic (C18:0), oleic (C18:1), linoleic (C18:2) and linolenic acid (C18:3). For the analysis, 10 mg sample of edible oil or fat is dissolved in acetone, spiked with deuterium labelled analogs of glycidyl esters and purified by a two-step chromatography on C18 and normal silica solid phase extraction (SPE) cartridges using methanol and 5% ethyl acetate in hexane, respectively. If the concentration of analytes is expected to be below 0.5 mg/kg, 0.5 g sample of oil is pre-concentrated first using a silica column. The dried final extract is re-dissolved in 250 μL of a mixture of methanol/isopropanol (1:1, v/v), 15 μL is injected on the analytical C18 LC column and analytes are eluted with 100% methanol. Detection of target glycidyl fatty acid esters is accomplished by LC-MS/MS using positive ion atmospheric pressure chemical ionization operating in Multiple Reaction Monitoring mode monitoring 2 ion transitions for each analyte. The method was tested on replicates of a virgin olive oil which was free of glycidyl esters. The method detection limit was calculated to be in the range of 70-150 μg/kg for each analyte using 10 mg sample and 1-3 μg/kg using 0.5 g sample of oil. Average recoveries of 5 glycidyl esters spiked at 10, 1 and 0.1 mg/kg were in the range 84% to 108%. The major advantage of our method is use of SIDA for all analytes using commercially available internal standards and detection limits that are lower by a factor of 5-10 from published methods when 0.5 g sample of oil is used. Additionally, MS/MS mass chromatograms offer greater specificity than liquid chromatography-mass spectrometry operated in selected ion monitoring mode. The method will be applied to the survey of glycidyl fatty acid esters in food products on the Canadian market.     

Combined solid-phase extraction and gas chromatography-mass spectrometry used for determination of chloropropanols in water

A sensitive and rapid derivatization method for the simultaneous determination of 1,3-dichloro-2-propanol (1,3-DCP) and 3-chloropropane-1,2-diol (3-MCPD) in water samples has been developed. The aim was to research the optimal conditions of the derivatization process for two selected reagents. A central composite design was used to determine the influence of derivatization time, derivatization temperature and reagent volume. A global desirability function was applied for multi-response optimization. The analysis was performed by gas chromatography-mass spectrometry. During the optimization of the extraction procedure, four different types of solid-phase extraction (SPE) columns were tested. It was demonstrated that the Oasis HLB cartridge produced the best recoveries of the target analytes. The pH value and the salinity were investigated using a Doehlert design. The best results for the SPE of both analytes were obtained with 1.5 g of NaCl and pH 6. The proposed method provides high sensitivity, good linearity (R(2)≥0.999) and repeatability (relative standard deviations % between 2.9 and 3.4%). Limits of detection and quantification were in the range of 1.4-11.2 ng/mL and 4.8-34.5 ng/mL, respectively. Recoveries obtained for water samples were ca. 100% for 1,3-DCP and 3-MCPD. The method has been successfully applied to the analysis of different samples including commercially bottled water, an influent and effluent sewage.     

Development and validation of a GC-EI-MS method with reduced adsorption loss for the quantification of olanzapine in human plasma

A simple and sensitive GC-EI-MS method using solvent extraction and evaporation was developed for the determination of olanzapine concentrations in plasma samples. Because olanzapine and promazine, which was used as the internal standard (IS), are nitrogenous bases, they can adsorb to the weakly acidic silanol groups on the surfaces of glass centrifuge tubes during solvent extraction and evaporation. Silylation of the glass tubes, addition of triethylamine (TEA), and use of a sample solution with a basic pH could prevent adsorption loss. The extraction method involved mixing plasma (500 μL) in a silylated glass tube with a promazine solution (2 μg/mL, 25 μL) in methanol containing 1% TEA. After addition of aqueous sodium carbonate (0.5 mol/L, pH 11.1, 1 mL) and extraction into 3 mL of dichloromethane/n-hexane (1:1, v/v) containing 1% TEA, the organic phase was evaporated to dryness in a silylated glass tube. The residue was dissolved in ethyl acetate containing 1% TEA (50 μL). For GC-EI-MS analysis, the calibration curves of olanzapine in human plasma were linear from 0.5 to 100 ng/mL. Intra- and interday precisions in plasma were both less than 7.36% (coefficient of variation), and the accuracy was between 94.6 and 110% for solutions with concentrations greater than 0.5 ng/mL. The limit of quantification was 0.5 ng/mL in plasma. The assay was applied to therapeutic drug monitoring in samples from three schizophrenic patients.     

油脂性食品中脂肪酸氯丙醇酯检测方法的研究进展

脂肪酸氯丙醇酯污染是近年来国际上新出现的热点食品安全问题之一,尤其是3-氯-1,2-丙二醇脂肪酸酯(3-MCPD酯)污染问题更为突出。3-MCPD酯在食用油、婴幼儿奶粉等多种食品中的含量较高,以3-MCPD的最大耐受剂量(TDI)评估时所引起的健康风险较高。国外已对3-MCPD酯等氯丙醇酯的检测方法、污染调查和形成机制等开展了不少的研究,国内开展的研究较少。本文主要对油脂食品中3-MCPD酯的检测方法(包括前处理过程,如3-MCPD酯的提取、水解和衍生)、3-MCPD酯总量以及3-MCPD单酯和双酯的检测方法进行了综述。     

高效液相色谱法测定胶粘剂中的游离甲醛

建立了胶粘剂中游离甲醛的高效液相色谱检测方法,对提取方法、衍生化条件及色谱条件进行了研究。结果表明,采用超声波萃取法代替经典的水蒸气蒸馏法能更快速、高效地提取目标物。液相色谱法对甲醛的检出限为0．024μg／mL,在0．1～12μg／mL范围内,线性相关系数R^2=0．9995,在1、2、8μg／mL三个添加水平下,回收率在98．73％～101．68％之间。五个实验室间的相对标准偏差为2．6％。对某白乳胶样品的测定结果表明,本法在定性检测、抗干扰能力及稳定性上都高于常用的乙酰丙酮比色法。     

Magnetic molecularly imprinted polymer for the efficient and selective preconcentration of diazinon before its determination by high‐performance liquid chromatography

A molecularly imprinted polymer was selectively applied for solid‐phase extraction and diazinon residues enrichment before high‐performance liquid chromatography. Diazinon was thermally copolymerized with Fe₃O₄@polyethyleneglycol nanoparticles, methacrylic acid (functional monomer), 2‐hydroxyethyl methacrylate (co‐monomer), and ethylene glycol dimethacrylate (cross‐linking monomer) in the presence of acetonitrile (porogen) and 2,2‐azobisisobutyronitrile (initiator). Then, the imprinted diazinon was reproducibly eluted with methanol/acetic acid (9:1, v/v). The sorbent particles were characterized by X‐ray diffraction, Fourier transform infrared spectroscopy, and scanning electron microscopy. The comprehensive study of variables through experimental design showed that the maximum performance was achieved under these conditions: pH 7, 10 mL sample volume, 15 mg sorbent, 10 min vortex time, 5 min ultrasonic time, 200 μL methanol/acetic acid (9:1, v/v) as eluent, and 5 min desorption time. Under optimized conditions, the molecularly imprinted polymer solid‐phase extraction method demonstrated a linear range (0.02–5 g/mL), a correlation coefficient of 0.997, and 0.005 g/mL detection limit.     

Application of NaClO-treated multiwalled carbon nanotubes as solid phase extraction sorbents for preconcentration of trace 2,4-dichlorophenoxyacetic acid in aqueous samples

Multiwalled carbon nanotubes functionalized by oxidation of original multiwalled carbon nanotubes with NaClO were prepared and their application as solid phase extraction sorbent for 2,4-dichlorophenoxyacetic acid (2,4-D) was investigated systemically, and a new method was developed for the determination of trace 2,4-D in water samples based on extraction and preconcentration of 2,4-D with solid phase extraction columns packed with NaClO-treated multiwalled carbon nanotubes prior to its determination by HPLC. The optimum experimental parameters for preconcentration of 2,4-D, including the column activating conditions, the amount of the sorbent, pH of the sample, elution composition, and elution volume, were investigated. The results indicated 2,4-D could be quantitatively retained by 100 mg NaClO-treated multiwalled carbon nanotubes at pH 5, and then eluted completely with 10 mL 3:1 (v/v) methanol-ammonium acetate solution (0.3 mol/L). The detection limit of this method for 2,4-D was 0.15 μg/L, and the relative standard deviation was 2.3% for fortified tap water samples and 2.5% for fortified riverine water sample at the 10 μg/L level. The method was validated using fortified tap water and riverine water samples with known amount of 2,4-D at the 0.4, 10, and 30 μg/L levels, respectively.     

Simultaneous determination of three organophosphorus pesticides in different food commodities by gas chromatography with mass spectrometry

A sensitive and selective gas chromatography with mass spectrometry method was developed for the simultaneous determination of three organophosphorus pesticides, namely, chlorpyrifos, malathion, and diazinon in three different food commodities (milk, apples, and drinking water) employing solid‐phase extraction for sample pretreatment. Pesticide extraction from different sample matrices was carried out on Chromabond C₁₈ cartridges using 3.0 mL of methanol and 3.0 mL of a mixture of dichloromethane/acetonitrile (1:1 v/v) as the eluting solvent. Analysis was carried out by gas chromatography coupled with mass spectrometry using selected‐ion monitoring mode. Good linear relationships were obtained in the range of 0.1–50 μg/L for chlorpyrifos, and 0.05–50 μg/L for both malathion and diazinon pesticides. Good repeatability and recoveries were obtained in the range of 78.54–86.73% for three pesticides under the optimized experimental conditions. The limit of detection ranged from 0.02 to 0.03 μg/L, and the limit of quantification ranged from 0.05 to 0.1 μg/L for all three pesticides. Finally, the developed method was successfully applied for the determination of three targeted pesticides in milk, apples, and drinking water samples each in triplicate. No pesticide was found in apple and milk samples, but chlorpyrifos was found in one drinking water sample below the quantification level.     

A rapid and sensitive LC-MS/MS method for determination of coenzyme Q10 in tobacco (Nicotiana tabacum L.) leaves

A rapid and sensitive liquid chromatography-tandem mass spectrometry method with multiple reaction monitoring has been proposed for the analysis of coenzyme Q10 in (CoQ10) tobacco leaves. The method used electrospray ionization with detection in positive ion mode. Sample pretreatment involved ultrasonic extraction of fresh tobacco leaves with anhydrous ethanol for 15 min and followed by extraction of the supernatant with hexane. The separation of CoQ10 was performed on a Symmetry Shield RP18 column with a mixture of acetonitrile and isopropanol (8:7, v/v) containing 0.5% formic acid as mobile phase. Quantification of CoQ10 was performed by the standard addition method. The limit of detection and limit of quantitation of CoQ10 were, respectively, 1.2 ng/mL (S/N = 3) and 4.0 ng/mL (S/N = 10). The relative standard deviations of peak area were 0.91% and 1.21% for intra-day and inter-day, respectively. The recoveries of CoQ10 ranged from 98.2 to 99.3% and the corresponding RSDs were less than 2.4%. Analysis took 5 min, making the method suitable for rapid determination of CoQ10 in tobacco leaves. The proposed method has been successfully applied to the analysis of CoQ10 in the leaves from eight varieties of tobacco.     

A high‐performance liquid chromatographic analysis and preliminary pharmacokinetic characterization of 3′‐hydroxypterostilbene in rats

A high‐performance liquid chromatographic method was developed for the analysis of 3'‐hydroxypterostilbene. This method involves the use of a Luna^® C₁₈ column with ultraviolet detection at 325 nm. The mobile phase consisted of acetonitrile, water and formic acid (50:50:0.01, v/v/v) with a flow rate of 0.8 mL/min. The calibration curves were linear over the range 0.5–100.0 µg/mL. The mean extraction efficiency was between 97.40 and 111.16%. The precision of the assay was 0.196–14.39% (RSD%), and within 15% at the limit of quantitation (0.5 µg/mL). The bias of the assay was <16% and within 15% at the limit of quantitation. This assay was successfully applied to pre‐clinical pharmacokinetic samples from rat urine and serum. Copyright © 2009 John Wiley & Sons, Ltd.     

An improved liquid chromatographic method for the analysis of tylosin and its impurities

A selective reversed-phase (RP) liquid chromatographic (LC) method coupled with UV for the determination of tylosin and its related substances is described. The gradient method uses a Capcell pak C18 ACR column (25 cm×4.6 mm id, 5 μm) maintained at a temperature of 60°C. The mobile phases consist of acetonitrile, phosphate buffer pH 5.5 and water: (A; 27.5:10:62.5 v/v/v) and (B; 50:10:40 v/v/v). The flow rate is 1.0 mL/min and UV detection is performed at 280 nm. It allows the separation of all known and 22 other unknown related substances (≥0.02%) from the main compound and from one another. The method shows good precision, sensitivity, linearity (between 0.2 μg/mL and 1.25 mg/mL) and robustness. The limit of quantification is 0.2 μg/mL, corresponding to 0.020%. Seven bulk tylosin samples containing a large number of impurities were examined using this method.     

Development and validation of an analytical method for determination of 3-chloropropane-1,2-diol in rat blood and urine by gas chromatography-mass spectrometry in negative chemical ionization mode

We have developed a highly selective and sensitive method using gas chromatography-mass spectrometry with negative chemical ionization for measuring 3-chloropropane-1,2-diol (3-MCPD) in rat blood and urine. Samples were adsorbed on silica gel, extracted with ethyl acetate, and derivatized by chemical derivatization with heptafluorobutyric acid anhydride. For quantification, matrix-based calibration curves and 3-MCPD-d ₅, as an isotope-labeled internal standard, were used. The relative recoveries of 3-MCPD were between 80 and 110% in most cases and the relative standard deviations were typically less than 10%, with some exceptions. The limit of quantification of the method was found to be about 2 ng/mL. In conclusion, a valuable, robust, and sensitive method for detection of 3-MCPD is now available for biokinetics studies.     

Vortex‐assisted liquid–liquid micro‐extraction and high‐performance liquid chromatography for a higher sensitivity methyl methacrylate determination in biological matrices

A vortex‐assisted liquid–liquid micro‐extraction coupled with high‐performance liquid chromatography, with UV–vis, is proposed to pre‐concentrate methyl methacrylate and to improve separation in biological matrices. The use of 1‐octanol as extracting phase, its volume, the need for a dispersant agent, the agitation conditions and the cooling time before phase separation were evaluated. In optimum conditions, enrichment factors of 20 (±0.5) and enrichment recovery of 99% were obtained. The straightforward association of this extraction process with the HPLC method, previously regulated by the International Organization for Standardization, afforded a detection limit of 122 ng/mL and a quantification limit of 370 ng/mL. The within‐batch precision, relative standard deviation, was 3% for a sample with 1.49 µg/mL and 4% for a sample with 13.4 µg/mL. The results showed a between batch‐precision of 21% for experiments performed on five different days, for a sample with a concentration of 1.10 µg/mL in methyl methacrylate. Copyright © 2013 John Wiley & Sons, Ltd.     

Fast and sensitive high performance liquid chromatography analysis of cosmetic creams for hydroquinone, phenol and six preservatives

A fast and sensitive HPLC method for analysis of cosmetic creams for hydroquinone, phenol and six preservatives has been developed. The influence of sample preparation conditions and the composition of the mobile phase and elution mode were investigated to optimize the separation of the eight studied components. Final conditions were 60% methanol and 40% water (v/v) extraction of the cosmetic creams. A C18 column (100 mm × 2.1 mm) was used as the separation column and the mobile phase consisted of methanol and 0.05 mol/L ammonium formate in water (pH=3.0) with gradient elution. The results showed that complete separation of the eight studied components was achieved within 10 min, the linear ranges were 1.0-200 μg/mL for phenol, 0.1-150 μg/mL for sorbic acid, 2.0-200 μg/mL for benzoic acid, 0.5-200 μg/mL for hydroquinone, methyl paraben, ethyl paraben and propyl paraben, butyl paraben, and good linear correlation coefficient (≥0.9997) were obtained, the detection limit was in the range of 0.05-1.0 μg/mL, the average recovery was between 86.5% and 116.3%, and the relative standard deviation (RSD) was less than 5.0% (n=6). The method is easy, fast and sensitive, it can be employed to analyze component residues in cosmetic creams especially in a quality control setting.     

同位素稀释-气相色谱-质谱法测定食用植物油中总氯丙醇脂肪酸酯

建立了食用植物油中总氯丙醇脂肪酸酯(氯丙醇酯)的同位素稀释-气相色谱-质谱(GC-MS)检测方法。样品经甲醇钠-甲醇溶液水解,硅藻土小柱净化,七氟丁酰咪唑(HFBI)衍生后,GC-MS 检测,同位素内标法定量。3-MCPD 酯、2-MCPD 酯、1,3-DCP 酯和2,3-DCP 酯在0.050~2.000 mg/ L 浓度范围内,均呈良好线性相关,相关系数(R)均大于0.9995。3-MCPD 酯、2-MCPD 酯、1,3-DCP 酯和2,3-DCP 酯的检出限分别为0.015,0.015,0.030和0.030 mg/ kg,定量限分别为0.050,0.050,0.100和0.100 mg/ kg。以空白特级初榨橄榄油为空白基质的加标回收实验的平均回收率为87.0%~110.5%,相对标准偏差(RSD)均小于10.1%。在74份食用植物油样品中,3-MCPD 酯、2-MCPD 酯和1,3-DCP 酯的检出率分别为94.6%,63.5%和5.4%,未检出2,3-DCP 酯;3-MCPD 酯、2-MCPD 酯和1,3-DCP 酯的含量分别在未检出(ND)~10.646 mg/ kg、ND ~3.617 mg/ kg 和ND ~0.089 mg/ kg 之间。本方法简便、准确、可靠,适用于食用植物油中总氯丙醇酯的测定。     

High‐performance liquid chromatographic analysis: applications to nutraceutical content and urinary disposition of oxyresveratrol in rats

A high‐performance liquid chromatographic (HPLC) method was developed for the analysis of the stilbene, oxyresveratrol. This method involves the use of a Luna® C₁₈ column with ultraviolet detection at 320 nm. The mobile phase consisted of acetonitrile, water and formic acid (30 : 70 : 0.04 v/v) with a flow rate of 0.6 mL/min. The calibration curves were linear over the range of 0.5–100.0 μg/mL. The mean extraction efficiency was between 98.9 and 109%. The precision of the assay was 0.069–18.4% (RSD%), and within 20% at the limit of quantitation (0.5 μg/mL). The bias of the assay was <15% and within 15% at the limit of quantitation. This assay was successfully applied to pre‐clinical pharmacokinetic samples from rat urine and to nutraceutical product analysis. Copyright © 2009 John Wiley & Sons, Ltd.     

气相色谱法同时测定溶剂型胶黏剂中的9种有害物质

建立了利用毛细管柱气相色谱同时测定溶剂型胶黏剂中苯、 甲苯、 对（间）二甲苯、 邻二甲苯、 二氯甲烷、1,2-二氯乙烷、1,1,2-三氯乙烷、三氯乙烯、甲苯二异氰酸酯（TDI）的方法,并对样品中有害物质的分离提取和色谱条件进行了研究.实验结果表明,方法化合物浓度在10~300 μg/mL时,线性相关系数不低于0.999 1,样品加标回收率在91.2%~104.1%之间,相对标准偏差均小于5%,检出限为0.1~3.0 μg/mL.方法不仅回收率高、重现性好,而且简便、快速.     

Extraction and preconcentration of formaldehyde in water by polypyrrole‐coated magnetic nanoparticles and determination by high‐performance liquid chromatography

In this study, a simple and rapid extraction method based on the application of polypyrrole‐coated Fe₃O₄ nanoparticles as a magnetic solid‐phase extraction sorbent was successfully developed for the extraction and preconcentration of trace amounts of formaldehyde after derivatization with 2,4‐dinitrophenylhydrazine. The analyses were performed by high‐performance liquid chromatography followed by UV detection. Several variables affecting the extraction efficiency of the formaldehyde, i.e., sample pH, amount of sorbent, salt concentration, extraction time and desorption conditions were investigated and optimized. The best working conditions were as follows: sample pH, 5; amount of sorbent, 40 mg; NaCl concentration, 20% w/v; sample volume, 20 mL; extraction time, 12 min; and 100 μL of methanol for desorption of the formaldehyde within 3 min. Under the optimal conditions, the performance of the proposed method was studied in terms of linear dynamic range (10–500 μg/L), correlation coefficient (R² ≥ 0.998), precision (RSD% ≤ 5.5) and limit of detection (4 μg/L). Finally, the developed method was successfully applied for extraction and determination of formaldehyde in tap, rain and tomato water samples, and satisfactory results were obtained.