在线固相萃取/高效液相色谱法测定环境水样中的4种痕量邻苯二甲酸酯

建立了一种在线固相萃取/高效液相色谱测定水样中4种痕量邻苯二甲酸酯(邻苯二甲酸甲酯、邻苯二甲酸乙酯、邻苯二甲酸丁酯和邻苯二甲酸(2-乙基)己酯)的新方法.样品由外加泵注入一根固相萃取小柱上进行富集,再将富集柱切换至高效液相色谱系统中,将富集在固相萃取小柱的邻苯二甲酸酯洗脱至分析柱进行分析.在线固相萃取柱为IonPac(...     

在线净化/固相萃取-高效液相色谱法测定饮用水和环境水体中的百草枯和敌草快

建立了在线净化/固相萃取(SPE)-高效液相色谱(HPLC)快速、准确测定饮用水和环境水体中的两种痕量除草剂百草枯和敌草快的方法。样品用大体积自动进样器注入在线净化小柱并流经固相萃取小柱,通过双梯度高效液相色谱系统中的上样泵实现净化和富集后,通过阀切换将固相萃取小柱切换至分析流路中;用分析泵将待测物从富集柱冲洗至分析柱进行测定。上样泵流速和分析泵流速分别为0.7和0.6 mL/min,采用等度洗脱方式完成两种除草剂的分离和检测。检测波长分别为260 nm (百草枯)和311 nm (敌草快),进样体积为2.5 mL,整个分析时间为16 min。该方法在1.0～20 μg/L范围内线性关系良好,两种除草剂的线性相关系数均大于0.9980,检出限分别为0.10和0.12 μg/L(S/N=3)。该方法前处理简单,快速,可用于饮用水和环境水体中痕量除草剂的测定。     

在线固相萃取-高效液相色谱法测定人体尿液中的N-乙酰-S-(N-甲基甲氨酰)半胱氨酸

建立了在线固相萃取-高效液相色谱法测定人体尿液中的N-乙酰-S-(N-甲基甲氨酰)半胱氨酸(AMCC)的分析方法。左泵以Amino Pac PA柱作为在线固相萃取柱、5 mmol/L KH2PO4溶液为流动相,将AMCC与样品基质分离;然后通过控制阀切换时间仅将含AMCC的部分样品溶液在线洗脱至Acclaim PAⅡC18分析柱上,右泵以0.1%H3PO4溶液(含5%乙腈)和乙腈为流动相对AMCC进行梯度洗脱分离和分析测定。结果表明,AMCC在1.0~100 mg/L范围内线性关系良好,相关系数r>0.999;上样量为10μL时,方法定量限为0.2 mg/L;回收率在85.9%~82.9%之间;相对标准偏差(n=6)分别为0.2%(保留时间)和4.0%(峰面积)。与传统的离线固相萃取-高效液相色谱法相比,本方法更为简便环保、高效稳定。用本方法测定了7份人体尿液,结果满意。     

固相萃取-高效液相色谱法测定枸杞中的类胡萝卜素

研究了固相萃取富集和预分离,高效液相色谱测定枸杞中的类胡萝卜素的方法;枸杞中的类胡萝卜素用WatersXterraTMRP18固相萃取小柱预分离,以WatersXterraTMRP18(3.9×150mm,5μm)液相色谱柱为固定相,甲醇 四氢呋喃(4 1)为流动相分离,用二极管矩阵检测器检测,检测波长为450nm。方法标准回收率为95%～103%。用该方法测定了几种枸杞样品中的类胡萝卜素。     

在线柱浓缩-超高效液相色谱法测定水体中的痕量甲萘威和呋喃丹

采用在线柱浓缩-超高效液相色谱联用技术测定水体中痕量甲萘威和呋喃丹。水样过滤后直接进样,采用固相萃取小柱富集待测物,梯度洗脱后,利用阀切换技术将待测物反冲至分析柱Acclaim RSLC C18(100 mm×2.1 mm, 2.2 μm)上进行色谱分离,以10 mmol/L醋酸铵缓冲溶液(pH 5.0,用醋酸调节)和乙腈分别为流动相A和B,梯度洗脱,泵流速为0.8 mL/min,检测波长为280 nm,二极管阵列检测器检测。甲萘威和呋喃丹在1.0～100 μg/L范围内线性良好(相关系数r2 ＞ 0.9999),检出限(S/N=3)分别为0.5和0.25 μg/L,加标回收率为76.0%～120.0%。用所建立的方法测定了水中痕量的甲萘威与呋喃丹的含量,结果令人满意。     

固相萃取高效液相色谱法快速测定红豆杉枝叶中的3种紫杉烷类化合物

研究了用固相萃取预分离高效液相色谱法测定红豆杉枝叶中紫杉醇、三尖杉宁碱和7 表紫杉醇的方法。其中,固相萃取使用了一种新型的PRP 6高分子树脂。红豆杉枝叶经干燥粉碎后用甲醇提取,提取液用PRP 6固相萃取小柱预分离,以V(乙腈)∶V(水)=45∶55为流动相,用C18色谱柱进行分离,紫外检测器227nm测定上述3种紫杉烷类化合物,该方法加标回收率为91%～98%。此法可以快速准确的测定不同红豆杉枝叶中上述3种紫杉烷类化合物。     

高效液相色谱法测定化妆品中乙内酰脲

建立了高效液相色谱-二极管阵列检测器(HPLC-PDA)测定化妆品中乙内酰脲的方法.取1.0 g样品,加入10 mL乙腈,均质、离心、上清液浓缩、水溶解后,用C18固相萃取小柱净化,用水定容.经C18液相色谱柱分离,以甲醇和水为流动相,梯度洗脱,检测波长为210 nm.在1～20 mg/L范围内,色谱峰面积与乙内酰脲的...     

固相萃取高效液相色谱法测定冬虫夏草中甘露醇

研究了用固相萃取预分离高效液相色谱法测定冬虫夏草中甘露醇的方法.冬虫夏草样品用水超声振荡提取后用Waters Sep-Pak-C18固相萃取小柱预分离,以Waters Sugar-Pak-1钙型阳离子交换柱为固定相,0.05g@L-1EDTA钙钠溶液为流动相,示差折光仪为检测器测定冬虫夏草样品中甘露醇含量.方法检出限为2.5μg@ml-1,RSD在0.86%～1.23%之间,回收率在97%～102%之间.方法用于冬虫夏草样品中甘露醇的测定,结果满意.     

高效液相色谱法快速测定三白草中黄酮类物质

研究了用固相萃取预分离,高效液相色谱法测定三白草中黄酮类物质。三白草中的黄酮用甲醇(90 10)加热回流提取,提取液用Waters Sep-Pak-C18固相萃取小柱预分离,以ZORBAXStable Bound(4.6 mm×50 mm,1.8μm)色谱柱为固定相,磷酸(2 998)和甲醇(以体积比50比50)为流动相,在该色谱条件下,三白草中主要的黄酮成分在1.5 min内可达到基线分离;用紫外二极管矩阵检测器检测。用该方法测定了5种三白草样品中的黄酮类物质,回收率在97%~103%之间,相对标准偏差在1.6%~2.2%之间。     

西瓜中4种植物生长调节剂残留的分析方法研究

建立了固相萃取/高效液相色谱法测定西瓜中24-二氯苯氧乙酸(24-D)、赤霉素(GA3)、多效唑(PP333)、6-苄氨基嘌呤(6-BA) 4种植物生长调节剂残留的方法.样品用80%甲醇溶液提取,采用Strata C18固相萃取小柱进行富集、净化,以甲醇-0.15%磷酸水溶液为流动相,梯度洗脱,经ZORBAX Ec...     

适用于质谱分析的在线固相萃取除盐方法

建立了一个简单、快速、有效的适用于质谱或液相色谱-质谱联用的在线固相萃取(SPE)高通量除盐方法。方法分为单柱和双柱模式,借助于包含双梯度泵(上样泵/分析泵)、自动进样器和配有十通切换阀的柱温箱的高效液相色谱系统,完成样品的自动化在线除盐。单柱模式通过上样泵实现在SPE柱上进样和除盐,被分析物则保留在SPE柱上;除盐完成后,通过阀切换利用分析泵洗脱富集在SPE柱上的被分析物。双柱模式则在单柱模式基础上增加了1根SPE柱,在色谱管理软件控制下2根SPE柱轮流工作,高效率完成样品的在线除盐。该方法在结合质谱分析蛋白质、多肽等领域具有较好的应用前景。     

固相萃取/气相色谱-质谱法测定玩具中10种有机物的迁移量

建立了玩具中10种有机物迁移量的固相萃取/气相色谱-质谱测定方法。样品在25 mL去离子水中迁移60min,得到的迁移液流经Chromabond Easy固相萃取柱,用乙酸乙酯洗脱5次,每次1 mL。洗脱液过滤膜后通过60m DB-624色谱柱分离,质谱进行检测,外标法定量。方法对于不同有机物的定量限(LOQ)在0.0...     

Determination of amphetamine, methamphetamine, 3,4-methylenedioxyamphetamine, 3,4-methylenedioxyethylamphetamine, and 3,4-methylenedioxymethamphetamine in urine by online solid-phase extraction and ion-pairing liquid chromatography with detection by electrospray tandem mass spectrometry

A method using an online solid-phase extraction (SPE) and ion-pairing liquid chromatography with electrospray tandem mass spectrometry (LC/ES-MS/MS) was developed for determination of amphetamine (Amp), methamphetamine (mAmp), 3,4-methylenedioxyamphetamine (MDA), 3,4-methylenedioxyethylamphetamine (MDEA), and 3,4-methylenedioxymethamphetamine (MDMA) in urine samples. A SPE cartridge column with both hydrophilic and lipophilic functions was utilized for online extraction. A reversed-phase C18 LC column was employed for LC separation and MS/MS was used for detection. Trifluoroacetic acid was added to the mobile phase as an ion-pairing reagent. This method was fully automated and the extraction and analysis procedures were controlled by a six-port switch valve. Recoveries ranging from 85-101% were measured. Good linear ranges (10-500 ng/mL) for Amp and mAmp were determined. For MDA, MDMA and MDEA, dual linear ranges were obtained from 5-100 and 100-500 ng/mL, respectively. The detection limit of each analytical compound, based on a signal-to-noise ratio of 3, ranged from 1-3 ng/mL. The applicability of this newly developed method was examined by analyzing several urine samples from drug users. Good agreement was obtained between the results from this method and a literature GC/MS method.     

Rapid determination of five antibiotic residues in swine wastewater by online solid-phase extraction–high performance liquid chromatography–tandem mass spectrometry

A simple and quick online solid-phase extraction (SPE) coupled to liquid chromatography (LC)/tandem mass spectrometry (MS/MS) for the determination of the five antibiotics (florfenicol, FF; lincomycin, LCM; oxytetracyclin, OTC; tylosin, TS; valnemulin, VLM) in swine wastewater has been developed. After filtration, aliquots (100 μl) of wastewater samples were directly injected to a column-switching LC system. Some matrix interference was removed by washing up SPE column with 0.2% formic acid solution and acetonitrile. Antibiotics eluted from SPE column were separated on analytical column by converting switching valve and were detected by MS/MS. Calibration curves using the method of standard addition had very good correlation coefficients (r > 0.99) in the range of 0.1 to 2 ng/ml. The intra-day precision of the method was less than 12% and the inter-day precision was between 6 to 17%. The detection limits were 0.01–0.1 ng/ml. When this method was applied to wastewater samples in swine facilities, four compounds (LCM, OTC, TS, and VLM) were detected.     

在线固相萃取-液相色谱法直接测定水中超痕量多环芳烃

建立了在线固相萃取-液相色谱直接测定水体中16种超痕量多环芳烃（PAHs）的方法。水样经高速离心后，加入适量甲醇，配制成40%（体积分数）甲醇水溶液，直接进样2 mL至在线固相萃取流路，进行萃取富集，再通过阀切换将洗脱的PAHs转移至分析流路进行分离检测。16种PAHs在各自范围内线性关系良好，相关系数均大于0.996；方法的检出限为0.14~12.50 ng/L，其中苯并[a]芘（B（a）P）的检出限为0.38 ng/L。实际水样在10、40和200 ng/L加标水平下的加标回收率为76.1%~134.9%，RSD为0.3%~16.6%。B（a）P在1 ng/L加标水平下的回收率为71.8%~92.7%，RSD为3.9%。结果表明，该方法操作简单，灵敏度高，溶剂消耗量少，可满足水样中PAHs，尤其是B（a）P的超痕量分析要求。     

Rapid and simultaneous determination of nonsteroidal anti-inflammatory drugs in human plasma by LC–MS with solid-phase extraction

A rapid, selective and sensitive analytical method for the simultaneous determination of 16 nonsteroidal anti-inflammatory drugs (NSAIDs) in human plasma was carried out using Oasis HLB solid-phase extraction (SPE), followed by reversed-phase high-performance liquid chromatography and quadrupole mass spectrometry with electrospray ionization operated in the negative ion mode. The recoveries of NSAIDs from human plasma by SPE were greater than 76.7%. The use of a short column packed with small particles enabled rapid and simultaneous determination within 7 min. The detection limits for the NSAIDs were 0.01–0.9 μg/ml using the selected ion monitoring mode.     

Fully automated trace level determination of parent and alkylated PAHs in environmental waters by online SPE-LC-APPI-MS/MS

Polycyclic aromatic hydrocarbons (PAHs) are ubiquitous compounds that enter the environment from natural and anthropogenic sources, often used as markers to determine the extent, fate, and potential effects on natural resources after a crude oil accidental release. Gas chromatography-mass spectrometry (GC-MS) after liquid–liquid extraction (LLE+GC-MS) has been extensively used to isolate and quantify both parent and alkylated PAHs. However, it requires labor-intensive extraction and cleanup steps and generates large amounts of toxic solvent waste. Therefore, there is a clear need for greener, faster techniques with enough reproducibility and sensitivity to quantify many PAHs in large numbers of water samples in a short period of time. This study combines online solid-phase extraction followed by liquid chromatography (LC) separation with dopant-assisted atmospheric pressure photoionization (APPI) and tandem MS detection, to provide a one-step protocol that detects PAHs at low nanograms per liter with almost no sample preparation and with a significantly lower consumption of toxic halogenated solvents. Water samples were amended with methanol, fortified with isotopically labeled PAHs, and loaded onto an online SPE column, using a large-volume sample loop with an auxiliary LC pump for sample preconcentration and salt removal. The loaded SPE column was connected to an UPLC pump and analytes were backflushed to a Thermo Hypersil Green PAH analytical column where a 20-min gradient separation was performed at a variable flow rate. Detection was performed by a triple-quadrupole MS equipped with a gas-phase dopant delivery system, using 1.50 mL of chlorobenzene dopant per run. In contrast, LLE+GC-MS typically use 150 mL of organic solvents per sample, and methylene chloride is preferred because of its low boiling point. However, this solvent has a higher environmental persistence than chlorobenzene and is considered a carcinogen. The automated system is capable of performing injection, online SPE, inorganic species removal, LC separation, and MS/MS detection in 28 min. Selective reaction monitoring was used to detect 28 parent PAHs and 15 families of alkylated PAHs. The methodology is comparable to traditional GC-MS and was tested with surface seawater, rainwater runoff, and a wastewater treatment plant effluent. Positive detections above reporting limits are described. The virtual absence of sample preparation could be particularly advantageous for real-time monitoring of discharge events that introduce PAHs into environmental compartments, such as accidental releases of petroleum derivates and other human-related events. This work covers optimization of APPI detection and SPE extraction efficiency, a comparison with LLE+GC-MS in terms of sensitivity and chromatographic resolution, and examples of environmental applications.     

在线固相萃取-超高效液相色谱-线性离子阱串联质谱法直接测定水中10种藻类毒素

建立了全自动在线固相萃取-超高效液相色谱-线性离子阱串联质谱法直接测定水中10种藻类毒素的方法.利用程序实现多次进样,通过在线固相萃取对藻类毒素进行富集,然后切换六通阀,将富集的目标物冲洗至分析柱进行分离后,进入线性离子阱质谱检测.10种藻类毒素在相应的浓度范围内线性关系良好,相关系数均大于0.99,检出限在0.0015~0.0050μg/L之间,3个浓度水平(0.02、0.10和1.00μg/L)的加标回收率为83.7%~98.5%.结果表明,在线固相萃取极大简化了前处理过程,线性离子阱串联质谱法提高了痕量藻类毒素测定的灵敏度,增强子离子扫描(EPI)谱库的建立为藻类毒素的确证提供保障.本方法适用于水体中多种藻类毒素的快速确证和定量测定.     

固相萃取法与基质固相分散法在橙子中有机磷农药残留分析中的应用

建立了固相萃取(SPE)-反相高效液相色谱(RP-HPLC)同时测定橙子中痕量辛硫磷、二嗪农有机磷农药残留量的方法。样品经甲醇超声提取、C18固相萃取柱净化后,采用液相色谱柱分离,以乙腈-水(体积比为85∶15)为流动相等度洗脱,于254 nm下紫外检测。结果表明:在0.1～10.0 mg/L和0.4～10.0 mg/L范围内,辛硫磷、二嗪农的质量浓度与峰面积呈良好的线性关系;样品的加标平均回收率为87.3%～102.7%,相对标准偏差(RSD)为0.9%～4.9%。将该分析结果与用基质固相分散法(MSPD)处理样品所得的结果相比较,发现SPE对二嗪农的提取效果较好,而MSPD对辛硫磷的提取效果较好,但两种方法都能较好地净化样品,均能满足残留量的分析要求。     

Simultaneous determination of anthracyclines and taxanes in human serum using online sample extraction coupled to high performance liquid chromatography with UV detection

An online SPE‐LC method that can determine both anthracyclines and taxanes simultaneously in human serum samples is reported. The entire method of extraction, separation and UV detection was achieved online by column switching between an SPE column (Biotrap 500 (20×4 mm)) and an analytical column (Zorbax XDB C18, 150×4.6 mm, 5 μm) with a 23 min total cycle time. The method is linear (r²>0.998) over the range of 0.5–25 μg/mL. The analytes of interest are retained on the SPE column with good recovery (84–117%), while proteins and other serum components elute to waste. This online clean‐up is much faster (150 s) and less manual than traditional off‐line extraction methods. Using 0.1 mL spiked serum samples, the LOQ was 0.5 μg/mL. Intra‐ and inter‐day precision were acceptable (≤15% RSD) at and above the LOQ. The method was applied to the analysis of serum samples from patients undergoing chemotherapy with these agents.