Simultaneous determination of kolliphor HS15 and miglyol 812 in microemulsion formulation by ultra-high performance liquid chromatography coupled with nano quantity analyte detector

A novel method for simultaneous determination of kolliphor HS15 and miglyol 812 in microemulsion formulation was developed using ultra-high performance liquid chromatography coupled with a nano quantitation analytical detector （UHPLC-NQAD）. All components in kolliphor HS15 and miglyo1812 were well separated on an Acquity BEH C18 column. Mobile phase A was 0.1% trifluoroacetic acid （TFA） in water and mobile phase B was acetonitrile. A gradient elution sequence was programed initially with 60% organic solvent, slowly increased to 100% within 8 min. The flow rate was 0.7 mL/min. Good linearity （r 〉 0.95） was obtained in the range of 27.6-1381.1 μg/mL for polyoxyl 15 hydroxystearate in kolliphor HS15, 0.8-202.0 μg/mL for caprylic acid triglyceride and 2.7-221.9μg/mL for capric acid triglyceride in miglyol 812. The relative standard deviations （RSD） ranged from 0.6% to 1.7% for intra-day precision and from 0.4% to 2.7% for inter-day precision. The overall recoveries （accuracy） were 99.7%-101.4% for polyoxyl 15 hydroxystearate in kolliphor HS15, 96.7%-99.6% for caprylic acid triglyceride, and 94.1%- 103.3% for capric acid triglyceride in miglyol 812. Quantification limits （QL） were determined as 27.6 μg/ mL for polyoxy115 hydroxystearate in kolliphor HS15, 0.8 μg/mL for caprylic acid triglyceride, and 2.7 μg/ mL for capric acid triglyceride in miglyol 812. No interferences were observed in the retention time ranges of kolliphor HSI5 and miglyol 812. The method was validated in terms of specificity, linearity, precision, accuracy, QL, and robustness. The proposed method has been applied to microemulsion for- mulation analyses with good recoveries （82.2%-103.4%）.

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.

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.

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.

Determination of 19 polyphenolic compounds in tea by ultra-high performance liquid chromatography combined with quadrupole-time of flight mass spectrometry

A rapid method was presented for the determination of 19 polyphenols in tea by ultra-high performance liquid chromatography coupled with quadrupole-time of flight mass spectrometry(UPLC-Q-TOF MS).Tea samples were extracted by 50%(V/V)ethanol,then separated by Waters Acquity BEH C18 column using a binary solvent system composed of acetonitrile and water(0.1%formic acid)by gradient elution.The analytes were determined by Q-TOF MS in TOF MS and information dependent acquisition(IDA)-MS/MS mode.The results showed that mass accuracy error of the 19 polyphenols were lower than 5.0×10^(-6),good linear relationship was got in range of 0.2–500μg/L and correlation coefficient was higher than 0.9990.The LOD was in the range of 0.002–0.100 mg/kg and the LOQ was in the range of 0.004–0.200 mg/kg.Recovery of the method was in range of 78.4%–109.2%with spike levels of 0.004–2.000 mg/kg,relative standard deviations were lower than 10%.The method was simple,rapid and accurate.It could be used for the rapid screening and quantitative analysis of 19 polyphenols in tea.

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.

On-line enrichment and determination of polycyclic aromatic hydrocarbons in atmospheric particulates using high performance liquid chromatography with fluorescence as detector

Seven polycyclic aromatic hydrocarbons （PAHs） in atmospheric particulates were determinated by high performance liquid chromatography （HPLC） with fluorescence detector using direction injection and an on-line enrichment trap column. The method simplified the sample pretreatment, saved time and increased the efficiency. With the on-line trap column, PAHs were separated availably even underground injecting 1.0 ml sample with relatively high column efficiency. The recoveries of the seven PAHs were from 85% to 120% for spiked atmospheric particulate sample. The limit of detection was 15.3-39.6 ng/L （S/N=3.3）. There were good linear correlations between the peak areas and concentrations of the seven kinds of PAHs in the range of 1-50 ng/ml with the correlation coefficients over 0.9970. Furthermore, it also indicated that the method is available to determine PAHs in atmospheric particulates well.

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.

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.

基于UHPLC-Q-Exactive Orbitrap HRMS技术结合化学计量学方法的不同干燥处理杜仲叶成分分析

采用基于液质联用的非靶向代谢组学技术结合化学计量学数据自动解析软件AntDAS-LCHRMS分析了4种不同干燥处理(冻干、热泵烘干、电热烘干、晒干)杜仲叶样本中的化合物。杜仲叶样本数据由超高效液相色谱-四极杆-静电场轨道阱高分辨质谱(UHPLC-Q-Exactive Orbitrap HRMS)分别在正、负离子模式下进行采集,经AntDAS-LCHRMS软件解析,共鉴定出71种差异性化合物,经标准品验证确定40种化合物,包括环烯醚萜类、有机酸类、黄酮类、氨基酸类、核苷类、维生素类等9类物质。其中,正、负离子模式下均可识别并验证的化合物有车叶草苷、绿原酸、芦丁、异槲皮苷、车叶草苷酸、京尼平苷等25种化合物。层次聚类分析(HCA)及主成分分析(PCA)结果均显示,相同处理的杜仲叶样本各自聚成一类,不同处理的杜仲叶样本可明显区分。热图分析进一步揭示了不同干燥处理杜仲叶样本中差异性化合物的含量变化。晒干处理样本中苯丙氨酸及色氨酸等氨基酸类物质的水平较高;冻干及热泵烘干处理样本中有机酸类、环烯醚萜类、糖类等含量较高;电热烘干样本中核苷类、黄酮类物质的含量较高;黄酮类物质在冻干、热泵烘干及晒干样本中差异较小。研究结果为不同干燥处理杜仲叶的成分分析、品质评价及其开发应用提供了科学依据,也可为其他复杂药用植物体系的化学成分分析提供参考。

基于UHPLC-QTOF-MS的兰州百合植物化学成分鉴定

为探究地理标志产品兰州百合(Lilium davidii var.unicolor)的植物化学成分,以甘肃省五个主要产区(兰州市榆中县、兰州市七里河区、定西市临洮县、定西市渭源县、临夏市永靖县)的兰州百合鳞茎为研究对象,基于超高效液相色谱串联四极杆飞行时间质谱法的非靶向代谢组学技术鉴定其植物化学成分。结果表明,在兰州百合鳞茎中初步鉴定出62种植物化学成分,包含谷胱甘肽等22种氨基酸、多肽及其衍生物,溶血磷脂酰胆碱等9种油脂和磷脂类,鼠李糖等7种糖类,阿魏酸、咖啡酸等7种酚酸类,山奈酚等4种黄酮类,核黄素、维生素C等4种天然维生素,阿魏酰腐胺等3种酚胺类,大丁苷等2种香豆素类,葫芦巴碱等2种生物碱,萜类组分松香酸和三萜皂苷类组分刺五加苷E。本研究丰富了兰州百合植物化学成分的现有数据,为兰州百合的研究与利用提供了科学依据。

基于UHPLC-Q-Orbitrap/MS鉴定当归四逆颗粒化学成分

本研究运用超高效液相色谱-四极杆-静电场轨道阱质谱(UHPLC-Q-Orbitrap/MS)技术快速鉴定当归四逆颗粒的化学成分。采用SUPELCO C18色谱柱(100 mm×4.6 mm×2.7μm),以0.1%甲酸水溶液-乙腈为流动相进行梯度洗脱,正、负离子模式下采集数据。根据精确质荷比和二级质谱碎片离子信息,结合相关文献快速鉴定当归四逆颗粒的成分,并对化合物的药味来源进行归属。结果表明,在正、负离子模式下,分别从当归四逆颗粒鉴定出34、38种化合物,其中包括20种黄酮类、15种有机酸类、11种皂苷类、9种萜类、5种苯酞类、1种苯丙素类、1种醛类、1种核苷类、1种木脂素类及8种其他类化合物。本研究可为阐释当归四逆颗粒的药效物质基础提供依据。

橘荔散结丸醇提物化学成分的UHPLC-QE-MS分析及其抗子宫肌瘤细胞的药效机制研究

【目的】运用超高效液相色谱-四极杆-静电场轨道阱串联质谱(UHPLC-QE-MS)技术分析橘荔散结丸醇提物的化学成分,并探讨其对子宫肌瘤细胞增殖的抑制作用及机制。【方法】(1)以UHPLC-QE-MS技术分析橘荔散结丸醇提物化学成分。(2)培养原代人子宫肌瘤细胞。采用细胞计数试剂盒8(CCK-8)测定不同浓度橘荔散结丸醇提物处理不同时间后的细胞增殖抑制率,并筛选后续实验中其2个高、低浓度。实验分为空白对照组,二甲基亚砜(DMSO)组,米非司酮组及橘荔散结丸醇提物高、低浓度组,分别给予相应处理后,采用流式细胞术检测细胞周期,Western Blot或定量聚合酶链反应(qPCR)法分别检测细胞Wnt/糖原合成酶激酶3β(GSK-3β)/β-连环蛋白(β-catenin)信号通路关键蛋白Wnt 5b、GSK-3β、p-GSK-3β、β-catenin、表皮生长因子受体(EGFR)和基质金属蛋白酶2(MMP2)的蛋白、mRNA表达水平。【结果】鉴别橘荔散结丸醇提物主要化学成分91个,橘荔散结丸醇提物冻干粉与中成药橘荔散结片主要化学成分共有22个。橘荔散结丸醇提物各浓度组细胞增殖抑制率均大于空白对照组(P<0.05);橘荔散结丸醇提物高、低浓度组及米非司酮组G0/G1期细胞数均大于空白对照组,而G2/M期细胞数小于空白对照组(P<0.05);橘荔散结丸醇提物高、低浓度组及米非司酮组Wnt 5b、β-catenin、EGFR、MMP2蛋白、mRNA表达水平均低于与空白对照组(均P<0.05),而GSK-3β蛋白及mRNA表达水平与空白对照组无显著性差异(P>0.05)。【结论】UHPLC-QE-MS技术分离橘荔散结丸醇提物化学成分众多,主要成分具有氧化应激调节作用;橘荔散结丸醇提物可有效抑制子宫肌瘤细胞增殖,其分子机制与抑制Wnt/GSK-3β/β-catenin信号通路关键蛋白表达,进而干预子宫肌瘤细胞微环境氧化应激反应有关。

人参皂苷Rb_(1)和Rg_(1)体外消化产物的UHPLC-TSQ MS分析

本研究采用超高效液相色谱-三重四极杆质谱(ultra-high-performance liquid chromatography-triple quadrupole mass spectrometry,UHPLC-TSQ MS)法分析人参皂苷Rb_(1)和Rg_(1)在模拟唾液、胃液和肠液中的降解产物。在人参皂苷Rb_(1)的消化产物中发现了Rd、Rg_(3)、Rg_(5)、Rk_(1),其中在肠液中还发现了F_(2),表明F_(2)是肠液中特有的降解产物,降解途径为Rb_(1)→Rd→Rg_(3)→Rg_(5)/Rk_(1),Rb_(1)→Rd→F_(2)。在人参皂苷Rg_(1)的消化产物中发现了F_(1)和Rh_(1),降解途径为Rg_(1)→F_(1)和Rg_(1)→Rh_(1)。定量结果表明:降解产物含量在消化液中随时间而变化;在胃液中,Rg_(3)、Rd、Rg_(5)、F_(1)、Rh_(1)和Rk_(1)的达峰时间分别为1、2、4、2、2、4 h;在肠液中,7种降解产物的达峰时间均为4~6 h。另外,皂苷在唾液中的降解较胃液和肠液温和,而在胃肠道中的降解更广泛;在消化过程中,Rg_(1)比Rb_(1)更易降解。人参皂苷在消化道内会发生水解反应生成多种小分子皂苷,为Rb_(1)和Rg_(1)开发和利用提供了重要的化学与生物学基础。

腊梅花中黄酮类化合物的UHPLC/QTOF-MS分析

目的采用液相色谱-四极杆-飞行时间质谱技术UHPLC/QTOF-MS对腊梅花乙醇提取物中的黄酮类化合物进行分析鉴定。方法色谱分离采用Agilent Eclipse XDB-C18色谱柱(100 mm×2.1 mm,1.7μm),0.1%甲酸水溶液-乙腈梯度洗脱。质谱分析采用电喷雾离子源,正离子模式检测。结果通过二级质谱裂解分析以及参考文献,从腊梅花中鉴定出了绿原酸、金丝桃苷、异槲皮苷、槲皮素-3'-葡萄糖苷、山柰酚-3-O-半乳糖苷、紫云英苷、槲皮苷、槲皮素、山柰酚和异鼠李素等1个多酚类和9个黄酮类化合物。结论本法为腊梅花黄酮类化合物的分析鉴定提供快速和准确方法。

基于UHPLC-Q-TOF MS/MS的胆南星中胆汁酸类成分的质谱裂解规律研究

采用超高效液相色谱-四极杆-飞行时间串联质谱(UHPLC-Q-TOF MS/MS)法研究胆南星中4种类型25种胆汁酸类成分在电喷雾离子源正、负离子模式下的质谱裂解规律。结果表明,一级质谱中,25种胆汁酸类成分均可得到加氢(脱氢)的准分子离子峰[M+H]+([M—H]^-);二级质谱中,不同类型胆汁酸类成分(包含多种同分异构体)的裂解途径大多是脱去母核上的取代基产生H 2O及CO 2的中性碎片丢失。尤其是甾体母核C17位的功能基团更易裂解,产生一系列特征性碎片离子。游离胆汁酸在正离子模式下可发生A环和C环开裂,产生m/z 175.1123、161.0966、147.0814离子;在负离子模式下可发生中性丢失,形成[M—H—CO 2]^-、[M—H—H 2CO 2]^-、[M—H—H 2O—H 2CO 2]^-离子。此外,在正离子模式下,牛磺酸型胆汁酸可形成牛磺酸基裂解碎片离子m/z 126.0226,甘氨酸型胆汁酸可形成甘氨酸基裂解碎片离子m/z 158.0818;在负离子模式下,牛磺酸型胆汁酸侧链断裂可产生丰度较强的磺酸基m/z 79.9568、牛磺酸基m/z 124.0073和牛磺酸脱氨m/z 106.9803碎片离子,甘氨酸型胆汁酸侧链断裂可产生丰度较强的m/z 74.0426碎片离子。在负离子模式下,单酮基胆汁酸母核裂解还可形成带有酮基的特征离子m/z 402.3013,而胆汁酸酯则难以形成稳定的负离子,在正离子模式下则可产生甘氨酸甲酯离子m/z 90.0557。这些质谱裂解规律有助于对胆南星中其它胆汁酸类化合物的结构进行解析与推断,也可为快速分析和鉴定含有胆汁酸类成分的样品提供依据。

UHPLC-LTQ Orbitrap MS快速鉴别无患子果皮中部分苷及苷元成分

建立了超高效液相色谱-线性离子阱/静电场轨道阱组合式高分辨质谱(UHPLC-LTQ Orbitrap MS)联用技术整合多种数据采集、挖掘策略快速分析无患子果皮中苷类化合物;总结了两类无患子皂苷标准品的质谱裂解规律及特征碎片离子,用于无患子果皮中苷类成分的快速筛查和鉴别;探索了母离子列表(parent ion list,PIL)-MS2、PIL-MS3和高能碰撞(high energy collision dissociation,HCD)技术,用于无患子果皮中母核结构相近化合物的精细区分和鉴别;最后通过智能化的In silico策略(Mass Frontier软件中的FISH和MS Tree Match技术)对无患子果皮中新的苷类成分进行高通量筛查,并用HCD碎裂模式验证其预测的可靠性。结果表明,在无患子果皮中共鉴别出67个苷类化合物,其中38个化合物被快速筛查和鉴别,18个母核结构相近的化合物得以精细区分,11个新成分被推测。该方法能够为无患子质量控制及药效学研究提供参考数据,有助于复杂中药成分的快速定性分析。

UHPLC-LTQ-Orbitrap HRMS法结合特征裂解途径分析鉴定薄荷水提物中4种类群化学成分

采用超高效液相色谱-线性离子阱-串联静电轨道阱高分辨质谱(UHPLC-LTQ-Orbitrap HRMS)法对薄荷水提物中4种类群化学成分进行分析鉴定。选取Acquity UPLC~BEH C18色谱柱(2.1mm×100mm×1.7μm),以乙腈-0.1%甲酸水溶液为流动相,流速0.30mL/min,梯度洗脱分析。根据高分辨质谱提供的准分子离子峰和碎片离子信息,获取目标化合物的相对分子质量和结构信息,并结合保留时间、对照品分析、参考文献数据和ClogP值等相关信息,鉴定了85种化学成分,包括38种黄酮、16种酚酸、7种苯丙素和24种萜类。结果表明,采用UHPLC-LTQ-Orbitrap HRMS技术能够提高中药化学成分的分析效率,该方法可为合理开发薄荷的药用和食用价值奠定化学基础。

基于UHPLC-Q-TOF/MS法同时检测猪肉中主要抗生素类兽药残留

建立了QuEChERS净化结合超高效液相色谱串联四级杆飞行时间质谱(UHPLC-Q-TOF/MS)法同时筛查猪肉中10种抗生素类兽药残留量的分析方法。样品经过Na;EDTA-Mcllvaine缓冲溶液-0.1%甲酸乙腈-NaCl-无水Na_(2)SO_(4)-C_(18)的提取净化。通过Infinity Lab Poroshell 120 EC-C_(18)色谱柱分离,在正离子多反应监测模式下分析。结果表明,10种兽药相关系数大于0.99,在5.0~100.0μg/kg范围内线性关系良好,在5、10、20μg/kg三个添加水平下平均回收率为72.3%~117.3%,日内相对标准偏差为(Relative Standard Deviation,RSD)0.9%~10.4%,日间RSD为1.1%~13.4%,检测限(Limit of Detection,LOD)为0.25~1.0μg/kg,定量限(Limit of Quantity,LOQ)为0.5~5.0μg/kg。采用本方法对市场购买的50份新鲜生猪肉样品进行检测,1份样品四环素呈阳性,其余样品均未检出。该方法操作简便、快速,具有良好的精密度和定量限,适用于猪肉中10种抗生素类兽药的快速检测。

漂浮固化分散液液微萃取-UHPLC-MS/MS法测定水产品中丁香酚的残留量

建立了漂浮固化分散液液微萃取(DLLME-SFO)前处理技术,结合超高效液相色谱-串联质谱(UHPLC-MS/MS)法测定水产品中丁香酚的残留量。通过考察萃取剂种类、萃取剂体积、分散剂种类、分散剂体积、氯化钠质量分数、萃取时间、离心温度对萃取效率的影响,确定了最佳萃取条件,即以30μL1-十一醇为萃取剂,800μL乙醇为分散剂,氯化钠质量分数为6%,于-3℃下以10 000r/min离心5min,将液体部分移除,待固体融化后取20μL供UHPLC-MS/MS分析。结果表明,在5~500μg/kg范围内,丁香酚的线性关系良好,相关系数为0.999 6,回收率在88.9%~103.4%之间,方法检出限和定量限分别为1.47μg/kg和4.91μg/kg,日内相对标准偏差(RSD)均低于7.5%(n=6),日间相对标准偏差(RSD)均低于9.8%(n=3)。该方法操作简单,溶剂用量少,快速、安全、重现性好,适用于水产品中丁香酚残留的分析。