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.

Dimension-Enhanced Ultra-High Performance Liquid Chromatography/Ion Mobility-Quadrupole Time-of-Flight Mass Spectrometry Combined with Intelligent Peak Annotation for the Rapid Characterization of the Multiple Components from Seeds of Descurainia sophia

The complex composition of herbal metabolites necessitates the development of powerful analytical techniques aimed to identify the bioactive components.The seeds of Descurainia sophia(SDS)are utilized in China as a cough and asthma relieving agent.Herein,a dimension-enhanced integral approach,by combining ultra-high performance liquid chromatography/ion mobility-quadrupole time-of-flight mass spectrometry(UHPLC/IMQTOF-MS)and intelligent peak annotation,was developed to rapidly characterize the multicomponents from SDS.Good chromatographic separation was achieved within 38 min on a UPLC CSH C18(2.1×100 mm,1.7μm)column which was eluted by 0.1%formic acid in water(water phase)and acetonitrile(organic phase).Collision-induced dissociation-MS^(2)data were acquired by the data-independent high-definition MS^(E)(HDMS^(E))in both the negative and positive electrospray ionization modes.A major components knockout strategy was applied to improve the characterization of those minor ingredients by enhancing the injection volume.Moreover,a self-built chemistry library was established,which could be matched by the UNIFI software enabling automatic peak annotation of the obtained HDMS^(E)data.As a result of applying the intelligent peak annotation workflows and further confirmation process,a total of 53 compounds were identified or tentatively characterized from the SDS,including 29 flavonoids,one uridine derivative,four glucosides,one lignin,one phenolic compound,and 17 others.Notably,four-dimensional information related to the structure(e.g.,retention time,collision cross section,MS^(1)and MS^(2)data)was obtained for each component by the developed integral approach,and the results would greatly benefit the quality control of SDS.

Determination of Ten Kinds of Alpha-2 Agonists Residues in Animal Derived Food by UHPLC-Triple Quadrupole/Composite Linear Ion Trap Mass Spectrometry

[Objectives]The paper was to establish an ultra high performance liquid chromatography-quadrupole/linear ion trap complex mass spectrometry for the determination of 10 kinds ofα2-receptor agonists in animal derived food.[Methods]The samples were extracted with sodium carbonate buffer solution and ethyl acetate,and analyzed by mass spectrometry after solid phase extraction and high performance liquid chromatography separation.[Results]Ten kinds ofα2-receptor agonists showed a good linear relationship in the range of 1-100μg/mL,with the average recovery of over 69%and the relative standard deviation less than 8.32%.The detection limit of 10 kinds of α_(2)-receptor agonists was up to 1μg/kg.[Conclusions]The method has good selectivity and strong anti-interference ability,and can meet the requirements of 10 kinds ofα2-receptor agonists residues in animal derived food.

Rapid Quantitative Determination of Isoprene Monomer in Living Taraxacum kok-saghyz by Ultra-High Performance Liquid Chromatography Tandem Mass Spectrometry

Taraxacum kok-saghyz(TKS)is rich in natural rubber(NR),a natural organic macromolecular compound composed of cis-1,4-polyisoprene,and may become the second NR-bearing plant for biochemical engineering development.In this paper,a rapid and quantitative ultra-high performance liquid chromatography tandem mass spectrometry(UHPLCMS/MS)method was established for determination of macromolecular biosynthesis substrate(dimethylallyl pyrophosphate,DMAPP)and initiator(farnesyl pyrophosphate,FPP)contained in TKS.A Kromasil C18 chromatographic column was used for separation,and the multi-reaction monitoring mode(MRM)of triple quadrupole mass spectrometry was used for detection.Quantification was performed by external calibration method.The results showed that the limit of detection(LOD)and the limit of quantitation(LOQ)of DMAPP were 2.42μg/L and 7.26μg/L,respectively,and the LOQ and the LOD of FPP were 1.02μg/L and 3.05μg/L,respectively.At a concentration of 1—1000μg/L,both analytes had good determination coefficients(>0.999)of calibration curve.The recoveries of DMAPP and FPP were between 99.0%and 117.1%.In real samples detection,the contents of DMAPP and FPP in TKS samples were between 23.32—82.77μg/L and 12.03—85.67μg/L,respectively.Thus,this approach is a reliable method to quantify DMAPP and FPP in TKS.

GLOBAL ANALYSIS OF THE METABOLITES OF CURCUMIN IN RATS BY ULTRA PERFORMANCE LIQUID CHROMATOGRAPHY COUPLED WITH QUADRUPOLE TIME OF-FLIGHT TANDEM MASS SPECTROMETRY

Curcumin,a safe natural yellow pigment with a wide range of pharmacological activities,is used both in herbal drugs and as a food coloring agents.Studies have shown that curcumin would suffer from extensive metabolism in vivoand the predominant metabolic pathways are reduction and conjugation.In order to comprehensively study the metabolism and enrich the metabolic profile of cxurcumin in vivo,we carried out this research.A systematic method with highly sensitive UPLC-Q/TOF-MS was established to analyze different biological samples of rats after

超高效液相色谱-三重四级杆串联质谱法测定化妆品中达克罗宁和新康唑

利用超高效液相色谱-三重四级杆串联质谱技术,建立化妆品中达克罗宁和新康唑非法添加物定性定量检测方法。样品经饱和氯化钠溶液分散,乙腈提取,超声波冰浴30 min助提。采用C18柱色谱柱(100 mm×2.1 mm,1.9μm),用流动相A(0.1%甲酸水)和流动相B(甲醇)进行梯度洗脱,流量为0.3 mL/min,柱温为30℃,进样体积为2μL。达克罗宁和新康唑的质量浓度在1~100 ng/mL范围内与色谱峰面积线性关系良好,相关系数均大于0.999。当取样质量为0.2 g时,质量分数定量限均为0.1μg/g,检出限均为0.03μg/g。该方法灵敏、快速,可用于化妆品中达克罗宁和新康唑两种目标物的测定。

基于超高效液相色谱-四极杆-飞行时间串联质谱联用技术的荆莲核消方化学成分分析

基于超高效液相色谱-四极杆-飞行时间质谱联用技术(UPLC-Q-TOF-MSE),结合UNIFI软件对荆莲核消方(JLHXF)进行化学成分解析。使用Supelco Ascentis?Express C18色谱柱(3.0 mm×50 mm,2.7μm)在乙腈(A)-0.1%甲酸水溶液(B)的流动相体系下进行梯度洗脱;利用电喷雾离子源(ESI)在正、负离子模式下进行扫描,借助UNIFI软件及相关文献对成分进行分析鉴定。通过UPLC-Q-TOF-MSE技术在正、负离子模式下采集复方的质谱数据,通过化合物的精确相对分子质量和串联质谱数据采用UNIFI软件辅助解析,结合对照品质谱信息及相关文献,共鉴定和推断出187个化学成分,其中黄酮类化合物77个、有机酸类化合物41个、萜类化合物26个、苯丙素类化合物24个、苯酞类化合物12个以及其他类化合物7个。UPLC-Q-TOF-MSE技术可快速鉴定出荆莲核消方中的化学成分,准确性较高,为该方药效物质基础研究提供了可靠依据。

自动QuEChERS结合UPLC-MS/MS测定莲雾中苯并咪唑类农药残留

为了建立自动QuEChERS结合高效液相色谱-串联质谱法测定莲雾中多菌灵、噻菌灵、苯菌灵及甲基硫菌灵4种苯并咪唑类农药残留量的检测方法。将莲雾样品采用混合试剂(5.5 g硫酸镁+1.5 g氯化钠+1.0 g柠檬酸钠+0.5 g柠檬酸二钠)进行净化,经QuEChERS自动样品制备系统进行制备后,应用超高效液相色谱-三重四级杆串联质谱法进行分析。结果表明,4种农药在1.00~10.00 ng/mL质量浓度范围内线性关系良好,决定系数(R2)均大于0.99;0.1、1.0、5.0 mg/kg 3个添加水平下,在莲雾基质中添加回收率为84%~105%,相对标准偏差为0.8%~9.5%(n=3),方法检出限和定量限分别为0.1~0.5μg/kg和0.5~10.0μg/kg。综上,该方法简便省时,净化效果好,灵敏度及准确度高,可用于同时测定莲雾中多菌灵、噻菌灵、苯菌灵及甲基硫菌灵4种苯并咪唑类农药的残留量。

配合饲料中64种药物超高效液相色谱-三重四极杆串联质谱检测方法的研究

[目的]建立同时检测配合饲料中64种药物的超高效液相色谱-三重四极杆串联质谱(ultra-high performance liquid chromatography-triple quadrupole tandem mass spectrometry,UHPLC-MS/MS)法,提高非法添加物的检测效率。[方法]采用Waters HSS T3型色谱柱(2.1 mm×100 mm,1.8?滋m)进行分离,流动相A为0.1%甲酸水溶液,流动相B为含0.1%甲酸的乙腈溶液,梯度洗脱,流速为0.40 mL/min,进样量为2?滋L;采用电喷雾离子源正离子扫描模式进行检测,多反应监测模式进行信号采集。比较4种样品提取溶剂以及2种固相萃取柱处理对目标药物的回收率,确定样品前处理的最佳方法。利用建立的UHPLC-MS/MS法对宁夏回族自治区不同来源的100批次配合饲料样品进行64种药物检测。[结果]配合饲料样品均质后,用含0.2%甲酸的乙腈水溶液(乙腈∶水=8∶2,V/V)提取,利用Oasis PRiME HLB型固相萃取柱对样品净化,多数目标药物的回收率在60%以上。64种药物在浓度为5.0~200.0?滋g/L的范围内线性关系良好,相关系数(R)均大于0.99;不同药物的定量限在5.0~10.0?滋g/kg;阳性添加5.0、20.0、50.0?滋g/kg 3个浓度的平均回收率在41.00%~120.49%,批内相对标准偏差(RSD)在0.54%~15.94%,批间RSD在1.25%~13.64%。在100个批次的配合饲料样品中均未检出目标药物。[结论]建立的UHPLC-MS/MS法线性关系良好、回收率高、精密度好,具有较高的重现性和较好的可操作性,可用于配合饲料中非法添加64种药物的筛查。

MDMB-4en-PINACA及其代谢标记物在大鼠体内降解规律及动态分布研究

本文旨在建立生物样品中MDMB-4en-PINACA及其代谢标记物的高效液相色谱–三重四极杆串联质谱(HPLC-MS/MS)检测方法,探索MDMB-4en-PINACA及其水解代谢物(M1)和脱烷基代谢物(M2)在大鼠体内降解规律及动态分布规律。将5只SD大鼠分为5组,一组为空白对照组,另外四组灌胃给药MDMB-4en-PINACA后分别置于干净代谢笼中,分别收集1~15 d的尿液;将60只SD大鼠随机分为15组,一组作为空白对照组,其余14组通过灌胃给药MDMB-4en-PINACA,分别在不同时间点(15min、30min、45min、1h、1.5h、2h、3h、4h、5h、6h、7h、8h、10h、12h)处死,立即取血、尿及组织(心、肝、脾、肺、肾、脑、肌肉)。用HPLC-MS/MS检测血液、尿液、各组织中MDMB-4en-PINACA及代谢标记物M1和M2的质量浓度。MDMB-4en-PINACA进入大鼠体内后,迅速分布代谢,各组织和血液中均在15 min内达最高浓度,MDMB-4en-PINACA在体内的分布特点为:脑>脾>血>肺>心脏>肝>肾>肌肉>尿;M1的分布特点为:血>脾>肺>脑>肝>肾>心脏>肌肉>尿;M2的分布特点为:血>肝>心脏>肺>脑>脾>肾>肌肉>尿。在0~12 h内MDMB-4en-PINACA及代谢标记物在各组织中呈不同规律的降解。在对1~15 d尿液的监控中,MDMB-4en-PINACA及其代谢标记物仅在少量样本中检出。本文建立的方法操作简单、检出限低、回收率高、重现性好,适用于生物样品中MDMB-4en-PINACA及代谢标记物的检验。经灌胃MDMB-4en-PINACA进入大鼠体内后,监测MDMB-4en-PINACA及代谢标记物在大鼠体内的动态分布及降解规律为体内MDMB-4en-PINACA检验提供科学依据。

基于UHPLC-Q-TOF-MS/MS技术分析大花萱草花的化学成分

目的采用超高效液相色谱串联四级杆飞行时间质谱对大花萱草花的化学成分进行分析。方法在负离子模式下,采用Waters HSS T3色谱柱,以0.1%甲酸乙腈(A)-0.1%甲酸水(B)为流动相进行梯度洗脱,流速为0.4 ml/min,柱温为35℃,进样量为4μl。建立萱草属化学成分数据库,通过精确的m/z值、特征二级数据、多种数据库和文献中的裂解途径等对化合物进行鉴定。结果共鉴定出59个化合物,包括25个黄酮类、22个苯丙素类、4个脂肪酸类、2个生物碱类以及6个其他类的化合物,其中12个化合物为首次在萱草属植物中发现。结论本方法首次系统、全面、快速地筛选并鉴别大花萱草花中的化合物,为大花萱草花的开发和深入研究提供基础。

基于超高效液相色谱-三重四极杆串联质谱法的黑蒜加工过程中特征成分变化规律

基于超高效液相色谱-三重四极杆串联质谱技术建立了黑蒜中10种风味前体物质和21种游离氨基酸同时测定的检测方法。将该方法应用于黑蒜加工过程中特征成分变化规律的研究,结果表明,在温度75℃、相对湿度85%条件下,黑蒜中的特征成分含量在加工过程中发生了较大改变。其中,γ-氨基丁酸、S-烯丙基-L-半胱氨酸、异蒜氨酸、谷氨酰胺、甲基蒜氨酸、蒜氨酸、色氨酸和γ-L-谷氨酰-S-烯丙基-L-半胱氨酸变化最为显著,是黑蒜加工过程中小分子代谢物变化的化学标志物。该方法灵敏度高、准确性好,可满足检测需求。

超高效液相色谱-三重四级杆串联质谱法测定壬二酸的含量

建立了一种超高效液相色谱-三重四级杆串联质谱法(UPLC-MS/MS),可快速准确地测定复杂样品体系中壬二酸的含量。壬二酸在0.05~20 mg·L^(-1)范围内呈良好的线性关系,相关系数(R^(2))为0.994 5;检出限为0.15mg·kg^(-1),定量限为0.5 mg·kg^(-1);采用化妆品配方基质(凝胶和霜)和透皮试验基质(皮中提取液和皮下接收液),进行加标试验(n=6),壬二酸的回收率为81.9%~105.4%,相对标准偏差(RSD)为2.2%~7.5%。该方法具有无需衍生化处理、专属性好、灵敏度高等优点,适用于复杂样品体系中壬二酸的快速测定。

三重四级杆液质法检测食品中毒黄素和米酵菌酸含量

旨在建立利用三重四级杆液相色谱质谱(UPLC-MS/MS)同时测定食品中毒黄素和米酵菌酸含量的方法。样品在80%甲醇水溶液体系中萃取,离心后上清液经QuEChERS EMR-Lipid净化处理,浓缩、复溶后,以0.1%甲酸水和乙腈为流动相经梯度洗脱,液质电喷雾离子源正负模式检测,使用外标法进行定量分析。实验结果显示,毒黄素和米酵菌酸在浓度为0.5~100μg/L的范围内表现出较好线性关系,线性线性相关系数r大于0.995,在不同基质多水平添加浓度下,回收率为86.8%~103.6%,相对标准偏差(RSD)小于5%,毒黄素方法检出限为0.1μg/kg,定量限为0.2μg/kg,米酵菌酸方法检出限为0.05μg/kg,定量限为0.1μg/kg。该方法灵敏度高、专属性好、准确可靠,适合食品中毒黄素和米酵菌酸含量的测定。

气相色谱——三重四极杆串联质谱法及高效液相色谱——串联质谱检法测定人参中禁用农药残留物

目的:建立使用气相色谱-三重四极杆串联质谱法及高效液相色谱-串联质谱检法测定人参中禁用农药残留物的测定方法。方法:参照2020年版《中国药典》通则2341第五法4.1方式操作步骤,分别采用岛津气相色谱-串联质谱GC-MSTQ8040、高效液相色谱-串联质谱Waters XEVO TQMS进行检测分析。结果:对空白样品按低中高浓度分别加入混合对照品溶液500μL、1000μL、1500μL(添加浓度以灭线磷计分别为:0.04 mg/kg;0.08 mg/kg;0.12 mg/kg)后,按照文中前处理方法处理后,在岛津气相色谱-串联质谱GC-MSTQ8040上机,每个浓度平行3份样品考察回收率和RSD,结果显示,低中高浓度加标回收率分别为:86.83%~108.43%;91.39%~112.99%;88.47%~115.09%。,RSD分别为:0.54%~9.74%;2.24%~4.20%;1.07%~2.96%。回收率高,重现性好。对空白样品按低中高浓度分别加入混合对照品溶液500μL、1000μL、1500μL(添加浓度以灭线磷计分别为:0.1 mg/kg;0.2 mg/kg;0.3 mg/kg)后,按照文中前处理方法处理后,在高效液相色谱-串联质谱WatersXEVOTQMS上机,每个浓度平行3份样品考察回收率和RSD,结果显示,低中高浓度加标回收率分别为:74.33%~103.29%;72.55%~105.16%;81.54%~103.41%。RSD分别为:0.29%~6.01%;1.07%~8.32%;0.41%~7.74%。回收率高,重现性好。结论:该方法便捷,回收率和稳定性良好,适用于人参中禁用农药残留物的测定。

超高效液相串联三重四极杆质谱法测定果冻中胭脂红酸

建立了超高效液相色谱串联三重四极杆质谱仪测定果冻中胭脂红酸含量的方法。样品通过盐酸水溶液酸化提取,并经过HLB固相萃取柱净化后,上机测定,基质外标法定量。胭脂红酸在5~200 ng·mL^(-1)线性关系良好,相关系数>0.999,方法的检出限为3.36 ng·g^(-1),定量限为11.21 ng·g^(-1)。在不同浓度的加标水平下,回收率为91.2%~98.2%,相对标准偏差均<2%。本方法污染小,操作简便,结果准确,适用于果冻中胭脂红酸的检测。

超高效液相色谱-串联四极杆质谱法测定蔡甸莲藕中吡虫啉含量的不确定度评定

目的评定超高效液相色谱-串联四极杆质谱法测定蔡甸莲藕中吡虫啉含量的不确定度。方法按照GB/T 20769—2008《水果和蔬菜中450种农药及相关化学品残留量的测定液相色谱-串联质谱法》对蔡甸莲藕中吡虫啉含量进行测定,构建数学模型,根据JJF 1135—2005《化学分析测量不确定度评定》和JJF1059.1—2012《测量不确定度评定与表示技术规范》的规定,科学分析量化不确定度,最终计算出蔡甸莲藕中吡虫啉含量的扩展不确定度。结果当蔡甸莲藕中吡虫啉含量为0.322 mg/kg时,相对标准合成不确定度为0.08689,扩展不确定度为0.0560 mg/kg,蔡甸莲藕中吡虫啉含量表示为X=(0.322±0.0560)mg/kg(P=95%,k=2)。结论超高效液相色谱-串联四极杆质谱法测定蔡甸莲藕中吡虫啉含量的不确定度主要来源为标准溶液配制、样品前处理操作和检测仪器测量过程。

基于脂质组学探究辐照对冷鲜乳鸽风味的影响

采用顶空固相萃取-气相色谱-质谱法和超高效液相色谱-串联四极杆飞行时间高分辨质谱分析辐照乳鸽中挥发性物质及脂类代谢物的变化,探究辐照乳鸽特征性风味物质并推测其可能的主要风味前体物质。结果表明:烃类和醛类物质是乳鸽中主要挥发性成分,乳鸽中共10种关键风味成分,其中壬醛、(E)-2-己烯醛、癸醛、己醛、(E)-2-辛烯醛、(E,E)-2,4-壬二烯醛、辛醛、2,4-癸二烯醛、1-辛烯-3-醇物质来源于脂质氧化,壬醛、癸醛、己醛等醛类可能是由油酸和亚油酸分解生成。脂肪酸、酰基肉碱(AcylCarnitine)、缩醛磷脂酰乙醇胺(plasmenylPE)、葡糖鞘氨醇神经酰胺(GlcCer_NDS)、酰基葡糖基二神经酰胺(AcyGlcADG)、溶血磷脂酰胆碱(lysoPC)、硬脂酰基鞘脂(Cer_BS)、溶血磷脂丝氨酸(lysoPS)是差异显著的脂质亚类。30种变量投影重要性值较高的脂质分子中,6种脂质分子的脂肪酸组成中含有油酸(C_(18:1)),10种脂质分子含有亚油酸(C_(18:2)),油酸和亚油酸作为形成乳鸽特征性风味物质的前体物质,可能由这16种脂质分子降解生成。

基于超高效液相色谱-三重四极杆串联质谱技术的柚果实不同成熟期生物活性成分的靶向筛查与定量

为探究柚果实生长过程中生物活性成分的动态变化规律,选取了西南地区6种特色柚果(东风早柚、琯溪蜜柚、长寿沙田柚、梁平柚、龙安柚和丰都红心柚),利用超高效液相色谱-三重四极杆串联质谱技术,靶向筛查和定量分析了5个成熟期、3个重要部位(外皮层、内皮层和果肉)中主要活性成分。结果表明,6~11月期间,在6个品种柚果实中共筛查出72种活性成分,包括34种类黄酮,8种酚酸、3种类柠檬苦素、5种生物碱和22种香豆素。对筛查出的活性成分进行了定量分析,共计26种,包括11种类黄酮(柚皮苷、维采宁-2和野漆树苷为主)、8种香豆素(橙皮内酯水合物、橙皮内酯、橙皮油素、6′,7′-二羟基香柠檬亭、6′,7′-环氧香柠檬亭为主)、4种酚酸(香草酸、对香豆酸、阿魏酸为主)和3种类柠檬苦素(柠檬苦素和诺米林为主)。随着成熟度的增加,外皮层和内皮层的柚皮苷含量均呈现先升高后降低趋势,且在生长膨大期达到最大值,果肉的柚皮苷和3个部位的维采宁-2和野漆树苷整体呈现下降趋势。较果肉,柚果实外皮层和内皮层有更丰富的香豆素,3个部位的香豆素含量随着成熟度大多呈现下降趋势。3个部位的类柠檬苦素含量随着成熟期均呈现降低的趋势,大多在膨大期附近达到最高值。该研究结果明确了柚果果实不同成熟期的生物活性成分差异,为柚果功能食品的开发、品种选育及深加工领域提供可靠的数据支撑。

UPLC-MS/MS法测定特殊医学用途配方食品中6种季铵盐类消毒剂残留

基于超高效液相色谱-串联三重四极杆质谱法建立含乳成分的特殊医学用途配方食品中6种季铵盐类消毒剂残留的检测分析方法。使用80%乙腈水溶液作为提取溶液对样品进行提取,采用RRHD Eclipse Plus C_(18)色谱柱进行分离,选择电喷雾离子源,在正离子模式下(ESI+)采用多反应监测模式进行检测,用基质匹配工作曲线进行定量。结果表明:6种季铵盐类消毒剂在0.1~5.0 ng/mL质量浓度范围内具有良好的线性关系,线性相关系数>0.9960,检出限为0.5μg/kg,定量限为1μg/kg;固体基质中加标回收率为72.8%~102.3%,相对标准偏差(relative standarddeviation,RSD)为0.25%~3.88%;液体基质中加标回收率为71.8%~100.8%,RSD为0.19%~2.51%。方法简单、高效、快捷、灵敏,能够很好地用于特殊医学用途配方食品中季铵盐类消毒剂的分析测定。