Determination of Oleuropein in Cosmetics by Ultra Performance Liquid Chromatography-Triple Quadrupole Tandem Mass Spectrometry

An ultrahigh performance liquid chromatography-triple quadrupole tandem mass spectrometry(UPLC-MS/MS)was established to quickly and accurately determine the content of oleuropein in cosmetics.The samples were extracted with methanol-aqueous solution,and the mobile phase with methanol-formic acid solution(0.1 mol/L)=40∶60 was separated by Agilent ZORBAX Eclipse Plus C18(2.1 mm×50 mm×1.8μm-Micron)column temperature 30℃,flow rate 0.3 mL/min.The MS end was detected by electrospray negative mode ionization(ESI-)and multiple reaction monitoring(MRM)mode.The results show a good linear relationship in the range of 0.002~5 mg/L,with a correlation coefficient R2 of 0.999,5.Method recovery range from 84.2%~107.6%and the relative standard deviation RSD is 5.8%.The detection time is 5 min,the detection limit is 0.000,6 mg/L,and the limit of quantification is 0.002 mg/L.This method has the advantages of convenient operation,low quantification limit,high precision and good repeatability,and is suitable for measuring the content of oleuropein in many kinds of cosmetics.

Chemical Components of Achyranthes bidentata Leaves by Ultra High Performance Liquid Chromatography-Mass Spectrometry

[Objectives] To study the chemical components and relative content of Achyranthes bidentata leaves and provide a scientific basis for further development and utilization of A. bidentata leaves.[Methods] The chemical components of A. bidentata leaves were rapidly analyzed using the ultra high performance liquid chromatography-time of flight-high resolution mass spectrometry (UHPLC-TOF-MS).[Results] Thirty eight chemical compounds were identified in samples of A. bidentata leaves collected from Wen County of Henan Province, in which seven chemical compounds had the relative content higher than 5%, linoleic acid reached 25.7% and inokosterone A reached 13.8%.[Conclusions] A. bidentata leaves contain many kinds of chemical compounds. This study is expected to provide a certain basis for further extraction of linoleic acid and inokosterone A.

UPLC-MS/MS法检测3种食品中松仁过敏原

基于食品基质中松仁过敏原Pin k 2建立了一种超高效液相色谱-串联质谱法。将松仁经过研磨、脱脂、浸提、酶解后经Easy-nLC 1000-QExactive高分辨质谱仪进行分离分析,结合Uniprot蛋白数据库以及ProteinPilotTM软件对质谱图进行数据处理,经BLAST验证特异性,最终筛选3条松仁特异性肽段。方法学验证结果表明,方法在0.001~50mg/mL范围内线性关系良好,定量限为1mg/kg;在饼干、巧克力和饮料3种空白基质中的平均回收率为88.50%~107.57%,相对标准偏差不高于6.08%,基质效应为89.77%~96.13%。该方法具有灵敏度高、特异性好的优势,可应用于饼干、巧克力、饮料等食品样品中松仁过敏原的检测,为我国食品标签真实性检验及食品中隐性过敏原的检测提供技术支持。

Uncertainty Evaluation of Determination of Microcystin MC-LR in Environmental Samples by Solid Phase Extraction-Ultra Performance Liquid Chromatography-Tandem Mass Spectrometry

To assess uncertainty of determination of MC-LR in environmental samples by solid phase extraction- ultra performance liquid chromatography- tandem mass spectrometry,the sources of the uncertainty were evaluated firstly,and the expanded uncertainty was calculated finally.The results show that when MC-LR concentration in the water samples was 0.50 μg/L,the expanded uncertainty was 0.00628 μg/L(k=2).

Determination of Steroid Hormone Residues in Fish Tissues Using Gel Permeation Chromatography and Ultra Performance Liquid Chromatography-Tandem Mass Spectrometry

A highly sensitive method was developed for the simultaneous determination of 8 steroid hormones in high-fat fish tissues using ultra high performance liquid chromatography-tandem mass spectrometry(UPLC-MS/MS).The 8 steroid hormones were extracted from the tissues with diethyl ether.Differing from other common purification methods,the extract solutions were cleaned by gel permeation chromatography(GPC) using ethyl acetate-cyclohexane solution(1:1,v/v) as the mobile phase.The separation of target compounds was carried out by a BEH C18 column and a gradient elution consisting of acetonitrile and 0.2% aqueous formic acid(v/v).The compounds were detected under the multiple reaction monitoring(MRM) mode and quantified with external standard method.This method was validated with respect to linearity,specificity,accuracy and precision.A linearity with correlation coefficient larger than 0.995 was achieved in the range of 0.5 to 50 ng m L^(-1).The average recoveries at the spiked levels of 1.0,5.0,and 10.0 μg kg^(–1) varied between 81.7% and 90.8%,with the relative standard deviations(n=5) ranged from 3.50% to 10.0%.The limit of quantification(LOQ) for 8 steroid hormones ranged from 0.2 to 1.5 μg kg^(-1).It was concluded that this method can be successfully applied for the determination of 8 steroid hormones in complicated matrices including high-fat fish tissues.

Simultaneous Determination of Ultraviolet Absorbers and Antibacterial Agents in Textiles by Ultra-High Performance Liquid Chromatography/Orbitrap High Resolution Mass Spectrometry

This paper reported a new analytical method for the simultaneous determination of seven benzotriazole ultraviolet absorbers and seven antibacterial agents in textiles. After ultrasonic extraction for the textile samples in methanol, the solutions were analyzed by ultra-high performance liquid chromotagraphy/orbitrap high resolution mass spectrometry (UPLC/Orbitrap HRMS). It showed that a good chromatographic separation for these target compounds was achieved by a Hypersil GOLD column (100 mm × 2.1 mm × 1.9 μm) with a gradient elution of methanol and 0.1% aqueous formic acid solution (containing 0.5 mmol/L ammonium acetate). Triclosan and 4-chloro-3,5-dimethyl phenol (PCMX) were detected by the orbitrap HRMS in an electrospray ionization (ESI) negative mode while the other twelve target compounds were detected by orbitrap HRMS in ESI positive mode. Full scan experiment was performed over the range from m/z 100 to m/z 500. These target compounds were routinely detected with mass accuracy below 2 × 10-6 (2 ppm) at the optimized conditions. The results showed that the limits of detection (LODs) were in the range from 0.1 to 0.3 μg/kg. The blank samples were spiked at three levels and their average recoveries varied from 80.5% to 96.3% while the relative standard deviation (RSD) changed from 3.2% to 9.9%. The present method was also applied for the determination of those ultraviolet absorbers and antibacterial agents in the commercial textiles.

Rapid Determination of Three Kinds of Microcystins in Environmental Water Samples by Disk SPE-Ultra Performance Liquid Chromatography-Tandem Mass Spectrometry

A method of rapidly detecting three kinds of microcystins( MCs) in environmental water samples by using disk SPE- ultra high performance liquid chromatography- tandem mass spectrometry( UPLC- MS / MS) was established. Firstly,environmental water samples were extracted by disk SPE column( C_(18)),and three kinds of MCs were separated by Waters BEH C_(18) chromatographic column with acetonitrile- 0. 2% formic acid solution as the mobile phase. After the gradient elution separation,the external standard method was used for quantitative and qualitative analysis under MRM of UPLC- MS / MS. The results showed that the three kinds of MCs in the range of 0. 05- 10 μg / L showed good linear relation,and the correlation coefficients were higher than 0. 999 4,while the method detection limit was 0. 04 ng / L. Under 0. 1,1,and 5 μg / L standard addition for the same environmental sample,the average recovery was 82. 8%- 108. 8%,and the relative standard deviation of determination results was2. 1%- 10. 1%( n = 6). This method is rapid,sensitive and accurate,so it can be effectively applied in the monitoring of MCs in environmental water samples.

Determination of thyreostats in bovine urine using ultra-high performance liquid chromatography-tandem mass spectrometry

Five thyreostats(TSs),namely tapazole,thiouracil,methylthiouracil,propylthiouracil,and phenylthiouracil,were determined in bovine urine using ultra-high performance liquid chromatography-tandem mass spectrometry(UHPLC-MS/MS)in positive electrospray ionization mode.Extraction and clean-up were achieved using a ChemElut cartridge with tert-butyl methyl ether,without a derivatization step.Separation was achieved on an Acquity UPLC SS T3 column.The mobile phase was acetonitrile and water containing 0.2%(v/v)formic acid.The mass spectrometer was operated in multiple reaction monitoring mode.Urine samples were spiked with TS solution at levels corresponding to 5,10,15,and 20μg/L.The accuracy(internal standard corrected)ranged from 92%to 107%,with a repeatability precision(relative standard deviation,RSD)less than 15%for all five analytes.The RSDs within-laboratory reproducibility was less than 26%.The decision limits(CCα)and detection capabilities(CCβ)were obtained from a calibration curve and were in the ranges of 3.1-6.1μg/L and 4.0-7.4μg/L,respectively.The CCαand CCβvalues were below the recommended concentration,which was set at 10μg/L.The results show that the described method is suitable for the direct detection of TSs in bovine urine.This method can also be used to determine TSs in porcine urine.

Lysophosphatidylcholine Biomarkers of Lung Cancer Detected by Ultra-performance Liquid Chromatography Coupled with Quadrupole Time-of-flight Mass Spectrometry

Centrifugal ultrafiltration after methanol extraction of whole plasma was used as an optimal condition for the preparation of blood plasma before metabonomic studies. The plasma samples from 102 lung cancer patients and 34 healthy volunteers were prepared with this approach. With ultra-performance liquid chromatography(UPLC) coupled with quadrupole time-of-flight mass spectrometry(Q-TOF MS) analysis, the samples were investigated in order to find potential disease biomarkers. After data acquisition, orthogonal signal correction partial least squares models were built to differentiate the healthy volunteers from lung cancer patients and to identify metabolites that showed significantly different expression between the two groups. Several metabolite ions were identified as potential biomarkers according to the variable importance in the project(VIP) value in both ion modes. Five lysophosphatidylcholines were further identified as specifically lysoPC 16:0, isomer of lysoPC 16:0, lysoPC 18:0, lysoPC 18:1 and lysoPC 18:2. These results suggest that UPLC coupled with Q-TOF MS is an effective technique for the analysis of plasma metabolites in metabonomic studies.

QuEChERS-UPLC-MS/MS同时测定畜禽肉中23种驱虫类药物残留量

研究旨在建立同时检测畜禽肉中多种驱虫类药物的分析方法,通过优化前处理方法和仪器分析条件,建立了分散固相萃取法-超高效液相色谱-串联质谱法(UPLC-MS/MS)同时测定畜禽肉中23种驱虫类药物残留的分析方法,目标物以乙腈提取,分散固相萃取法(QuEChERS)净化,用乙腈+0.1%甲酸水作为流动相、UPLC-MS/MS确证检测、外标法定量。结果显示:所建立的方法定量限为0.2~1.0μg/kg,回收率为71.4%~107.5%,相对标准偏差为0.9%~8.8%。表明该方法定量限低,稳定性好,适用于畜禽肉中23种驱虫类药物残留的同时检测。

UPLC-MS/MS法检测血浆内源性大麻素在预测先兆流产孕妇妊娠结局中的应用

目的:研究孕妇外周血内源性大麻素水平周期变化规律,并分析基于孕早期内源性大麻素水平预测先兆流产孕妇妊娠结局的临床应用价值。方法:选择2020年5月至2022年5月在山东第一医科大学第一附属医院产检的1080例孕妇,其中880例孕早期发生先兆流产孕妇和200例正常妊娠孕妇,超高效液相色谱串联质谱(UPLC-MS/MS)法检测血中内源性大麻素水平,通过logistic回归分析先兆流产发展为难免流产的风险因素,并用ROC曲线评估孕酮、β-人绒毛膜促性腺激素(β-HCG)、花生四烯酸乙醇胺(AEA)预测先兆流产孕妇妊娠结局的性能。结果:发生难免流产的孕妇外周血AEA平均水平为(3.96±2.04)nmol/L,显著高于持续妊娠孕妇[(2.16±2.00)nmol/L](P<0.001)。年龄、AEA、孕酮、β-HCG、胎龄及阴道流血量是先兆流产发展为难免流产的风险因素(P<0.05)。孕早期内源性大麻素AEA,当阈值为2.565nmol/L时,用于预测先兆流产孕妇妊娠结局的准确率为86.7%,具有最优预测性能。结论:孕妇外周血内源性大麻素AEA水平测定是预测先兆流产患者妊娠结局的有效工具。

UPLC-MS/MS法同时测定白酒中21种氨基酸的含量

该研究建立了一种采用超高效液相色谱-串联质谱(UPLC-MS/MS)同时测定白酒中21种氨基酸含量的检测方法。白酒样品经过12000 r/min离心5 min后,将上清液直接用于色谱分析,外标法定量。结果表明,在10~1000 ng/mL质量浓度范围内,氨基酸含量线性关系良好,相关系数(R2)均>0.995,检出限和定量限分别为0.1~5.0 ng/m L和0.2~20 ng/mL,其保留时间相对标准偏差(RSD)<0.29%,峰面积RSD为1.54%~10.33%,加标回收率为80%~130%。该方法准确可靠,重复性好,可以用于白酒中21种氨基酸的含量的测定。

基于硅烷化三聚氰胺海绵的改良QuEChERS结合UPLC-MS/MS快速测定猪肉中49种抗生素多残留

采用十八烷基三氯硅烷(octadecyltrichlorosilane,OTS)与N-[3-(三甲氧基硅基)丙基]乙二胺(N-[3-(trimethoxysilyl)propyl]ethylenediamine,ATS)改性三聚氰胺海绵(melamine sponge,MeS)制备得到2种新型弹性多孔硅烷化MeS(OTS@MeS和ATS@MeS)净化材料,将其用于改良QuEChERS(quick,easy,cheap,effective,rugged and safe)基质净化过程,通过溶液自发浸润和物理挤压过程即可快速、高效分离干扰基质,结合超高效液相色谱-串联质谱技术建立了同时测定猪肉中49种抗生素多残留的分析方法。样品用1.0%乙酸-乙腈溶液提取并用2.0 g Na_(2)SO_(4)和0.5 g NaCl盐析,离心后取1 mL上清液复配使用OTS@MeS与ATS@MeS净化,随后使用Agilent ZORBAX Eclipse Plus C_(18)色谱柱,以甲醇溶液和含有0.1%甲酸、5 mmol/L乙酸铵的甲醇-水溶液(5∶95,V/V)为流动相进行梯度洗脱,采用电喷雾电离源、正离子多反应监测模式进行定性定量分析。结果表明:49种抗生素的相关系数均大于0.999,基质效应为-13.5%~10.9%,检出限在0.1~10μg/kg之间,定量限在0.3~30.3μg/kg之间;利用该方法在低、中、高3个加标水平下进行回收率实验,回收率范围为65.0%~112.7%,日内和日间相对标准偏差分别为0.3%~11.8%和2.4%~18.4%。该方法样品前处理过程简单、快捷、灵敏度高、准确性好,可用于猪肉中49种抗生素多残留的高效快速检测。

UPLC-MS/MS法同时测定蛋白饮料和液体调味品中36种防腐剂

采用提取和净化相结合的前处理方式,建立并优化了同时测定蛋白饮料、液体调味品中36种防腐剂的超高效液相色谱-串联质谱检测方法。样品采用饱和NaCl溶液(用磷酸调节pH=3)净化和乙腈-甲醇(9∶1,体积比)(含体积分数为0.2%的甲酸)提取。采用C18反向色谱柱进行分离,以甲醇和5 mmol/L乙酸铵为流动相梯度洗脱,采用电喷雾离子源正负离子同时扫描,动态多反应监测模式,基质匹配标准曲线,外标法定量。结果表明,36种防腐剂在1~250 ng/mL线性良好(相关系数≥0.999),方法定量限为0.04~0.2 mg/kg;空白样品不同加标水平下的平均加标回收率为75%~119%;相对标准偏差为0.90%~9.8%。建立的高通量检测方法灵敏、快速,准确度高,操作简便且能有效减少基质干扰、降低检测成本,极大提高多种防腐剂的定性定量检测效率。

UPLC-MS/MS测定小麦粉及其制品与小麦粉添加剂中新型非法添加物乙酰氧肟酸

建立了超高效液相色谱-串联质谱法(UPLC-MS/MS)测定小麦粉及其制品与小麦粉添加剂中新型非法添加物乙酰氧肟酸的分析方法。方法选取小麦粉、小麦粉添加剂、面皮、面条、馒头等5种具有代表性的样品为研究基质,以甲醇为提取溶剂,经超声和涡旋振荡提取,高速离心、过滤,通过T3色谱柱(2.1 mm×150 mm,3μm)分离,以0.10%(体积分数)甲酸溶液和甲醇作为洗脱流动相,采用大气压化学电离源、多反应监测模式检测,外标法定量。结果表明,乙酰氧肟酸的溶剂和基质标准曲线在0.075~5.00 mg/L范围内线性关系良好,相关系数均大于0.999,检出限为0.25 mg/kg,加标回收率为78.49%~108.61%,相对标准偏差(RSD,n=6)为1.67%~7.50%。该方法抗干扰能力强,准确度高,适用于小麦粉及其制品与小麦粉添加剂中乙酰氧肟酸的测定。

UPLC-MS/MS同时测定牙膏中7种人工甜味剂的含量

采用超高效液相色谱-串联质谱(UPLC-MS/MS)建立牙膏产品中7种人工合成甜味剂的快速检测方法。样品通过体积分数50%乙醇溶液提取并稀释后,以Acqutiy UPLC BEH C18(100 mm×2.1 mm×1.7μm)色谱柱进行分离,乙腈-体积分数0.1%甲酸水溶液为流动相进行梯度洗脱,多反应监测(MRM)模式下正负离子同时进行定性和定量分析。结果表明,阿斯巴甜在4~120 ng/mL范围内线性良好,其他6种人工甜味剂(糖精钠、安赛蜜、甜蜜素、三氯蔗糖、纽甜和阿力甜)在10~300 ng/mL范围内线性关系良好(r^(2)≥0.9989),平均加标回收率在96.51%~104.87%,相对标准偏差(RSD)在0.83%~2.73%,检出限为0.004~0.050 g/kg。本方法简便易行,准确度高,重现性好,适用于牙膏中7种人工甜味剂的快速定量检测分析。

快速过滤净化-UPLC-MS/MS同时测定畜禽肉中12种兽药残留

采用功能化聚苯乙烯/苯聚合物为填料的快速过滤净化柱萃取畜禽肉中的兽药,再结合超高效液相色谱-串联质谱(UPLC-MS/MS)高通量分析,建立了一种可同时测定12种兽药残留的方法。通过正交试验设计筛选前处理的最佳条件,样品经pH 4.0的EDTA-Mcllvaine缓冲液提取,按压式固相过滤柱快速净化,UPLC-MS/MS检测,外标法定量。结果表明,12种兽药在较宽的线性范围内拟合良好,相关系数均大于0.99,方法检出限0.3~3μg/kg,定量限1.0~10μg/kg。在3个不同添加水平下,猪肉、鸡肉、牛肉样品中的回收率分别为82.8%~110.4%、80.2%~108.4%、75.8%~107.1%,RSDs为0.51%~10.23%。该方法用于市售猪肉中的兽药检测,其中恩诺沙星、环丙沙星、金霉素、土霉素、四环素和强力霉素被检测出,与国标方法的测定结果相一致。该方法简单、快速、准确,适合多种兽药残留的同步筛查和准确定量。

UPLC-MS/MS测定猪肉中头孢类药物的残留量

本文采用超高效液相色谱-串联质谱对猪肉中头孢类药物残留量进行分析。样品经乙腈-水溶液和磷酸盐缓冲溶液提取,HLB固相萃取柱纯化后用超高效液相色谱质谱联用仪进行测定。结果表明,3种头孢类药物浓度在0~200 ng·mL^(-1)时,相关系数大于0.996,线性关系良好;检出限为0.001~0.365μg·kg^(-1),定量限为0.003~1.220μg·kg^(-1)。不同浓度下样品的加标回收率为83.2%~95.2%,相对标准偏差为1.9%~7.5%,标准偏差为0.078~2.817μg·kg^(-1)。

UPLC-MS/MS法测定苯磺酸氯吡格雷中5种遗传毒性杂质

利用超高效液相色谱-三重四级杆质谱联用仪(ultra performance liquid chromatography-tandem mass spectrometry,UPLC-MS/MS)建立了一种测定苯磺酸氯吡格雷中5种苯磺酸酯类遗传毒性杂质的方法,并进行了方法学验证。结果表明,方法的定量限和检出限均较低,其中,对硝基苯磺酰氯、对硝基苯磺酸的检出限和定量限分别为0.045 ng/mL和0.150 ng/mL,对硝基苯磺酸甲酯、对硝基苯磺酸乙酯、对硝基苯磺酸异丙酯的检出限和定量限分别为0.113 ng/mL和0.375 ng/mL。5种遗传毒性杂质在其线性范围内线性关系良好,相关系数在0.9987~0.9998之间,重复性RSD值在0.69%~1.85%之间,加标回收率在82.98%~119.92%之间,方法的线性、精密度、准确度、耐用性等均满足定量分析要求。因此,该方法适用于苯磺酸氯吡格雷中5种遗传毒性杂质的检测。

基于UPLC-MS/MS和GC-IMS技术分析采前套袋与未套袋油㮈果实品质差异

采用超高效液相色谱-串联质谱(ultra-high performance liquid chromatography-tandem mass spectrometry,UPLC-MS/MS)和气相-离子迁移谱(gas chromatography-ion mobility spectrometry,GC-IMS)技术结合多元统计分析方法,分析采前套袋对油㮈果实代谢产物、代谢途径以及挥发性成分的影响。结果表明,采前套袋后油㮈果皮和果肉着黄色。基于UPLC-MS/MS技术鉴定到604个油㮈果实代谢物,采前套袋改变果实代谢特征和代谢途径,筛选出显著差异代谢物58个,上调物质22个,下调物质36个;其中,与滋味相关的糖类和有机酸等物质含量差异不显著,而与滋味相关的氨基酸部分差异显著。基于GC-IMS技术鉴定到油㮈果实含有醛类14种、酯类5种、醇类4种、酮类3种和其他1种共27个挥发性物质,多数酯类物质在未套袋果实中含量较高,多数醇类物质在套袋果实中含量较高。采前套袋与未套袋油㮈果实挥发性成分具有不同的指纹图谱。基于中药数据库和已鉴定代谢物查询到199个活性成分,根据筛选标准得到37个关键活性成分,其中,采前套袋果实的槲皮素含量下调。由此说明,采前套袋可提高油㮈果实外观品质,对果实滋味、香气和功效成分等部分有影响。