超高效液相色谱-串联质谱法测定啤酒中的真菌毒素

建立啤酒样品中脱氧雪腐镰刀菌烯醇、3-乙酰基脱氧雪腐镰刀菌烯醇、15-乙酰基脱氧雪腐镰刀菌烯醇、玉米赤霉烯酮、去环氧脱氧雪腐镰刀菌烯醇、脱氧雪腐镰刀菌烯醇-3-葡萄糖苷、雪腐镰刀菌烯醇等7种真菌毒素的超高效液相色谱-串联质谱测定方法。啤酒样品经过Mycosep226多功能净化柱净化后,取净化液吹干浓缩后,经Acquity UPLC BEH C18色谱柱（100 mm×2.1 mm,1.7μm）分离,在负离子模式下,用电喷雾电离串联质谱以多反应监测模式（MRM）进行检测分析,同位素内标法进行定量。结果表明,7种真菌毒素在2～1000μg/L浓度范围内线性关系良好（r＞0.999）,最低检出浓度为0.03μg/L,在20μg/L、200μg/L、500μg/L 3个加标水平下进行了验证试验,平均回收率为82.7%～115%,相对标准偏差为1.94%～9.87%。该方法简便、快速、准确,满足实验要求,可用于啤酒样品中真菌毒素的多残留的检测分析。     

液相色谱串联质谱法测定肉中丙硫咪唑及其代谢物

建立同时测定肉中丙硫咪唑及其代谢物丙硫咪唑砜、丙硫咪唑亚砜、2-氨基丙硫咪唑砜的液相色谱串联质谱法。样品用乙腈提取,液液分配净化后,XDB-C18色谱柱分离,流动相乙腈:0.1%甲酸溶液(1:1,V/V),外标法定量。丙硫咪唑及其3种代谢物的检出限均为0.010mg/kg,在0.010～1.0mg/L范围内其质量浓度与峰面积呈良好的线性关系,相关系数大于0.99。添加量为0.010～0.050mg/kg时的回收率为82.3%～97.6%,相对标准偏差为4.9%～12.9%。该方法简便、快速、准确,可用于猪肉、牛肉、羊肉、鸡肉、香肠中丙硫咪唑及其代谢物的定性、定量检测。     

超高效液相色谱-串联质谱法快速分析氰霜唑及其代谢物CCIM在水果中的残留

为评价氰霜唑及其主要代谢物4-氯-5-(4-甲苯基)-1H-咪唑-2-腈（CCIM）在水果中的安全性,建立了同时检测氰霜唑及其代谢物CCIM的高效液相色谱-串联质谱法。待测样品采用含体积分数1.0%乙酸的乙腈溶液提取,经十八烷基硅烷键合相（C18）粉末和弗罗里硅土粉末净化后,以Capcell PAK C18色谱柱（150 mm×2.0 mm,5μm）进行UPLC分离,采用质谱多重反应监测模式（MRM）进行测定。结果表明,氰霜唑和CCIM在0.001～0.040μg/mL时,质量浓度与峰面积呈良好的线性关系（R≥0.999 3）,在0.004～0.080 mg/kg添加水平内,氰霜唑和CCIM回收率分别为80.71%～103.27%和76.62%～100.20%;相对标准偏差分别为4.14%～11.15%和3.24%～11.16%,检出限和定量限分别为0.001 5～0.003 8 mg/kg和0.003 0～0.007 9 mg/kg。该方法简单快速、分析时间短、灵敏度及准确度高,能够满足快速定性、定量检测水果样品中氰霜唑及CCIM的残留量。     

Bioactives Screening in Overripe Fruits and Vegetables by Liquid Chromatography Coupled to Photodiode Array and Mass Spectrometry Detection

Food waste production generated by large distribution represents an emerging issue due to the large polluting impact and, at the same time, due to the enormous increase of nutrients’ need worldwide. Overripe fruits are considered as “food wastes” despite they could be yet rich sources of food ingredients and bioactives, such as carotenoids and polyphenols. In this work, a phytochemical screening of 20 selected overripe vegetables and fruits was accomplished by liquid chromatography coupled to photodiode array and mass spectrometry detection. The obtained results showed that the low-sugar-content fruits and vegetables had a higher bioactive content compared to the high-sugar fruits; in particular, tomato, wild swiss chard, green bell pepper, and lettuce leaves were the richest in bioactive phytochemicals. Green bell peppers showed the highest pigment content (875.3 mg/kg), whereas tomato, wild swiss chard, and lettuce leaves showed the highest polyphenol contents, 4541.9, 1692.4, and 712.9 mg/kg, respectively. This is the first work where a large-scale monitoring of bioactives in overripe fruits was carried out and two mixtures of fresh and dry material for animal feed are presented.     

Determination of Phenolic Compounds in Artichoke,Garlic and Spinach by Ultra-High-Performance Liquid Chromatography Coupled to Tandem Mass Spectrometry

Phenolic compounds were determined in artichoke (Cynara scolymus), garlic (Allium sativium) and spinach (Spinacia oleracea) using a single method based on simple extraction and ultra-high-performance liquid chromatography coupled to triple quadrupole tandem mass spectrometry (UHPLC-QqQ-MS/MS). Several compounds belonging to different families, such as phenolic acids, isoflavones, flavones and flavonols, were determined. The analytical procedure was validated in all the matrices, obtaining recoveries ranging from 60 to 120 % with reproducibility values (expressed as relative standard deviations (RSDs)) lower than 26 %. Limits of quantification (LOQs) were always equal to or lower than 50 μg/kg, except to kaempferol and its glucosides in spinach (LOQs?=?75 μg/kg). Artichoke showed higher concentration of phenolic compounds (837.2 mg/kg dry weight (DW)) than garlic (26.5 mg/kg DW) or spinach (64.5 mg/kg DW). Apigenin 7-O-glucoside (from 147.0 to 722.7 mg/kg DW) was found to be the major flavonoid in all samples of artichoke investigated, while chlorogenic acid, whose concentration ranged from 37.8 to 734.7 mg/kg DW, is the major phenolic acid in this matrix. Regarding garlic, caffeic acid (from 1.7 to 28.3 mg/kg DW) and quercetin (from 9.0 to 18.9 mg/kg DW) were the compounds detected at higher concentrations, although in general the total content was very low in relation to other matrices. In relation to spinach, ferulic acid was the major phenolic compound, and its concentration ranged from 18.0 to 41.4 mg/kg DW.     

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.     

Determination of Antimicrobial Residues in Honey by Liquid Chromatography Tandem Mass Spectrometry

Antibiotics are generally used worldwide against bacterial diseases in the treatment of food-producing animals. Since the residues of active agents or their metabolites can appear in these foods, the European Union, for instance, has set maximum residue limit concentrations for authorised veterinary drugs in foodstuffs. However, as yet, regulatory limits have not been established for honey and thus far, only recommendations exist. The aim of this study is to present a multiscreening method for residues in honey for the determination of 36 antimicrobial residues associated with several antibiotics of the B1 group (sulfonamides, trimethoprim, aminoglycosides, tetracyclines, quinolones and lincomycin) as well as the antibiotic griseofulvin. During the screening analysis, samples are hydrolysed in an acidified medium, purified on polymeric solid-phase extraction cartridges and subsequently analysed by reversed phase ion pair liquid chromatography tandem mass spectrometry. The liquid chromatographic separation was optimised by computer simulation with DryLab software. The positive identification of target compounds in suspicious samples was confirmed using earlier developed antibiotic class specific methods of which the aminoglycoside method is herein described in detail. The developed approaches were then applied to samples in the national monitoring program after their successful validation. Moreover, the screening and confirmatory methods were applied to proficiency test samples resulting in satisfactory identification and quantification. However, the analysis of real samples revealed that co-eluting target compounds can have considerable influence on the accuracy of this semi-quantitative multiscreening method.     

LC-MS-MS同时定量检测硒蛋氨酸和硒胱氨酸

目的 建立同时测定硒蛋氨酸(SeMet)和硒胱氨酸(SeCys)含量的液相色谱-串联质谱法(LC-MS-MS).方法色谱柱:Waters Symmetry C18(150 mm×3.9 mm,5μm);流动相:甲醇+0.1%七氟丁酸水溶液(35+65),流速为500μl/min;以氮气为碰撞气,利用多反应离子监测方式测定SeMet(MRM m/z 198.1→181.0,198.1→152.0)和SeCys(MRM m/z 337.0→248.0,337.0→88.2)信号.结果 SeCys和SeMet检出限分剐为2.0 ng/ml和0.5 ng/ml;以198.1→181.0为定量分析离子对.SeMet的线性回归方程为:y=707x+990,r=0.999 3;以337.0→248.0为定量分析离子对,SeCys的线性回归方程为:y=64.3x+695,r=0.999 9.结论该方法能够使2种含硒化合物在一次进样中实现完全分离和在线测定.能够满足快速准确检测SeCys和SeMet含量要求.     

HPLC-MS/MS法检测桶装饮用水中壬基酚污染水平

建立高效液相-质谱法(HPLC-MS/MS)检测饮用水中壬基酚的方法,并对天津市桶装水企业从水源、生产、储存到消费全过程中壬基酚的污染水平进行调查。壬基酚的方法检出限为0.1μg/L,加标回收率为86.3%~92.2%,相对标准偏差为3.1%~4.6%。通过对饮用水检测,发现所采集样品企业的水源中壬基酚浓度范围在5.97μg/L~12.40μg/L,表明其水源已受到壬基酚的污染,而盛装容器无壬基酚明显迁移,桶装水的生产环节能有效去除部分壬基酚。     

液相色谱串联质谱对掺假牛肉的鉴别及定量研究

本文以差异蛋白质组学为理论研究基础,利用高效液相色谱串联质谱(HPLC-MS/MS)实现了对猪肉或鸡肉掺假的牛肉的定性鉴别及定量分析。首先采用高分辨质谱仪(nLC-QE)分别找出牛肉、猪肉和鸡肉的相对专属性多肽链,并对其进行二级扫描,得到了三个物种的特异性离子对,进一步利用HPLC-MS/MS的多反应监测模式(MRM)对掺杂猪肉或鸡肉的牛肉进行特异性离子对验证,分别选择了牛肉、猪肉和鸡肉的9、8和7条多肽进行定性研究;并与聚合酶链式反应(PCR)技术进行比对,得到的结果一致;此外将鸡肉和猪肉以0.5、1.0、5.0、10.0、25.0%的比例掺杂于牛肉中,各选择3组离子对进行定量分析,其各自的线性相关系数均大于0.99,最低定量限为0.5%。由此表明,液相色谱串联质谱的方法可以快速地对牛肉中的猪肉和鸡肉进行鉴别并能准确定量分析。     

液相色谱-串联质谱法测定皮革中PFOS及PFOA盐类

建立了皮革中全氟辛烷磺酸盐(PFOS)及全氟辛酸盐(PFOA)的萃取及液相色谱-串联质谱(LC-MS/MS)的检测方法.采用索氏抽提进行萃取,溶剂为甲醇,萃取液经弱阴离子固相萃取柱(Oasis WAX)净化处理后,采用负离子电喷雾电离、多级反应离子监测(MRM)模式进行LC-MS/MS检测.结果表明,PFOS和PFOA浓度在1 ～50 μg/L范围内,线性相关系良好,相关系数均大于0.995,在10 ～160 mg/kg范围内的添加水平回收率为80%～105%,相对标准偏差为6.3%～15.5%(n=6),定量检出限均为0.5 mg/kg.该方法可用于皮革中PFOS及PFOA盐类物质的测定.     

HPLC-MS/MS法测定曲霉菌代谢物中黄曲霉毒素及同系物

建立了同时检测曲霉菌代谢物中黄曲霉毒素和同系物的高效液相色谱-线性离子阱质谱测定方法。产黄曲霉毒素B1(AFB1)寄生曲霉(菌株3.124)经PDA固体培养基培养,提取净化后经线性离子阱(QTrap)质量分析器分析(正离子模式,多反应检测),以AFB1二级碎片(MS2)信息和其同系物分子式信息预测代谢物MRM方法,检出3.124代谢物中黄曲霉毒素B2(AFB2)、黄曲霉毒素G1(AFG1)、黄曲霉毒素G2(AFG2)、O-甲基杂色曲霉素(MST)、杂色曲霉素(ST)5种真菌毒素,并用标准品进行了确证。结果表明,AFB2和AFG2在0.5μg/L~40μg/L,其它4种代谢物在0.2μg/L~40μg/L范围内线型关系良好,相关系数均大于0.99。本方法 6种代谢物日内回收率81.3%~92.3%,相对标准偏差(RSD)为3.4%~6.2%;日间回收率82.1%~91.7%,RSD为3.8%~7.7%。该方法为快速检测霉菌代谢物中的同系物提供新的方法。     

低温下采用快速液相色谱-质谱联用法分析包装食品中UV油墨光引发剂的迁移

A fast method of liquid chromatography coupled to tandem mass spectrometry(LC-MS/MS) was developed for the analysis of eleven UV ink photoinitiators in packaged food.Chromatographic separation was achieved in a pentafluorophenylpropyl (PFPP) column at 5X2 and acetonitrile:25mM formic acid-ammonium formate(pH 2.7) in gradient elution. To reduce sample treatment,a QuEChERS(quick,easy,cheap,effective,rugged and safe) method for the extraction and clean-up of UV photoinitiators in packaged foods was evaluated.Triple quadrupole working in H-SRM on Ql mode was used for both quantitation and confirmation purposes and the most intense and selective transitions were chosen.Quality parameters of the developed QuEChERS LC-MS/MS method were established and applied for the analysis of photoinitiators in food packaged at ng/kg levels.     

Determination of Ochratoxin A in Cereals and Feeds by Ultra-performance Liquid Chromatography Coupled to Tandem Mass Spectrometry with Immunoaffinity Column Clean-up

This paper describes the preparation of reusable immunoaffinity columns and the development of an ultra-performance liquid chromatography tandem mass spectrometry method combined with immunoaffinity column clean-up (IAC-UPLC-MS/MS) for the determination of ochratoxin A (OTA) in cereals and feeds. The monoclonal antibody (mAb) was produced from a stable hybridoma cell line (4H10), which belongs to the immunoglobulin G1 (κ-light chain) isotype. A competitive indirect enzyme-linked immunosorbent assay was used to characterize the mAb. The concentrations causing 50 % inhibition of binding of mAb to OTA-ovalbumin by free OTA, ochratoxin B, and ochratoxin C were 1.29, 4.78, and 0.94 ng mL^?1, respectively. The IAC-UPLC-MS/MS method offers a limit of quantification (LOQ, S/N >10) ranging from 0.5 to 1.0 μg kg^?1 and a limit of detection (LOD, S/N >3) ranging from 0.2 to 0.3 μg kg^?1 in cereal and feed samples. The IAC-UPLC-MS/MS method offers a good LOQ and LOD for OTA in cereal and feed samples. The accuracy and precision at this level fall within the EU regulatory limit. This methodology has been validated in four different matrices (millet, maize, soybean, and swine finisher diet) with highly satisfactory results and applied to the analysis of samples collected from the markets.     

高效液相色谱-电感耦合等离子体-串联质谱测定水产品中5种形态砷

建立高效液相色谱-电感耦合等离子体-串联质谱法（high performance liquid chromatography-inductively coupled plasma tandem mass spectrometry,HPLC-ICP-MS/MS）测定水产品中5 种形态砷的检测方法。利用MS/MS模式,以质量转移的方式消除干扰,流动相由10 mmol/L C2H3NaO2、3 mmol/L KNO3、12 mmol/L NaH2PO4等组成,采用梯度洗脱,As7阴离子交换色谱柱分离。结果表明：5 种形态砷可完全分离,三价砷、二甲基砷、一甲基砷、五价砷和砷甜菜碱都具有良好的线性相关系数,检出限依次为0.005 94、0.005 28、0.008 17、0.008 41、0.011 70 mg/kg,满足检测要求;加标回收率为83%～116%,相对标准偏差均小于5%;该方法具有简便快捷、准确度高、分离明显、检测效率高等特点,可对水产品中多种形态砷进行评价分析。     

Citrinin Determination in Red Fermented Rice Products by Optimized Extraction Method Coupled to Liquid Chromatography Tandem Mass Spectrometry (LC‐MS/MS)

A rapid and sensitive method was developed and validated for citrinin determination in red fermented rice products by liquid chromatography tandem mass spectrometry (LC‐MS/MS) under the selected reaction monitoring mode. Sample preparation was especially focused, and the quantitative methods of LC‐MS/MS and high‐performance liquid chromatography with fluorescence detection (HPLC‐FLD) were compared. In red fermented rice samples, the limit of detection was 1.0 μg/kg for LC‐MS/MS compared to 250 μg/kg for HPLC‐FLD, the limit of quantification was 3.0 μg/kg for LC‐MS/MS compared to 825 μg/kg for HPLC‐FLD. High correlation coefficient was obtained (R² = 0.999) within the linear range (0.1 to 100 μg/L) in the MS method. The recoveries ranging from 80.9% to 106.5% were obtained in different spiking concentrations. The average intra‐ and inter‐day accuracy ranged from 75.4% to 103.1%, and the intra‐ and inter‐day precisions were from 3.3% to 7.9%. The developed method was applied to 12 commercial red fermented rice products, and citrinin was found in 10 samples ranging from 0.14 to 44.24 mg/kg. Compared to traditional qualitative and quantitative methods, the newly developed LC‐MS/MS method for citrinin determination includes the merits of using a small amount of extraction solvent, simple preparation steps, and high sensitivity.     

QuEChERS-气相色谱-串联质谱法测定果蔬中乙烯菌核利及其代谢物的残留量

建立了改进的QuEChERS方法结合气相色谱/质谱(GC/MS)法快速测定果蔬中乙烯菌核利及其代谢物3,5-二氯苯胺残留量的方法.研究改良了QuEChERS方法中吸附剂的种类和用量,用乙酸乙酯提取番茄、黄瓜、生菜、芹菜、柑橘和葡萄中乙烯菌核利及其代谢物残留,经乙二胺-N-丙基硅烷(PSA)粉80 mg、石墨化碳黑(GC...     

Multiclass Determination of Phenolic Compounds in Different Varieties of Tomato and Lettuce by Ultra High Performance Liquid Chromatography Coupled to Tandem Mass Spectrometry

Tomato and lettuce are main components of the Mediterranean Diet and it is important to know their content in phenolic compounds, considering they have beneficial effects on human health. In this work, more than 25 phenolic compounds were simultaneously analyzed by ultra-high performance liquid chromatography coupled to triple quadrupole tandem mass spectrometry, including phenolic acids, flavonols, and flavones. Several varieties of lettuce and tomato were evaluated and total phenolic content ranged from 68 to 212 mg/kg dry weight for lettuce, and from 341 to 1296 mg/kg dry weight for tomato, being the chlorogenic acid the compound detected at the highest concentration in both types of vegetables (lettuce from 9 to 126 mg/kg dry weight, tomato from 96 to 538 mg/kg dry weight), although in tomato the content of quercetin-3-O-rutinoside (from 29 to 460 mg/kg dry weight) was also important. On the other hand, the minor compounds detected were quercetin-3-O-derivate (up to 1 mg/kg dry weight) in tomato, and apigenin O derivate, luteolin C glucoside, and isorhamnetin 3-O-glucoside in lettuce. It was observed that the total phenolic content in the plum cherry tomato was significantly higher than in the other varieties, whereas in lettuce, the differences were not statistically different.     

液相色谱串联质谱法测定猪肉中克伦特罗手性对映体残留量

建立测定猪肉中克伦特罗手性对映异构体残留量的液相色谱串联质谱分析方法。5 g猪肉样品在碱化的条件下用乙酸乙酯提取,提取后用稀盐酸进行反萃取,萃取液过SCX固相萃取小柱,最后用5%氨化甲醇洗脱,洗脱液经氮气吹干后用500μL甲醇(含0.02%的乙酸和0.1%的乙酸铵)定容。采用Astec CHIROBIOTICTM V手性色谱柱,以甲醇∶冰乙酸∶乙酸铵=99.88∶0.02∶0.10(V/V)为流动相进行液相分离,电喷雾正离子(ESI+)模式电离,多反应监测(MRM)模式检测,内标法定量。克伦特罗单一对映体在2.0~200μg/L质量浓度范围内呈良好的线性,线性相关系数均大于0.997 0,猪肉样品中克伦特罗最低检测限和定量限分别为0.10μg/kg和0.25μg/kg。猪肉中克伦特罗手性对映体在0.25~0.75μg/kg范围内的回收率为95.8%~102.1%之间,相对标准偏差均小于5%。     

金属罐内层涂料三聚氰胺迁移量的测定

利用液相色谱-串联质谱(LC-ESI-MS/MS)测定食品接触材料中三聚氰胺迁移量.通过不同试验条件对比,结合国家标准,并通过实际样品测试发现:在食品加工、包装、消毒过程中,在一定条件下会使有些材料发生三聚氰胺迁移情况,带来食品质量安全问题.本试验结果为食品包装材料生产企业、食品生产加工企业提供了一定的技术支持,同时为...