Determination of genotoxic phenylhydrazine agaritine in mushrooms using liquid chromatography-electrospray ionization tandem mass spectrometry

A new method with good sensitivity and specificity for detecting and quantifying genotoxic hydrazines, agaritine and 4-(hydroxymethyl)phenylhydrazine (HMPH), was developed using liquid chromatography-electrospray tandem mass spectrometry (MS). Synthetic agaritine and HMPH were structurally assigned by ¹H-, ¹³C- and two-dimensional nuclear magnetic resonance (NMR) analysis (HMBC and HMQC), high-resolution fast-atom bombardment (HR-FAB) MS and time of flight (TOF) MS. The polar molecule agaritine was separated on an ODS column using 0.01% AcOH-MeOH (99:1, v/v) as an eluent with a simple solid-phase extraction cleanup. There were no interference peaks for any of the mushrooms. Agaricus spp. contained 1247 and 2017 µg g^-1 agaritine. Other species of mushroom had no agaritine. Recoveries of agaritine from spiked mushroom samples were 60.3-114%. Intra-day precision values were 5.5 and 4.2%, and the inter-day precision values were acceptable (15.0 and 23.0%), as agaritine is unstable. The limit of quantification was 0.003 µg g^-1. Even a trace amount of agaritine in mushrooms can, therefore, be determined using this method. We also directly analysed HMPH, an active free hydrazine form of genotoxic agaritine, and obtained direct evidence of its absence from mushrooms. A precursor ion scan confirmed that agaritine derivatives, which could exert similar toxicity, were absent. The results indicate that this specific and sensitive analytical method for detecting and quantifying agaritine and its derivatives could help evaluate the risk of mushroom hydrazines to humans.     

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。     

LC-MS-MS法测定包装材料中壬基酚含量及其迁移量

采用冷冻高速离心去除油脂及杂质干扰的样品前处理方式,应用高效液相色谱柱进行分离,采用电喷雾(ESI),以负离子检测模式进行质谱分析,同位素内标法定量,建立了液相色谱-质谱(LC-MSMS)法检测ARADHA产品及包装材料壬基酚(NP)的含量检测分析方法。实验结果表明,壬基酚质量浓度在5~500μg/kg范围内与色谱峰面积呈良好的线性关系,相关系数R2=0.9998,检出限为0.3μg/kg,定量限为1.0μg/kg。ARADHA的微胶囊样品、油脂样品及包装袋三种不同样品的壬基酚不同添加量加标回收率在93.2%~102.9%之间,相对标准偏差(RSD)在2.2%~7.0%之间(n=6)。该方法前处理简便、选择性好、灵敏度高,运用此方法同时研究了包装袋中的壬基酚在ARADHA油脂及微胶囊样品中的迁移量,结果表明,壬基酚含量高的包装袋存在显著的壬基酚迁移现象,故需对包装袋的壬基酚进行严格控制。     

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%。     

Simultaneous determination of synthetic food additives in kimchi by liquid chromatography-electrospray tandem mass spectrometry

Food Science and Biotechnology - A new analytical method was developed for the simultaneous determination of seven food additives (Ponceau 4R, Allura Red AC, Amaranth, 4-hydroxymethyl benzoic acid,...     

Characterization of new nitrosamines in drinking water using liquid chromatography tandem mass spectrometry

N-Nitrosodimethylamine (NDMA), a member of a group of probable human carcinogens, has been detected as a disinfection byproduct (DBP) in drinking water supplies in Canada and the United States. To comprehensively investigate the occurrence of possible nitrosamines in drinking water supplies, a liquid chromatography-tandem mass spectrometry technique was developed to detect both thermally stable and unstable nitrosamines. This technique consisted of solid-phase extraction (SPE), liquid chromatography (LC) separation, and tandem quadrupole linear ion trap mass spectrometry (MS/MS) detection. It enabled the determination of sub-ng/L levels of nine nitrosamines. Isotope-labeled N-nitrosodimethylamine-d6 (NDMA-d6) was used as the surrogate standard for determining recovery, and N-nitrosodi-n-propylamine-dl4 (NDPA-dl4) was used as the internal standard for quantification. The method detection limits were estimated to be 0.1-10.6 ng/L, and the average recoveries were 41-111% for the nine nitrosamines; of these, NDMA, N-nitrosopyrrolidine (NPyr), N-nitrosopiperidine (NPip), and N-nitrosodiphenylamine (NDPhA) were identified and quantified in drinking water samples collected from four locations within the same distribution system. In general, the concentrations of these four nitrosamines in this distribution system increased with increasing distance from the water treatment plant, indicating that the amount of formation was greater than the amount of decomposition within this time frame. The identification of NPip and NDPhA in drinking water systems and the distribution profiles of these nitrosamines have not been reported previously. These nitrosamines are toxic, and their presence as DBPs in drinking water may have toxicological relevance.     

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 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.     

液相色谱-串联质谱法测定河豚鱼和鳗鱼中 9种青霉素类抗生素

目的 建立高压液相色谱-电喷雾串联质谱(HPLC-MS-MS)同时测定河豚鱼和鳗鱼中9种青霉素残留量的检测方法。方法 样品经乙腈-氨水溶液提取后, 用C18色谱柱分离, 乙腈-乙酸为流动相梯度洗脱, 最后采用液相色谱-电喷雾串联质谱在正离子多反应监测模式下测定。结果 在1.0~20 μg/kg(LOQ~10LOQ)范围时, 方法线性关系良好, 相关系数大于0.999。在LOQ、2 LOQ、4 LOQ、10 LOQ四个添加水平下青霉素的回收率在81.4%~109.7%之间, 相对标准偏差2.81%~7.12%之间, 方法检出限是: 萘夫西林、青霉素 G、哌拉西林、青霉素 V、苯唑西林为1.0 μg/kg; 阿莫西林、氨苄西林、氯唑西林、双氯西林为2.0 μg/kg。结论 此方法灵敏度高, 准确性好, 适用于水产品中青霉素的定量检测。     

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。     

Monitoring algal toxins in lake water by liquid chromatography tandem mass spectrometry

Microcystins (MCs) and cylindrospermopsin (CYL) are potent natural toxins produced by cyanobacteria (blue-green algae) that grow worldwide in eutrophic freshwaters and cause animal and human water-based toxicoses. The main purpose of this work has been assessing the contamination levels of some MCs and CYL in eutrophic Italian lake (Albano) water. To do this, we have developed an original analytical method involving MC extraction with a sorbent (Carbograph 4) cartridge. CYL is a highly polar compound that is scarcely retained by any sorbent material. To analyze this toxin, we directly injected 0.5 mL of filtered lake water into the liquid chromatography (LC) column. Analytes were quantified by LC coupled to tandem mass spectrometry in the multireaction monitoring mode. The recovery of five selected MCs added to an analyte free lake water sample at three different concentrations (50, 150, and 500 ng/L) ranged between 93 and 103% with RSD values no larger than 8%. Limits of quantification (LOQ) of the five MCs were within the 2-9 ng/L range, whereas the LOQ of CYL was 300 ng/L. The occurrence and abundance of cyanotoxins in Lake Albano was monitored over four months (Sept-Dec 2004) by analyzing water samples collected monthly at the center of the lake and at different depths (from 0 to -30 m). During survey and with the MS/MS system operating in the parent ion scan mode, we individuated two demethylated forms of MC-RR and one demethylated variety of MC-LR. Demethylated MC-RRs are known to be even more toxic than MC-RR toward zooplanktic grazers. CYL was the most-abundant toxin during the first three monitoring months. To the best of our knowledge, this is the first work reporting concentration levels of CYL in lake water.     

液相色谱-串联质谱法测定茶叶中二氰蒽醌残留量

目的建立液相色谱-串联质谱法(liquidchromatographytandemmassspectrometry,LC-MS/MS)测定茶叶中二氰蒽醌残留。方法茶叶用乙腈(含0.1%甲酸)提取,经固相萃取柱(HC-C18 SPE)净化后采用多反应监测(multiplereactionmonitoring,MRM)模式进行检测,外标法定量。结果目标化合物在一定范围内(0.391～12.5μg/L)线性关系良好,相关系数(r2)大于0.995。样品中二氰蒽醌的定量限(limitofquantification,LOQ)和检出限(limitofdetection,LOD)分别为10.0、5.00μg/kg;不同加标浓度样品10.0μg/kg(LOQ)、20.0μg/kg(2×LOQ)、50.0μg/kg(5×LOQ)的平均回收率为84.1%～103%,相对标准偏差(RSDs)为3.18%～4.62%。25份市售茶叶中均未检出二氰蒽醌。结论该方法简便、快速,准确。各项性能参数均能符合技术规范的要求,已应用于市售茶叶的检测。     

A novel method to determine valnemulin in feedingstuffs for several animal species by liquid chromatography-electrospray tandem mass spectrometry

A new method specific for the determination and unambiguous confirmation of the antibiotic valnemulin in feed for all animal species is described. Simple clean-up based on solvent extraction and liquid partition is carried out prior to determination by liquid chromatography coupled to electrospray tandem mass spectrometry on a hybrid QTRAP 4000 system, in multiple reaction monitoring mode. Valnemulin is licensed in the European Union as a veterinary drug for use in feed for pigs and rabbits, but unavoidable carryover in feed for non-target species should be monitored. The method is rapid and reliable, and was validated in-house at 10, 100 and 750 ng g^–1, evaluating the analytical performances according to Commission Regulation (EC) No. 882/2004. Good mean recoveries from 79.7% to 92.6%, and within-laboratory reproducibility RSDs, ranging from 6.2% to 12.1%, were measured; the limit of quantification at 10.0 ng g^–1 also allows for sensitive evaluation of undesirable carryover in feed for non-target species. The results of monitoring 24 compound feeds for several animal species are also reported.     

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.     

食品添加剂红花黄色素化学成分的HPLC-ESI-MS分析

目的:采用HPLC-ESI-MS分析方法,鉴定其化学成分。方法:高效液相色谱采用Phenomenex Gemini-C18(4.6 mm×250 mm,5μm),以0.01%三氟乙酸水溶液(A)-乙腈(B)为流动相,梯度洗脱,检测波长为全波长;质谱使用ESI离子源,正、负离子分别检测。结果:通过质谱分析以及参照相关文献共鉴定出11个成分,其中羟基红花黄色素A和脱水红花黄色素B为期主要的有效成分。结论:该方法灵敏度高、分离度好,为红花黄色素物质基础的研究提供一种快速准确的分析方法。对比了现行最新红花黄色素标准,建议现行红花黄色素标准规定的有效成分修改为羟基红花黄色素A和脱水红花黄色素B。     

Analysis of pharmaceuticals in water by isotope dilution liquid chromatography/tandem mass spectrometry

A method has been developed for the trace analysis of 15 pharmaceuticals, four metabolites of pharmaceuticals, three potential endocrine disruptors, and one personal care product in various waters. The method employs solid-phase extraction (SPE) and liquid chromatography/tandem mass spectrometry (LC-MS/MS), using electrospray ionization (ESI) in both positive and negative modes. Unlike many previous LC-MS/MS methods, which suffer from matrix suppression, this method uses isotope dilution for each compound to correct for matrix suppression, as well as SPE losses and instrument variability. The method was tested in five matrices, and results indicate that the method is very robust. Matrix spike recoveries for all compounds were between 88 and 106% for wastewater influent, 85 and 108% for wastewater effluent, 72 and 105% for surface water impacted by wastewater, 96 and 113% for surface water, and 91 and 116% for drinking water. The method reporting limits for all compounds were between 0.25 and 1.0 ng/L, based on 500 mL of sample extracted and a final extract volume of 500 microL. Occurrence of the compounds in all five matrices is also reported.     

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。      

UPLC-MS/MS法与分光光度法测定乳及乳制品中左旋肉碱的比较

文中建立了超高效液相色谱-质谱联用仪(UPLC-MS/MS)和分光光度计测定乳及乳制品中L-肉碱的方法。超高压液相色谱-质谱联用法采用C8(3.5μm,50 mm×2.1 mm)色谱柱,0.1%七氟丁酸/水溶液和甲醇作为流动相分离样品,L-肉碱-(甲基-d3)内标物质用以消除信号抑制和基质干扰,质谱采用ESI+电离模式、多离子反应监测(MRM)方式进行检测。分光光度法采用高氯酸沉淀蛋白质,碱皂化使溶液中结合态的左旋肉碱游离出来,通过酶促反应,使用分光光度计间接测定左旋肉碱。结果表明:分光光度法的检出限为2.0 mg/100 g,回收率在96.2%¹04.7%,相对标准偏差RSD在1.34%104.7%,相对标准偏差RSD在1.34%³.69%。UPLC-MS/MS法的检出限为2 ng/100 g,回收率在97.8%3.69%。UPLC-MS/MS法的检出限为2 ng/100 g,回收率在97.8%¹09%,相对标准偏差RSD为1.77%109%,相对标准偏差RSD为1.77%⁵.65%。以上2种方法均适用于乳及乳制品中L-肉碱的检测,且测定结果无显著性差异。UPLC-MS/MS法具有操作简便、快速、高效、可控性强等特点,更适用于大量样品的集中快速检测。