Quantitative Analysis of 10 Mycotoxins in Wheat Flour by Ultrahigh Performance Liquid Chromatography‐Tandem Mass Spectrometry with a Modified QuEChERS Strategy

A simple and sensitive analytical method for quantitative analysis of 10 mycotoxins was developed and validated by a combination of modified QuEChERS (quick, easy, cheap, effective, rugged, and safe) procedure with ultrahigh performance liquid chromatography‐tandem mass spectrometry (UHPLC‐MS/MS). Sample preparation involved QuEChERS with dispersive solid phase extraction for clean‐up, and analysis was performed by reversed‐phase UHPLC‐MS/MS using electrospray negative ionization and multiple reaction monitoring. Under optimized conditions, the calibration curves displayed good linear relationships with all coefficients of determinations (r²) higher than 0.998. The limits of quantification for all target mycotoxins were lower than 7 μg/kg. Trueness and precision for the analytes were 70% to 116% average recoveries and 2% to 13% relative standard deviations (RSDs). The validated method was used to analyze 46 wheat flour samples for the targeted mycotoxins. The method can be used as a rapid and robust tool for screening mycotoxin in cereal products.     

Development of a liquid chromatography-tandem mass spectrometric method for the simultaneous determination of tropane alkaloids and glycoalkaloids in crops

A new, rapid and sensitive multiresidue method is reported for the simultaneous determination of tropane alkaloids (tropine, atropine, scopolamine, homatropine, anisodamine) and glycoalkaloids (α-solanine, α-chaconine) in grains and seeds (wheat, rye, maize, soybean, linseed). Dispersive solid phase extraction (DSPE) was performed with 0.5% formic acid in acetonitrile/water and a mixture of magnesium sulphate, sodium chloride and sodium citrate. For a fast and effective clean-up procedure for oily matrices such as soybean and linseed, matrix solid phase dispersion (MSPD) C₁₈ material was used to remove co-extracted non-polar components. No clean-up was necessary for less oily matrices following extraction. The analytes were separated by isocratic HPLC on a Chirobiotic V column and detected using a triple quadrupole mass spectrometer with electrospray ionization (ESI). All analytes were monitored in the positive ion mode. The method performance is presented in terms of linearity in the range 5–80?ng/g (r ^2?=?0.998), specifity, selectivity, accuracy (recoveries from 61–111%), precision (CV?<?5%) and ruggedness. The limits of quantitation (LOQ) were in the range 2.2–4.9?ng/g.     

通过式SPE-UPLC-MS/MS测定植物油中的9 种酚类抗氧化剂

建立采用通过式固相萃取柱净化，超高效液相色谱-串联质谱法同时检测植物油中9 种酚类抗氧化剂的方法。油样品中酚类抗氧化剂用酸化乙腈提取，正己烷除脂，上清液经Oasis? PRIME HLB通过式固相萃取柱净化，C18色谱柱分离，采用乙腈-水流动相进行梯度洗脱，三重四极杆质谱电喷雾多反应监测模式检测，外标法定量。结果表明：采用本实验建立的方法，没食子酸丙酯、2,4,5-三羟基苯丁酮、叔丁基对苯二酚、去甲二氢愈创木酸、叔丁基对羟基茴香醚、2,6-二叔丁基-4-羟甲基苯酚、没食子酸辛酯、2,6-二叔丁基对甲基苯酚及没食子酸十二酯9 种抗氧化剂在各自质量浓度范围内线性关系良好，相关系数（R2）大于0.994。其中9 种抗氧化剂的方法检出限（RSN=3）在0.003～0.02 mg/kg范围，定量限（RSN=10）在0.01～0.05 mg/kg范围。在0.05、5.0、50.0 mg/kg三个添加水平下，9 种抗氧化剂平均加标回收率在82.2%～115.2%之间，相对标准偏差均小于9.3%。该方法简单、高效、灵敏度高，适用于植物油中抗氧化剂的快速定性、定量分析。     

超高效液相色谱-串联质谱法同时测定鱼、肉类罐头食品中的BADGE、NOGE及其衍生物

建立了一种罐头食品中的BADGE(bisphenol A diglycidyl ether,双酚A-二环氧甘油醚)、NOGE(novolacglycidyl ether,酚醛清漆甘油醚)及其衍生物含量的超高效液相色谱-串联质谱检测法。前处理包括正己烷/丙酮微波辅助萃取,Varain-PS-DVB固相萃取柱净化等。样品经BEH C18色谱柱(100 mm×2.1 mm,1.7μm)分离,以乙腈和0.2%甲酸水为流动相,进行梯度洗脱,在API 4000-QTRAP质谱仪电喷雾正离子、多反应监测(MRM)模式下进行检测。分析物检出限达到0.010 2 ng/g到0.197 2 ng/g,三水平加标回收率在65.7%～99.1%。     

Development of a liquid chromatography-tandem mass spectrometric method for the simultaneous determination of tropane alkaloids and glycoalkaloids in crops

A new, rapid and sensitive multiresidue method is reported for the simultaneous determination of tropane alkaloids (tropine, atropine, scopolamine, homatropine, anisodamine) and glycoalkaloids (α-solanine, α-chaconine) in grains and seeds (wheat, rye, maize, soybean, linseed). Dispersive solid phase extraction (DSPE) was performed with 0.5% formic acid in acetonitrile/water and a mixture of magnesium sulphate, sodium chloride and sodium citrate. For a fast and effective clean-up procedure for oily matrices such as soybean and linseed, matrix solid phase dispersion (MSPD) C(18) material was used to remove co-extracted non-polar components. No clean-up was necessary for less oily matrices following extraction. The analytes were separated by isocratic HPLC on a Chirobiotic V column and detected using a triple quadrupole mass spectrometer with electrospray ionization (ESI). All analytes were monitored in the positive ion mode. The method performance is presented in terms of linearity in the range 5-80 ng/g (r(2)=0.998), specifity, selectivity, accuracy (recoveries from 61-111%), precision (CV<5%) and ruggedness. The limits of quantitation (LOQ) were in the range 2.2-4.9 ng/g.     

高分辨质谱定性筛查牛奶和奶粉中兽药残留

目的 建立高分辨质谱定性筛查牛奶和奶粉中兽药残留的高通量方法。方法 样品经乙腈、QuEChERS盐包提取, 采取改良的3种不同方式[QuChERS、高分辨质谱(high resolution mass spectrometry, EMR)、固相萃取(solid phase extraction, SPE)]净化提取液, 用液相色谱联用高分辨质谱(liquid chromatography-high resolution mass spectrometry, LC-HRMS)筛查了牛奶和奶粉中138种兽药残留, 建立兽药信息数据库, 并用截断值(Vcut-off, 判断阳性和阴性样品的临界值)作为评估筛查方法的指标。结果 改良的QuChERS可以获得更高的回收率, 当截断值(Vcut-off)设定为0.2时, 在2种加标水平下, 有109种兽药通过了筛查方法验证的要求, 假阳性和假阴性概率均低于5%。结论 此方法适用于牛奶和奶粉中多兽药残留的定性筛查, 一针进样可以得到109种兽药残留的筛查信息, 方法假阳性和假阴性概率在规定的目标物浓度下都低于5%。     

Rapid detection of chloramphenicol in animal products without clean-up using LC-high resolution mass spectrometry

A rapid confirmatory and quantitative method using liquid chromatography-high resolution mass spectrometry (LC-HRMS) was developed to determine sub-μg/kg levels of chloramphenicol (CAP) in meat products. The sample plus deuterated chloramphenicol internal standard was homogenised, extracted with ethyl acetate, centrifuged and the supernatant evaporated to dryness. The residue was re-dissolved in methanol/5% ammonium acetate solution (20:80, v/v), defatted with hexane and directly injected into the LC-MS. Chromatographic separation was performed on a C(18) column using methanol/water (60:40, v/v) as the mobile phase. CAP was detected using selected ion monitoring of the high accurate mass of the molecular ion [M-H](-) of CAP using a LTQ-Orbitrap mass spectrometer in negative electrospray ionisation mode (ESI(-)). The limit of quantification of the method was 0.1?μg/kg using isotope internal standard. Recoveries of CAP spiked at levels of 0.1-1.0?μg/kg ranged from 73 to 99%, and the relative standard deviation ranged 3.9-8.1%.     

Simultaneous Determination of Eight Tranquilizers in Pork by Ultra-Performance Liquid Chromatography Coupled with Electrospray Tandem Mass Spectrometry

An ultra-performance liquid chromatography/electrospray ionization tandem mass spectrometry (UPLC-ESI-MS/MS) method was developed and validated for quantification of eight tranquillizers (chlorpromazine, imipramine hydrochloride, diazepam, nitrazepam, nordazepam, oxazepam, flurazepam, and haloperidol) in pork. Sample pretreatment consisted of extraction by acetonitrile, defatted by n-hexane, and further solid phase extraction by hydrophilic-lipophilic balance (HLB) extraction cartridges. The triple quadrupole mass spectrometer was operated in positive ion mode, and multiple reaction monitoring was used for drug quantification. The method was validated over the concentration ranges of 1.0 ～ 250 μg kg^?1 for the eight tranquillizers. The calibrations were performed in sample matrices, and the interference effect of sample matrices on the ionization was effectively eliminated. Good linear relationship (R ² > 0.99) was observed within the concentration range of 1.0–250 μg kg^?1. The average recoveries of the eight tranquillizers spiked at three levels ranged from 63.7 to103.2 % with the relative standard deviation below 11.8 %. The limits of detection were between 0.06 and 0.30 μg kg^?1, and the limits of quantification were between 0.2 and1.0 μg kg^?1 for all analytes in pork. This validated method has been successfully used to quantify the concentration of the eight tranquillizers in pork samples.     

PRiME HLB固相萃取柱结合气相色谱-串联质谱法快速测定茶叶中200种农药残留

目的 建立PRiME HLB固相萃取柱结合气相色谱-串联质谱法(gas chromatography-tandem mass spectrometry,GC-MS/MS)快速测定茶叶中200种农药残留量的分析方法.方法 样品用乙腈提取,经PRiME HLB通过式固相萃取柱净化,残留量采用气相色谱-串联质谱法进行检测.结...     

The Determination of PCBs in Meat and Sea Food by GC-QqQ-MS/MS

A new method was developed for the determination of 12 polychlorinated biphenyls (PCBs) in meat and sea food by gas chromatography coupled to triple quadrupole mass spectrometry using selected reaction monitoring technique. The method was based on ultrasonic extraction and florisil column cleaning up. Recoveries of the 12 PCBs ranged from 70.4?% to 100.6?% and the relative standard deviations were from 0.5?% to 12.6?%. The limits of detection ranged from 0.006 to 0.009 μg/kg and the limits of quantitation ranged from 0.02 to 0.03 μg/kg. Eight meat and sea food samples were analyzed for the analysis of the polychlorinated biphenyls using the proposed method.     

气相色谱-串联质谱法测定5种植物源性食品中氯肽酸和草芽畏残留量

摘 要: 目的 建立气相色谱-串联质谱法测定水果、蔬菜、茶叶、粮谷及花生油等植物源食品中氯肽酸和草芽畏两种农药残留的分析方法。方法 针对非油基质样品, 选取柚子、生菜、茶叶及小麦粉样品, 经2%甲酸乙腈溶液提取, 三甲基硅烷化试剂衍生, MAS-Q盐包吸附色素等杂质, 再经HLB柱净化的前处理方法; 针对含油基质, 选取花生油样品, 经甲醇提取, 三甲基硅烷化试剂衍生, 再经HLB柱净化。净化后样品用气相色谱-串联质谱仪进行检测。结果 为消除基质效应影响,补偿前处理提取过程中的损失,采用过程标准校正法, 两种农药在不同基质样品中呈现良好的线性关系, 相关系数均大于0.99。在0.01、0.02、0.05 mg/kg加标水平下, 两种农药在不同基质中的回收率均在93.6%~113.6%之间, 相对标准偏差在0.9%~9.8%之间 (n=6)。结论 该方法灵敏度高, 选择性好, 在水果、蔬菜、粮谷、乃至茶叶、花生油等复杂基质中, 氯酞酸和草芽畏的定量限均可达到0.01 mg/kg, 满足GB 2763-2021《食品安全国家标准 食品中农药最大残留限量》临时限量的要求。     

UPLC-MS/MS法同时检测食品中3种主要牛奶过敏原

为准确定量食品中的牛奶过敏原，采用超高效液相色谱-串联质谱法同时检测3?种主要牛奶过敏原β-乳球蛋白、αs1-酪蛋白和αs2-酪蛋白，避免单一致敏蛋白在加工中的降解和灵敏度不高导致的假阴性。标准蛋白酶解液经纳升液相色谱-串联轨道阱高分辨质谱分析后，筛选得到8?条特征肽段。利用三重四极杆质谱多反应监测模式，选择面粉作为空白基质进行方法学验证。结果表明，该方法在1.6～30?000?ng/mL范围内线性良好，R2＞0.999；定量限分别为β-乳球蛋白50?μg/g、αs1-酪蛋白3.2?μg/g、αs2-酪蛋白40?μg/g；平均回收率为86.41%～98.60%，相对标准偏差不大于8.95%；基质效应在86.04%～97.48%之间。此方法可应用于含牛奶和不含牛奶的实际商品，旨在鉴别食品中过敏原标签与产品实际过敏原间的差异，降低牛奶过敏消费者的健康隐患。     

固相微萃取-气相色谱-质谱法测定食品塑料包装袋中6 种酞酸酯类化合物

建立固相微萃取-气相色谱-质谱同时测定食品塑料包装袋中6 种酞酸酯类化合物的分析方法,并对固相微萃取方式、萃取溶剂、萃取头涂层、萃取温度等参数进行优化。采用85 μm PA固相微萃取纤维头、正己烷为萃取溶剂,90 ℃平衡5 min后萃取吸附30 min,在250 ℃进样口解吸5 min后供气相色谱-质谱分析。结果表明：该方法的线性范围为0.25～50 mg/L,方法检出限为0.049～0.920 mg/L,回收率为82.2%～109.0%,相对标准偏差（n=6）为4.0%～12.0%,该方法能很好地富集基体中的目标化合物,满足食品塑料包装袋中多种酞酸酯类化合物的分析要求。     

A Novel Method for Bisphenol A Analysis in Dairy Products Using Graphene as an Adsorbent for Solid Phase Extraction Followed by Ion Chromatography

A novel and reliable ion chromatography (IC) method using graphene (G) as a solid phase extraction (SPE) adsorbent for the rapid analysis of bisphenol A (BPA) in dairy products was developed. The performances of graphene (G) and commercial C18 for BPA extraction from dairy samples were evaluated; results showed that G had higher adsorption efficiency. IC coupled with an electrochemical detector (ED) is eco-friendly, labor and time saving compared to liquid chromatography mass spectrometry (LC-MS) and gas chromatography mass spectrometry (GC-MS). The effects of the experimental parameters of the IC-ED system were assessed, and the parameters were optimized to provide maximum sensitivity. The linear range is 5–20,000 ng?mL^?1 with an R value of 0.999. The limit of the detection is 0.8 ng?mL^?1 for a 25-μL injection loop. The mean relative recoveries ranged between 83.3 % and 104.6 %, the corresponding inter-day precision was below 5.3 % for 20, 200, 2,000, and 15,000 ng?mL^?1. This method was successfully employed to analyze BPA in dairy samples.     

Quick screening of priority β-agonists in urine using automated TurboFlow™-LC/Exactive mass spectrometry

This paper describes a method for the determination of priority β-agonists in urine based on a fully automated sample preparation procedure using an online TurboFlow? chromatography clean-up step and determination with Orbitrap? mass analyser technology. The principle of the method was the enrichment of the β-agonists after enzymatic hydrolysis overnight on a small column packed with a special stationary phase (TurboFlow?) while flushing away sample matrix and interfering compounds. Thereafter, the analytes were transferred onto an analytical column and detected by liquid chromatography/high-resolution mass spectrometry in full-scan mode at a resolution of R?=?50,000 FWHM (full width at half maximum) and in higher energy collisional dissociation (HCD) scan mode at a resolving power of 10,000 FWHM. The optimisation of each step of the method, such as selection of the TurboFlow? and analytical column as well as sample loading and elution parameters were performed using a standard solution containing salbutamol, clenbuterol and mabuterol at a concentration of 100?μg?l(-1). The developed automated sample preparation significantly improved the throughput and efficiency of the previously used screening method and it resulted in a considerable reduction in analysis time. Validation experiments including 24 β-agonists in urine gave decision limits (CCα) between 0.05 and 0.35?μg?l(-1). The repeatability of analyses for urine samples spiked at 0.5?μg?l(-1) was within the range of 5-26% and recoveries for all compounds were within 89-107%.     

Simple and high-throughput method for the multimycotoxin analysis in cereals and related foods by ultra-high performance liquid chromatography/tandem mass spectrometry

A rapid, reliable and sensitive method was developed to determine 12 mycotoxins (deoxynivalenol, aflatoxins B1, B2, G1, G2 and M1, fumonisins B1 and B2, ochratoxin A, HT-2 and T-2 toxin and zearalenone) simultaneously in maize, walnuts, biscuits and breakfast cereals. The method is based on a single extraction step using acetonitrile/water mixture (80/20 v/v) followed by ultra-high performance liquid chromatography coupled with tandem mass spectrometry (UHPLC–MS/MS). The selectivity of the MS/MS detection allowed the elimination of further clean up steps. Extraction, chromatographic and detection conditions were optimised in order to increase sample throughput and sensitivity. Matrix-matched calibration was used for quantification and recoveries of the extraction process ranged from 70.0% and 108.4%, with relative standard deviations lower than 25% in all the cases, when samples were fortified at 5 and 50 μg/kg. Limits of detection ranged from 0.01 to 2.1 μg/kg and limits of quantification ranged from 0.03 to 6.30 μg/kg, which were always below the tolerance levels of mycotoxins set by European Union in the matrices evaluated. Several samples were analysed and aflatoxins B1, B2, G1, G2 and T-2 toxin were detected in one maize sample, with concentrations lower than 6.0 μg/kg and deoxynivalenol was detected in a breakfast cereal at 42.1 μg/kg.     

QuEChERS法-液相色谱-串联质谱法测定蔬菜中7种农药及其代谢物的残留量

样品经乙腈提取,C_(18)吸附剂和石墨化碳黑分散固相萃取净化,液相色谱-三重四极杆串联质谱在动态多反应监测模式下检测,基质匹配标准曲线外标法进行定量,建立了蔬菜中7种农药及其代谢物的多残留分析方法。在10、20μg/kg 7种农药及其添加物添加水平下,农药及其代谢物的平均回收率为71.9%~117.8%,相对标准偏差为0.8%~9.6%,定量限为0.2~10μg/kg。该方法简便、快速、灵敏,适用于蔬菜中多种农药及其代谢物的同时检测。     

超高效液相色谱-串联三重四极杆质谱法同时检测鸡肉中7种兽药残留

目的 建立超高效液相色谱-串联三重四极杆质谱(ultra performance liquid chromatography-tandem triple quadrupole mass spectrometry, UPLC-MS/MS) 同时检测鸡肉中7种兽药残留的分析方法。方法 采用固相萃取提取方法, 运用Waters液相色谱柱BEH C18色谱柱进行分离, 甲醇(含0.2甲酸%)-0.2%甲酸水溶液作为流动相进行梯度洗脱, 串联质谱电喷雾正离子同时扫描, 多反应监测(multiple response monitoring, MRM)模式检测, 外标法定量。结果 该方法线性良好, 相关系数均大于0.992, 检出限为0.003~0.01 mg/kg, 平均回收率为78.8%~94.1%, 相对标准偏差(relative standard deviations, RSDs)为1.58%~5.12%。结论 该方法简便、快速、准确, 适用于鸡肉中7种兽药残留的定量分析。     

QuEChERS-SPE-超高效液相色谱-串联质谱法测定调味面制品中的12种真菌毒素

建立了QuEChERS-SPE-超高效液相色谱-串联质谱法检测调味面制品中12种真菌毒素残留量的方法.样品由甲酸-乙腈-水溶液提取,加入氯化钠和无水硫酸镁盐析分层,取部分上层清液经Prime HLB小柱萃取净化,净化后的液体再加入无水硫酸镁、乙二胺-N-丙基硅烷(PSA)、C18和中性氧化铝粉末(Al-N)净化;以Wa...     

Occurrence of pesticide residues and transformation products in different types of dietary supplements

The purpose of this study was to evaluate the presence of pesticide residues and transformation products in dietary supplement products. Thirty-two samples were analysed to determine 177 pesticides by gas chromatography–tandem mass spectrometry (GC-MS/MS) and 333 pesticides by liquid chromatography–high-resolution mass spectrometry (LC-HRMS). Pesticides were extracted from different kinds of dietary supplements by the use of a modified QuEChERS extraction method. Six samples contained pesticide residues at concentration up to 92.7 µg kg^?1, but only butralin exceeded the maximum residue limits set for raw material. In addition to target compounds, LC-HRMS enables the simultaneous detection of non-target pesticides. In this case, transformation products of pesticides were detected in the analysed samples using HRMS analyser (Exactive-Orbitrap). These compounds were not included in the original method, and they were monitored as post-target compounds, knowing their molecular formula and exact mass. Mass accuracy was always < 2 ppm, corresponding to a maximum mass error. The positive findings endorse the idea that a deeper and continuous investigation of pesticide residues and transformation products in dietary supplement products is necessary in order to guaranty consumer’s safety.