液相色谱-串联质谱法测定鱼肉中的七种全氟有机物

建立了液相色谱-串联质谱检测鱼肉中七种全氟有机物残留的分析方法。通过优化和比较,样品选用甲醇均质提取,C18固相萃取小柱净化,以乙腈-5mmol/L乙酸铵为流动相经C8反相色谱柱分离后,采用多反应监测(MRM)负离子模式检测。阴性样品添加实验结果表明,特征离子相对强度比值稳定,基质效应干扰少,结合保留时间可实现准确的定性定量,方法检出限为0.01～0.03μg/kg(S/N=3),不同鱼肉基质样本添加水平在0.05～1.0μg/kg时,平均回收率为80.0%～120.0%,相对偏差(n=6)为2.9%～7.6%。     

分散固相萃取-超高压液相色谱-串联质谱法测定黄瓜中的嗪胺灵

目的 建立黄瓜中嗪胺灵残留的液质串联快速分析检测方法。方法 样品中的嗪胺灵经乙腈提取用N-丙基乙二胺(PSA)和石墨化碳黑(GCB)净化, 利用超高压液相色谱-串联质谱(UPLC-MS/MS)在多反应监测模式下进行检测。结果 以碎片离子对 432.8>212.9、432.8>82.9定性、离子对432.8>97.8进行外标法定量。仪器在0.01~1.00 mg/kg范围内, 具有良好线性关系。在0.02~1.00 mg/kg添加水平范围内, 嗪胺灵在黄瓜中的平均回收率为85.3%~92.2%, 其相对标准偏差为2.8%~7.5%。该方法的检出限(LOD)为2.0 μg/kg, 定量限为(LOQ)为20 μg/kg。结论 本方法简便、快速、准确, 能满足国内外法规的要求, 可用于黄瓜样品中嗪胺灵的农药残留确证检测。     

水果中噻虫嗪农药残留LC/MS/MS测定

目的建立一种简单、快速、灵敏的水果中噻虫嗪农药残留的液相色谱-串联质谱(liquid chromatography-mass spectrometry/mass spectrometry,LC-MS/MS)分析方法。方法称取水果样品5 g,加入乙腈20 m L在超声波振荡条件下提取,提取液使用20 mg石墨化炭黑(Carb)和60 mg N-丙基乙二胺(PSA)粉末进行分散固相萃取净化,经液相色谱质谱联用仪检测,外标法定量。结果噻虫嗪农药残留的色谱图分离效果良好,方法的检出限为0.3μg/kg,线性相关系数为0.9999,噻虫嗪在苹果、梨、桃中的添加水平为0.01、0.05、0.10 mg/kg,回收试验表明该方法平均回收率为88.9%~100.3%(n=6),相对标准偏差为1.98%~4.53%。结论该方法简单、快速、灵敏、净化效果好、回收率高,适合水果中噻虫嗪农药残留的检测和安全监控。     

Multi-residue method for the analysis of pesticides in Arabica coffee using liquid chromatography/tandem mass spectrometry

Coffee is a major tropical agricultural commodity and represents a significant fraction of the economy of many countries. However, certain plant and animal species can damage coffee crops, affecting trade. A solution to this issue is the use of pesticides, some of which are harmful to human health and the environment. This work consisted of the development of a multi-residue method for the analysis of pesticides in coffee by using LC-MS/MS. The QuEChERS extraction procedure was used. The following analytical parameters were optimised: selectivity, analytical range, linearity, LOD, LOQ, precision (RSD%) and recovery of the method. The results showed that the method is selective, as they were linear in the range of 10.0–100.0 µg kg^?1. The sensitivity, recovery and precision were adequate for the multi-residue analysis of pesticides in coffee. The method was applied to the analyses of 15 Brazilian coffee samples.     

Determination of γ-glutamyl-valyl-glycine in raw scallop and processed scallop products using high pressure liquid chromatography–tandem mass spectrometry

The determination of the kokumi peptide, γ-glutamyl-valyl-glycine (γ-Glu-Val-Gly) in raw scallop and processed scallop products was carried out using high pressure liquid chromatography–tandem mass spectrometry (LC/MS/MS). The detection of γ-Glu-Val-Gly was achieved using a multiple reaction monitoring (MRM) method. The optimised condition enabled the precise determination of γ-Glu-Val-Gly. Raw scallop contained 0.08 μg/g γ-Glu-Val-Gly, and the γ-Glu-Val-Gly levels in processed scallop products, such as dried-scallop and scallop extract, were measured to be 0.64 and 0.77 μg/g, respectively. This is the first report to confirm the existence of γ-Glu-Val-Gly in foodstuff.     

液相色谱-串联质谱法快速测定食品中的可乐定

目的 采用超高压液相色谱-电喷雾串连四极杆质谱分析食品基质中的可乐定, 为可乐定中毒事件的 样本分析提供依据。方法 食物样本粉碎后经甲醇水溶液超声提取, 低温离心后, 上清液用 Waters ACQUITY UPLCTM BEH C18 色谱柱分离, 以 0.1%甲酸和甲醇溶液为流动相梯度洗脱, 最后用串联四极杆质谱在正离子 MRM 模式下进行测定。结果 以淀粉和炸鸡为加标基质, 三个加标水平下可乐定的平均回收率为 91.5%~127.8%, 相对标准偏差小于 16%, 定量限为 0.02 mg/kg。结论 该方法操作快速简单、重现性好, 成功 用于 2010 年 4 月怀柔水岸山吧可乐定中毒事件的食品检测。     

超高效液相色谱-串联质谱法测定谷物中的总烟酸

建立一种快速、准确的测定谷物中总烟酸含量的超高效液相色谱-串联质谱方法。样品加入烟酸-D4同位素内标校正,经氢氧化钠水解,采用HLB固相萃取柱净化后,以10 mmol/L乙酸铵溶液（含0.1%甲酸）和乙腈作为流动相进行梯度洗脱,采用HSS T3液相色谱柱分离,正离子MRM模式进行定性定量分析。实验结果表明,烟酸在0.1²00 ng/m L浓度范围内线性关系良好,相关系数r>0.999。线性范围内,平均加标回收率为99.3%¹02.6%,相对标准偏差在4.24%⁴.74%。仪器的检出限为0.04 ng/m L,定量限为0.1 ng/m L。该方法具有灵敏度高、重现性好、分析时间短等优点,可以为谷物中总烟酸含量的测定提供技术支持。      

Determination of chloramphenicol in shrimp by liquid chromatography-electrospray ionization tandem mass spectrometry (LC-ESI-MS-MS)

A liquid chromatographic method with electrospray ionization tandem mass spectrometric (LC-ESI-MS-MS) detection and identification is described for the determination of chloramphenicol (CAP) in shrimp tissue. Homogenized shrimp samples were extracted by liquid-liquid extraction using ethyl acetate. d5-Chloramphenicol (5D-CAP) was used as the internal standard. Data acquisition was in negative-ion multiple reaction monitoring (NMRM) mode using three transition reactions for CAP (m/z 321 --> 152, m/z 321 --> 257 and m/z 321 --> 194) and two for d5-chloramphenicol (m/z 326 --> 262 and m/z 326 --> 157). Method validation was carried out according to European Commission decision 2002/657/EC. The calibration curve was linear in the range 0.10-2.00 microg l(-1), with typical r2 > 0.99. The decision limit (CC alpha) and detection capability (CC beta) were 0.06 and 0.10 microg kg(-1), respectively. There was no influence of the matrix on the determination of chloramphenicol.     

Acrylamide levels in Finnish foodstuffs analysed with liquid chromatography tandem mass spectrometry

Sample clean-up and HPLC with tandem mass spectrometric detection (LC-MS/MS) was validated for the routine analysis of acrylamide in various foodstuffs. The method used proved to be reliable and the detection limit for routine monitoring was sensitive enough for foods and drinks (38 microg/kg for foods and 5 microg/L for drinks). The RSDs for repeatability and day-to-day variation were below 15% in all food matrices. Two hundred and one samples which included more than 30 different types of food and foods manufactured and prepared in various ways were analysed. The main types of food analysed were potato and cereal-based foods, processed foods (pizza, minced beef meat, meat balls, chicken nuggets, potato-ham casserole and fried bacon) and coffee. Acrylamide was detected at levels, ranging from nondetectable to 1480 microg/kg level in solid food, with crisp bread exhibiting the highest levels. In drinks, the highest value (29 microg/L) was found in regular coffee drinks.     

Determination of chloramphenicol in shrimp by liquid chromatography-electrospray ionization tandem mass spectrometry (LC-ESI-MS-MS)

A liquid chromatographic method with electrospray ionization tandem mass spectrometric (LC-ESI-MS-MS) detection and identification is described for the determination of chloramphenicol (CAP) in shrimp tissue. Homogenized shrimp samples were extracted by liquid–liquid extraction using ethyl acetate. d₅-Chloramphenicol (5D-CAP) was used as the internal standard. Data acquisition was in negative-ion multiple reaction monitoring (NMRM) mode using three transition reactions for CAP (m/z 321?→?152, m/z 321?→?257 and m/z 321?→?194) and two for d₅-chloramphenicol (m/z 326?→?262 and m/z 326?→?157). Method validation was carried out according to European Commission decision 2002/657/EC. The calibration curve was linear in the range 0.10–2.00 µg l^?1, with typical r ²?>?0.99. The decision limit (CCα) and detection capability (CCβ) were 0.06 and 0.10 µg kg^?1, respectively. There was no influence of the matrix on the determination of chloramphenicol.     

Determination of chloramphenicol in shrimp by liquid chromatography-electrospray ionization tandem mass spectrometry (LC-ESI-MS-MS).

A liquid chromatographic method with electrospray ionization tandem mass spectrometric (LC-ESI-MS-MS) detection and identification is described for the determination of chloramphenicol (CAP) in shrimp tissue. Homogenized shrimp samples were extracted by liquid-liquid extraction using ethyl acetate. d5-Chloramphenicol (5D-CAP) was used as the internal standard. Data acquisition was in negative-ion multiple reaction monitoring (NMRM) mode using three transition reactions for CAP (m/z 321 --> 152, m/z 321 --> 257 and m/z 321 --> 194) and two for d5-chloramphenicol (m/z 326 --> 262 and m/z 326 --> 157). Method validation was carried out according to European Commission decision 2002/657/EC. The calibration curve was linear in the range 0.10-2.00 microg l(-1), with typical r2 > 0.99. The decision limit (CC alpha) and detection capability (CC beta) were 0.06 and 0.10 microg kg(-1), respectively. There was no influence of the matrix on the determination of chloramphenicol.     

高效液相色谱-串联质谱联用测定农产品中双氰胺

建立了高效液相色谱-串联质谱检测农产品中双氰胺残留量的检测方法。以氘代试剂为内标,样品经氨化乙腈萃取后,平行定量浓缩仪浓缩,用正己烷脱脂,采用HPLC-MS/MS选择反应监测(SRM)正离子模式测定。双氰胺的检出限可达10μg/kg,最低定量限可达40μg/kg。在10¹ 000 ng/mL内峰强度与质量浓度的线性关系良好(r>0.999)。方法的平均回收率在94.8%1 000 ng/mL内峰强度与质量浓度的线性关系良好(r>0.999)。方法的平均回收率在94.8%¹03.3%。     

Determination of naturally occurring progestogens in bovine milk as their oxime derivatives using high performance liquid chromatography–electrospray ionization–tandem mass spectrometry

BACKGROUND: Hormones and hormone‐like substances which are present in the environment have been repeatedly accused of being the cause of most endocrine disruption. However, the possible role of endogenous hormones in food of animal origin deserves to be discussed as well. The relation between steroid hormones and several human health problems has been previously reported, such as prostate and breast cancer, perturbation of human reproduction and endocrine disruption on humans and wildlife. This research is particularly concerned with cow's milk, which contains a considerable amount of sex hormones. RESULTS: A liquid chromatography–tandem mass spectrometry method has been developed for the simultaneous detection and quantification of four naturally occurring steroid hormones in commercial bovine milk (pregnenolone (P₅), progesterone (P₄), 17‐hydroxypregnenolone (17‐OHP₅), 17‐hydroxyprogesterone (P₄)). Oxime derivatives of steroids were analyzed in positive ionization and multiple reaction monitoring mode. Methodology has been validated according to Decision 2002/657/EC criteria. CONCLUSION: This method has been successfully used in real samples. It is fast and easy‐handling and provides a useful tool for the assessment of progestogens in bovine milk. Copyright © 2010 Society of Chemical Industry     

Determination of naturally-occurring formaldehyde in raw and cooked Shiitake mushrooms by spectrophotometry and liquid chromatography-mass spectrometry

The initial objective was to check samples of Shiitake mushrooms for potential contamination with formaldehyde. A small number of UK retail samples were analysed using a spectrophotometric method and were found to produce formaldehyde concentrations ranging from 110-240 mg kg^-1. A more specific method, based on a derivative that could be measured and characterized by LC-MS, confirmed these results. A secondary objective tested the hypothesis that the formaldehyde might be of natural origin. Samples of UK and Chinese Shiitake, verified as being produced without any formaldehyde treatments, were found to produce similar levels of formaldehyde ranging from 100-320 mg kg^-1. Frying for 6 min significantly reduced formaldehyde concentrations, whereas storage for up to 10 days had no effect on the concentrations. The relatively harsh analytical conditions used may have produced some of the formaldehyde measured during extraction, from a number of chemical precursors.     

Determination of mycotoxins in cereals by liquid chromatography tandem mass spectrometry

A liquid chromatography tandem mass spectrometry (LC–MS/MS) method is described for simultaneous determination of aflatoxins (AFB₁, AFB₂, AFG₁ and AFG₂), ochratoxin A (OTA), zearalenone (ZEA), deoxynivalenol (DON), fumonisins (FB₁ and FB₂), T2 and HT2-toxin in cereals. One-step extraction using solvent mixtures of acetonitrile:water:acetic acid (79:20:1) without any clean-up was employed for extraction of these mycotoxins from cereals. The mean recoveries of mycotoxins in spiked cereals ranged from 76.8% to 108.4%. Limits of detection (LOD) and quantification (LOQ) ranged 0.01–20 and 0.02–40 ng/g, respectively. The developed method has been applied for the determination of mycotoxins in 100 cereal samples collected from Malaysian markets. A total of 77 cereal samples (77%) contaminated with at least one of these mycotoxins. Occurrence of mycotoxins in commercial cereal samples were 70%, 40%, 25%, 36%, 19%, 13%, 16, and 16% for aflatoxins, OTA, ZEA, DON, FB₁, FB₂, T2 and HT2-toxin, respectively. The results demonstrated that the procedure was suitable for the determination of mycotoxins in cereals and could be implemented for the routine analysis.     

超声波萃取-液相色谱-质谱法测定蔬菜中的酞酸酯

采用超声波萃取-液相色谱-质谱法测定保护地蔬菜中4种酞酸酯(PAEs)含量,研究保护地不同品种蔬菜中PAEs的污染状况.PAEs的添加回收率为82.7%～106.9%,RSD为1.9%～6.7%,检出限酞酸二甲酯(DMP)为0.988 ng,酞酸二乙酯(DEP)为0.749 ng,酞酸二丁酯(DBP)为0.702 ng,酞酸二异辛酯(DEHP)为1.920 ng.该方法前处理简单,具有较高的准确度和灵敏度.     

Improved method for the determination of 12 non-nutritive sweeteners and monitoring in various foods using liquid chromatography–tandem mass spectrometry

An improved and highly sensitive method was developed and validated for the determination of 12 (7 permitted and 5 non-permitted in Korea) non-nutritive sweeteners in various foods using liquid chromatography-electrospray ionisation-tandem mass spectrometry. The chromatographic separation was performed on an Xbridge BEH C18 column (3 mm × 100 mm, 2.5 μm) with gradient elution using 10 mM ammonium acetate in water and 10 mM ammonium acetate in methanol. Sample preparation consisted of simple dilution, homogenisation, centrifugation and purification with a C18 cartridge prior to analysis. The relative matrix effect (%ME) was within ±20% for all sweeteners. The method also showed good linearity (R² > 0.99). The limit of detection and limit of quantification values in sample were in the range of 0.02–2.66 and 0.06–8.05 mg kg^?1, respectively. The recoveries at three concentration levels ranged between 80% and 119%, with relative standard deviation values below 10%. In addition, the expanded uncertainties determined for 12 sweeteners in 5 different food matrices were confirmed to be <14%. Finally, the method was successfully applied to the analysis of sweeteners in 681 food samples purchased in Korea, Australia and Turkey. These results demonstrate that the method is suitable for the simultaneous determination of multiple-sweeteners in a variety of foods.     

液相色谱-串联质谱法测定猪肉及组织中沙丁胺醇的含量不确定度评定

目的分析液相色谱一串联质谱法检测猪肉及组织中沙丁胺醇的不确定度,探讨各因素对检验结果的影响。方法依据JJG1059.1-2012《测量不确定度评定与表示》和CNAS-GL06《化学分析中不确定度的评估指南》规定的方法和程序,分析影响测量不确定的来源,并对各不确定度分量进行了评估。结果合成各变量的不确定度,最终得到测定结果的扩展不确定度:(11.05±0.77)μg/kg(k=2)。结论影响检测结果不确定度的主要因素为回收率和标准曲线拟合,在实际测量过程严格控制实验条件可提高检测的准确性和可靠性。     

Proteome analysis of Pithecellobium dulce seeds using two‐dimensional gel electrophoresis and tandem mass spectrometry

BACKGROUND: Pithecellobium dulce Benth. belongs to the Leguminosae family, which contains several members that are important components of human diets owing to their high protein content and quality. In this study the seed proteins from P. dulce were separated and identified using two‐dimensional gel electrophoresis (2‐DE) and mass spectrometry respectively. RESULTS: The 2‐DE protein map revealed a total of 317 distinct protein spots, including a cluster of about 12 proteins located in the region of pI 5–6 with molecular masses of 55–97 kDa that accounted for more than 50% of the total proteins. Ninety‐six of the most abundant protein spots were analysed using nano liquid chromatography/tandem mass spectrometry (LC/MS/MS), from which 27 were successfully identified through the query of acquired tandem mass spectral data used in MASCOT searching against a custom legume protein database. A further four proteins from the highly abundant protein cluster were putatively identified using mass spectrometry‐driven BLAST (MS‐BLAST) homology searches. CONCLUSION: This research has generated a 2‐DE proteome reference map for P. dulce seeds and used LC/MS/MS to characterise the proteins. The identification of proteins from P. dulce was carried out using the sequence database successively for MASCOT and MS‐BLAST homology‐based searches. Copyright © 2009 Society of Chemical Industry