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%。      

高效液相色谱-串联质谱法测定婴幼儿米粉中12种全氟烷基化合物

目的 建立了高效液相色谱-串联质谱(high performance liquid chromatography-tandem mass spectrometry, HPLC-MS/MS)测定婴幼儿辅食米粉中12种全氟烷基化合物(perfluorinated compounds, PFCs)的方法。方法 样品经酸化乙腈提取, 加入乙二胺-N-丙基硅烷(ethylenediamine-n-propylsilane, PSA), C18, 石墨化碳黑(Graphitized carbon black, GCB)3种吸附剂后, 涡旋振荡对样品进行净化。利用C18反相色谱柱对婴幼儿辅食米粉中12种PFCs进行分离, 负离子模式电喷雾电离, 配合多级反应离子扫描(multiple reaction monitoring, MRM)定性定量分析目标化合物。考察了流动相和色谱柱对分离检测的影响, 优化了主要影响因素和实验条件, 在条件优化过程中采用外标法进行定量分析。结果 12种PFCs标准曲线的线性相关系数大于0.995, 检出限为0.07~0.15 μg/kg, 在0.2、0.5、1.0 μg/kg加标水平下, 样品的加标回收率为68.8%~115.4%, 相对标准偏差(relative standard deviation, RSD)为1.25%~15.6% (n=6)。结论 该方法操作简便, 分离效果好, 检出限低, 适用于婴幼儿辅食米粉中PFCs的检测。     

高效液相色谱-串联质谱法测定烟草中的七种糖类物质

建立了一种能够同时快速测定烟叶及卷烟中七种主要糖类物质的液相色谱-串联质谱（LC/MS/MS）的定量分析方法。以乙腈:水（82:18）为流动相,经高效液相色谱分离,MS/MS使用多反应监测（MRM）扫描方式,在18min内,可完成烟草中七种主要糖类物质的定量分析,七种糖类物质在2～100μg/mL内线性良好（r>0.999）,检出限均在50.0ng/mL以内。本方法操作简便、灵敏度高、分析速度快,可以应用于烟叶及卷烟中七种主要糖类物质含量的测定。      

液相色谱-串联质谱法测定食品用纸容器中全氟辛酸

建立高效液相色谱-串联质谱结合加速溶剂萃取测定食品用纸容器中全氟辛酸的方法。样品用甲醇作为溶剂进行快速溶剂萃取。萃取液经C18固相萃取柱富集净化后,以C18柱为分离柱,以甲醇、水为流动相,梯度洗脱,电喷雾负离子模式下多反应监测模式检测。全氟辛酸在0.5～50ng/mL范围内线性良好(R2=0.9993),回收率为90.2%～103.3%,相对标准偏差为2.74%～6.03%,检出限为0.1μg/kg(RSN=3)。该方法操作简便,灵敏度高,适用于食品用纸容器中全氟辛酸及其盐类残留分析。     

同位素稀释-超高效液相色谱-串联质谱法测定鱼肉中8 种全氟化合物

建立鱼肉中8 种全氟化合物的同位素稀释-超高效液相色谱-串联质谱快速分析方法。鱼肉加入同位素内标 后使用乙腈超声萃取,经WAX固相萃取小柱净化后,采用C18反相色谱柱进行分离,用配有电喷雾离子源的三重四 极杆质谱进行多反应离子监测,同位素稀释内标法定量。8 种全氟化合物在0.1～50.0 μg/L范围内线性关系良好, 相关系数不低于0.998,方法检出限在0.03～0.15 μg/kg之间,平均加标回收率为87.7%～104.4%,相对标准偏差为 4.1%～10.7%。该法灵敏度高、快速准确,适用鱼肉中全氟化合物的定性和定量检测。     

高效液相色谱-串联质谱法检测纺织品中26种全氟和多氟化合物

通过液相色谱-串联质谱法对纺织品中的26种全氟和多氟化合物进行了分析检测。采用超声波萃取方法,甲醇作为溶剂,对纺织品常用的阴性贴衬布样品进行了加标试验,回收率和相对标准偏差分别在80.03%～103.82%和2.92%～9.47%范围,定量限为0.01mg/kg,符合日常检测的要求。本研究确定的检测全氟和多氟化合物的方法具有前处理简单、检测灵敏度高、定量限低的特点,为纺织品中全氟和多氟化合物检测标准的制定提供了技术支持。     

茶叶中10种农药残留的液相色谱-串联质谱法和气相色谱-串联质谱法测定

建立了茶叶中啶虫脒、乐果、吡虫啉、灭多威、甲基嘧啶磷、腐霉利共6种农药残留的液相色谱-串联质谱(LC-MS/MS)测定方法和溴氰菊酯、乐果、高效氯氟氰菊酯、p,p'-滴滴伊、甲基嘧啶磷、腐霉利、哒螨灵共7种农药残留的气相色谱-串联质谱(GC-MS/MS)测定方法。其中,乐果、甲基嘧啶磷和腐霉利三种农药均能通过两种方法测定。LC-MS/MS法测定的6种农药,在5~200 μg/L范围内线性关系良好(R²>0.995),在10、50、100 μg/kg加标水平下的回收率为70.0%~105.0%,相对标准偏差为0.3%~18.7%。GC-MS/MS法测定的7种农药,在10~500 μg/L范围内线性关系良好(R²>0.996),在10、50、300 μg/kg加标水平下的回收率为82.0%~110.0%,相对标准偏差为1.8%~12.0%。该方法完善了茶叶中10种农药残留检测方法针对实际样品的检测,灵敏度满足国外限量标准要求,适合出口茶叶中农药残留的测定。     

液相色谱-串联质谱法测定豆类中左旋多巴

文章建立一种豆类中左旋多巴的液相色谱-串联质谱测定方法。样品经0.3 mol/L乙酸水溶液超声提取,Agilent Proshell 120 SB-C18(2.1 mm×150 mm,2.7μm)色谱柱分离,以0.1%甲酸水-甲醇为流动相进行梯度洗脱,多反应监测(MRM),内标法定量。结果表明,左旋多巴在0.1~5.0 mg/L范围内线性关系良好,相关系数为0.9994,检出限为1.5 mg/kg,定量限为5.2 mg/kg,方法的平均加标回收率为96.9%~105.5%,日内精密度和日间精密度均小于4%,具有操作简单、灵敏度高、准确度高、重现性好等特点,能够很好满足豆类中左旋多巴含量的检测需要。     

高效液相色谱-串联质谱法测定黄瓜中的4种甜味剂

本方法以超纯水作为萃取试剂,通过高效液相色谱-串联质谱仪,同时测定黄瓜中阿斯巴甜、安赛蜜、糖精钠和甜蜜素4种甜味剂。该方法可准确测定黄瓜中4种甜味剂且有较好的线性关系,在线性范围1～100 ng/mL,相关系数大于0.99,检出限均为0.01 mg/kg,加标回收率在82.1%～98.2%,相对标准偏差为1.8%～5.8%。     

液相色谱-串联质谱法与离子色谱-串联质谱法测定食品中氯酸盐和高氯酸盐方法比较研究

目的 考察离子色谱-串联质谱法（ion chromatography-tandem mass spectrometry,IC-MS/MS）和液相色谱-串联质谱法（liquid chromatography-tandem mass spectrometry,LC-MS/MS）在测定不同食品中氯酸盐和高氯酸盐的一致性。方法 利用乙腈/水（3:2, V:V）提取鸡蛋、奶粉和菠菜中的目标物,经石墨化炭黑（graphitized carbon black, GCB）小柱净化,以IonPacTM AS20离子色谱柱和CSHTM Fluoro-Phenyl液相色谱柱为分析柱,三重四极杆质谱仪检测,内标法定量。对两种方法测得的数据进行正态性检验和差异性分析。比较两种方法的保留时间漂移,考察色谱稳定性。对两种方法测得的浓度进行线性回归和B-AbBland -aAltman（B-A）图可视化考察方法一致性。结果 两种方法测得氯酸盐（高氯酸盐）的浓度在1~500（0.1~50.0） ?g/L范围内线性良好（r2＞0.999）。IC-MS/MS与LC-MS/MS测定高氯酸盐的定量限均为0.5 ?g/kg,氯酸盐的定量限分别为5.7 ?g/kg和4.2 ?g/kg。回收率范围分别为82.3%~107.4%和94.8%~109.4%,相对标准偏差分别为1.5%~13.6%和1.2%~9.6%。IC-MS/MS（LC-MS/MS）测得鸡蛋、奶粉、菠菜中氯酸盐和高氯酸盐的基质效应分别为12.1%（22.1%）、9.0%（27.4%）、-11.8%（-24.0%）和-16.8%（-18.5%）、-18.6%（-28.4%）、-20.2%（-21.1%）。线性回归法显示两种方法测定氯酸盐和高氯酸盐浓度的回归曲线斜率分别为1.0144和1.0908。B-A图显示绝大多数数据点位于平均值±1.96标准偏差范围。结论 两种方法的准确度和精密度均符合化学检验方法验证通则的要求,两种方法测得的氯酸盐、高氯酸盐浓度结果基本一致,但氯酸盐在LC-MS/MS系统中的保留时间稳定性更好,IC-MS/MS在测定食品中氯酸盐、高氯酸盐时的抗基质干扰能力更强。     

SPE-LC-MS/MS测定快餐纸袋中7种全氟有机物

建立了快餐纸袋中7种全氟有机物（全氟己酸、全氟庚酸、全氟辛酸、全氟壬酸、全氟十二烷酸、全氟十四烷酸、全氟辛烷磺酸盐）残留的固相萃取-液相色谱串联质谱（SPE-LC-MS/MS）分析方法。样品以1%甲酸-甲醇溶液超声提取,经C18固相萃取小柱净化,以0.1%甲酸乙腈-2mmol/L乙酸铵水溶液为流动相,经C8反相色谱柱分离,采用多反应监测（MRM）负离子模式检测,外标法定量。阴性样品添加实验表明:方法的检出限为0.008⁰.104μg/kg（S/N=3）;平均回收率为:80.2%¹06.0%;相对偏差为:2.2%⁸.1%（n=6）。该方法前处理简单,回收率高,精密度高,适用于各类快餐纸袋中全氟化合物的定量检测,为食品接触材料中全氟有机物的定量检测提供了方法。      

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.     

基于液相色谱-串联质谱法的纺织品中痕量全氟化合物的测定

采用超声法提取纺织品中的全氟化合物。以C18为分析柱,甲醇-5 mmol/L乙酸铵为梯度洗脱淋洗液, 13 min内即可分离全氟己酸(PFHxA),全氟辛酸(PFOA),全氟壬酸(PFNA),全氟癸酸(PFDA),全氟十一酸(PFuDA),全氟十二酸(PFDoA), 全氟丁烷磺酸(PFBS),全氟己烷磺酸(PFHxS),全氟辛烷磺酸(PFOS),全氟癸烷磺酸(PFDS) 10种分析物。以313.1/268.9,412.9/368.9,462.9/418.9,512.7/468.9,562.7/518.9,612.8/568.9,298.8/99,399.2/99,498.8/99,599/99分别对PFHxA,PFOA,PFNA,PFDA,PFuDA,PFDoA,PFBS,PFHxS,PFOS,PFDS进行监控和定量分析。利用同位素内标法进行定量,线性范围和添加回收率分别为0.5～10 µg/m2、84.6%～111.8%,检出限为0.5 µg/m2,低于欧盟指定针对纺织品1 µg/m2 的限定。结果表明,本方法准确、快速,并成功用于20种纺织品实样的检测。     

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。     

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。     

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.     

高效液相色谱串联质谱法测定鲢鱼中的微囊藻毒素

建立了高效液相色谱/串联质谱法（HPLC-MS/MS）同时定量检测洪泽湖鲢鱼中微囊藻毒素（MC-RR,MC-LR和MC-YR）的方法,用甲醇提取鲢鱼肉中的微囊藻毒素,用C18固相萃取柱净化。以甲醇和0.1%的甲酸水溶液为流动相,采用梯度洗脱用C18色谱柱对鱼肉中的微囊藻毒素进行分离,用电喷雾质谱正离子选择模式进行检测。三种微囊藻毒素MC-RR,MC-LR,MC-YR的线性良好,检出限分别为0.2、0.4、0.4μg·L-1,定量限分别为0.8、0.9、0.9μg·L-1。对链鱼样品进行加标回收,回收率在87.1%～101.2%,10次平行测定的相对标准偏差均小于8%。该方法具有准确、快速、简单以及灵敏度高的特点,能够适应大规模样品的快速分析要求。      

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.     

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.