气相色谱-质谱联用检测稻田水中的双甲脒农药残留

建立了用于检测稻田水中双甲脒农药残留的液液萃取/气质联用方法。使用GC-MS选择离子监测模式检测,考察了不同的提取溶剂和pH对检测结果的影响。在优化条件下,双甲脒在20~2000ng/mL范围内具有良好的线性关系,相关系数为0.9991,平均回收率为86.7%,精密度(n=5)为5.3%,检出限为10ng/mL。该方法快速、灵敏、准确,可用于稻田水中双甲脒的定性定量分析检验。     

β-环糊精修饰SiO_2复合材料固相萃取-高效液相色谱法测定环境水样中芴、菲和荧蒽

采用β-环糊精修饰SiO_2复合材料(β-CD@SiO_2)固相萃取,高效液相色谱法测定,建立了环境水样中3种多环芳烃芴、菲和荧蒽的分析方法。考察了影响该复合材料固相萃取芴、菲、荧蒽的各种因素,在选定实验条件下,方法对目标物的富集倍数为30倍,芴、菲和荧蒽线性范围分别为17.0~3 300ng/mL、7.0~3 300ng/mL和3.0~3 300ng/mL,检出限分别为2.10、0.50和0.47ng/mL,回收率范围为96.3%~106.0%。所建立的方法成功用于湖水和下水道污水中芴、菲和荧蒽的检测。     

浊点萃取-石墨炉原子吸收光谱法测定痕量钯

建立了浊点萃取-石墨炉原子吸收光谱法(GFAAS)测定痕量金属钯的新方法,利用表面活性剂Triton X-114和络合剂2-(5-溴-2-吡啶偶氮)-5-二甲氨基苯胺(5-Br-PADMA)对钯进行浊点萃取。研究了溶液pH、试剂浓度、平衡温度和加热时间等因素对浊点萃取及测定灵敏度的影响。优化条件为:pH 5.50 HAc-NaAc缓冲,0.08 mL 5×10-4 mol/L 5-Br-PADMA,0.70 mL10g/L Triton X-114。在最佳条件下,方法的线性范围为0.1～10 ng/mL,钯的检出限为0.068 ng/mL,富集倍率为45倍。该方法可用于环境样品中痕量钯的富集和测定,结果令人满意。     

中空纤维膜液相微萃取-气相色谱/质谱法检测尿液中的苯丙胺类兴奋剂

建立了尿液中痕量苯丙胺类毒品的中空纤维膜液相微萃取-气相色谱/质谱检测方法。采用中空纤维膜液相微萃取技术萃取尿液中4种苯丙胺类毒品,研究萃取剂类型、体积、溶液pH、萃取时间和温度等对萃取效果的影响。尿液中4种苯丙胺类毒品的最佳萃取条件为:样品溶液pH 13,甲苯为萃取剂,搅拌速度500 r/min,30℃条件下萃取15 min;此条件下苯丙胺(AM)、甲基苯丙胺(MAM)、3,4-亚甲二氧基苯丙胺(MDA)、3,4-亚甲二氧基甲基苯丙胺(MDMA)的检出限(S/N=3)分别为1.0,0.75,1.0,0.64 ng/mL,相对标准偏差分别为6.62%,3.98%,4.57%,2.35%,富集倍数分别为155,170,132,218倍。本方法可用于尿液中痕量苯丙胺类毒品的分析测定。     

固相萃取-气相色谱/质谱联用测定环境水中噻唑硫磷农药残留

建立了对环境水中噻唑硫磷农药残留进行检测的离线固相萃取-气相色谱/质谱联用(SPE-GC/MS)的方法。固相萃取采用C18柱,用甲醇洗脱;GC/MS采用选择离子监测模式。该方法具有较高的灵敏度和选择性,对环境水中噻唑硫磷的最低检测质量浓度为56.4 ng/L(S/N=3);在0.282~141 μg/L时,响应值与样品浓度呈良好的线性关系;加样回收率大于85.5%,相对标准偏差（RSD）小于4.42%。方法操作简便、快速,可用于施用噻唑硫磷后环境水中痕量农药的监测。     

顶空固相微萃取-气相色谱质谱联用测定烷基铅的研究

建立了顶空固相微萃取(HS SPME)与气相色谱 质谱(GC/MS)联用测定水样中四甲基铅和四乙基铅的方法,探讨了SPME萃取烷基铅的实验条件,并对GC/MS条件进行了优化。结果表明:四甲基铅和四乙基铅分别在5～1000ng/mL和1～500ng/mL范围内有良好的线性关系,检出限分别为四甲基铅5.19ng/mL,四乙基铅1.05ng/mL。方法用于合成水样分析,四甲基铅和四乙基铅的回收率在87.5%～110.6%之间,相对标准偏差在1.7%～6.5%之间。     

聚[2-(丙烯酰氧基)乙基]三甲基氯化铵-乙二醇二甲基丙烯酸酯整体柱固相萃取结合高效液相色谱法测定尿液中3种苯二氮■类药物

以[2-(丙烯酰氧基)乙基]三甲基氯化铵(DAC)为单体,乙二醇二甲基丙烯酸酯(EDMA)为交联剂在注射器中制备聚合物整体柱,用其固相萃取尿液中溴西泮(BRZ)、劳拉西泮(LRZ)和地西泮(DZP)3种苯二氮■类药物(BZDs),并采用高效液相色谱法(HPLC)分析。实验考察了整体柱聚合时间及固相萃取条件(淋洗溶液、洗脱溶剂种类和体积)对BZDs萃取效率的影响。结果表明,仅聚合4 h得到的整体柱对BZDs吸附效率为100%。取尿液样品4 mL上样,用4 mL H_2O冲洗,1 mL乙酸乙酯洗脱,采用高效液相色谱分析。在最优条件下,3种BZDs在4.0～1 000 ng/mL范围内线性关系良好(r=0.999),检出限(S/N=3)和定量限(S/N=10)分别为1.0～1.2 ng/mL和3.3～4.0 ng/mL;在10、25和50 ng/mL加标水平下回收率为81.4%～102%,日内(n=3)和日间(n=3)相对标准偏差分别为1.2%～4.5%和2.5%～8.3%。该整体柱可对尿液中3种BZDs有效净化,且富集达12～15倍。方法构筑的聚合物整体柱制备简单,萃取高效,可成功用于尿液中3种BZDs的分析。     

环境水样中百菌清残留的单滴微萃取-反相液相色谱测定

应用单滴微萃取(SDME)-反相液相色谱(RPLC)检测了环境水样中的百菌清残留.优化了单滴微萃取条件:环己烷萃取剂6 μL、单滴体积2 μL、搅拌速率350 r/min、萃取时间40 min、水溶液温度35 ℃、无盐度.水样经单滴微萃取后,使用Hypersil C18柱反相液相色谱分离测定百菌清.反相液相色谱条件:100%甲醇流动相、流速1.0 mL/min、柱温25 ℃、224 nm检测.方法的线性范围、检出限、相对标准偏差和富集倍数分别为1.0 ～50 μg/L、0.02 μg/L、6.1%和427倍.采用该法对环境水样中的百菌清残留进行了测定,环境水样的加标回收率为98% ～106%.     

浊点萃取-石墨炉原子吸收光谱法测定环境样品中的痕量镉

研究了浊点萃取-石墨炉原子吸收光谱法(GFAAS)测定痕量镉的新方法,利用表面活性剂Triton X-100和络合剂1-(2-吡啶偶氮)-2-萘酚(PAN)对镉进行浊点萃取。详细探讨了影响浊点萃取及测定灵敏度的因素。优化条件为:0.25 mL 30%NaC l,pH 8.5,0.50 mL、4.0×10-4mol/L PAN,0.2 mL 1.0%TritonX-100。在最佳条件下,镉的富集倍率为50倍,检出限为5.9 ng/L,RSD为2.1%。该方法用于环境样中痕量镉的富集和测定,结果令人满意。     

基于β-环糊精的分散液液微萃取分析蜂蜜中金霉素和强力霉素

建立一种简便、高效、环保型分散液液微萃取方法用于分析蜂蜜中金霉素和强力霉素的含量。采用分散液液微萃取法,考察了影响萃取效率的因素,得到最佳萃取条件:萃取溶剂为1-丁基-3-甲基咪唑六氟磷酸盐,体积为100μL;分散剂为0.1 mg/mLβ-环糊精;萃取方式为涡旋2 min。在该条件下对蜂蜜中的金霉素和强力霉素进行萃取、浓缩,两者的线性范围分别为5.0~161.6μg/mL和5.2~166.4μg/mL,相关系数(r)分别为0.9993,0.9992,定量限分别为0.10,0.15μg/mL。该方法仅使用环保型溶剂离子液体,以β-环糊精为分散剂,便可有效地对蜂蜜样品中金霉素和强力霉素进行萃取、浓缩,且萃取效率高,可用于蜂蜜中金霉素和强力霉素的残留分析。     

Polyimidazolyl acetate ionic liquid grafted on cellulose filter paper as thin-film extraction phase for extraction of non-steroidal anti-inflammatory drugs from water

Recently, pharmaceuticals and personal care products in the water environment exhibited potential risks to both human and aquatic organisms. In order to improve the sensitivity and accuracy of pharmaceutical detection, the polyimidazolyl acetate ionic liquid was synthesized by Radziszewski reaction and coated on cellulose filter papers as a thin-film extraction phase for extraction of non-steroidal anti-inflammatory drugs from water. The attenuated total reflection-infrared spectrometry, thermogravimetric analysis, and scanning electron microscope analyses demonstrated that the polyimidazolyl acetate ionic liquid was successfully prepared and attached to the surface of the cellulose filter paper through chemical bonding. The adsorption capacity of the homemade thin-film extraction material for the four non-steroidal anti-inflammatory drugs was greater than 8898 ng/cm² under the optimum conditions, and the desorption rate was over 90%. Then, a paper-based thin-film extraction phase-high-performance liquid chromatography-tandem mass spectrometry method was established for the extraction of non-steroidal anti-inflammatory drugs in water. This method provided limits of detection and limits of quantification were in the range of 0.02–0.15 and 0.17–0.50 μg/L, respectively. Hence, the obtained thin-film extraction phase showed excellent recovery and reproducibility for the target non-steroidal anti-inflammatory drugs with carboxyl groups from water.     

Simultaneous quantitation of etoricoxib, salicylic acid, valdecoxib, ketoprofen, nimesulide and celecoxib in plasma by high-performance liquid chromatography with UV detection

A specific, accurate, precise and reproducible high performance liquid chromatography (HPLC) method was developed and validated for the simultaneous quantitation of etoricoxib, salicylic acid, valdecoxib, ketoprofen, nimesulide and celecoxib in human plasma. The method employed a simple liquid-liquid extraction of etoricoxib, salicylic acid, valdecoxib, ketoprofen, nimesulide and celecoxib and internal standard (IS, DRF-4367) from human plasma (500 microL) into acetonitirile. The organic layer was separated and evaporated under a gentle stream of nitrogen at 40 degrees C. The residue was reconstituted in the mobile phase and injected onto a Kromasil KR 100-5C18 column (4.6 x 250 mm, 5 microm). The chromatographic separation was achieved by gradient elution consisting of 0.05 M formic acid (pH 3)-acetonitrile-methanol-water at a flow rate of 1.0 mL/min. The eluate was monitored using an ultraviolet (UV) detector set at 235 nm. The ratio of peak area of each analyte to IS was used for quantification of plasma samples. Nominal retention times of etoricoxib, salicylic acid, valdecoxib, ketoprofen, nimesulide, IS and celecoxib were 15.63, 17.20, 21.66, 24.95, 26.27, 30.24 and 32.22 min, respectively. The standard curve for etoricoxib, salicylic acid, valdecoxib, ketoprofen and celecoxib was linear (r2 > 0.999) in the concentration range 0.1-50 microg/mL and for nimesulide (r2 > 0.999) in the concentration range 0.5-50 microg/mL. Absolute recovery was >83% from human plasma for all the analytes and IS. The lower limit of quantification (LLOQ) of nimesulide was 0.5 microg/mL and for etoricoxib, salicylic acid, valdecoxib, ketoprofen and celecoxib the LLOQ was 0.1 microg/mL. The inter- and intra-day precisions in the measurement of QC samples, 0.1, 0.3, 15.0 and 40.0 microg/mL (for all analytes except nimesulide), were in the range 2.29-9.37% relative standard deviation (RSD) and 0.69-10.28% RSD, respectively. For nimesulide the inter- and intra-day precisions in the measurement of quality control (QC) samples, 0.5, 1.5, 15.0 and 40.0 microg/mL, were in the range 3.21-7.37% RSD and 0.97-7.06% RSD, respectively. Accuracy in the measurement of QC samples for all analytes was in the range 91.03-106.38% of the nominal values. All analytes including IS were stable in the battery of stability studies, viz. bench top, autosampler and freeze-thaw cycles. Stability of all analytes was established for 21 days at -20 degrees C. The application of the assay in an oral pharmacokinetic study in rats co-administered with celecoxib and valdecoxib is described.     

Quantification of nimesulide in human plasma by high-performance liquid chromatography/tandem mass spectrometry. Application to bioequivalence studies.

A method based on liquid chromatography with negative ion electrospray ionization and tandem mass spectrometry is described for the determination of nimesulide in human plasma. Liquid-liquid extraction using a mixture of diethyl ether and dichloromethane was employed and celecoxib was used as an internal standard. The chromatographic run time was 4.5 min and the weighted (1/x) calibration curve was linear in the range 10.0-2000 ng x ml(-1). The limit of quantification was 10 ng x ml(-1), the intra-batch precision was 6.3, 2.1 and 2.1% and the intra-batch accuracy was 3.2, 0.3 and 0.1% for 30, 300 and 1200 ng x ml(-1) respectively. The inter-batch precision was 2.3, 2.8 and 2.7% and the accuracy was 3.3, 0.3 and 0.1% for 30, 300 and 1200 ng x ml(-1) respectively. This method was employed in a bioequivalence study of one nimesulide drop formulation (nimesulide 50 mg x ml(-1) drop, Medley S/A Indústria Farmacêutica, Brazil) against one standard nimesulide drop formulation (Nisulid, 50 mg x ml(-1) drop, Astra Médica, Brazil). Twenty-four healthy volunteers (both sexes) took part in the study and received a single oral dose of nimesulide (100 mg, equivalent to 2 ml of either formulation) in an open, randomized, two-period crossover way, with a 2-week washout interval between periods. The 90% confidence interval (CI) for geometric mean ratios between nimesulide and Nisulid were 93.1-109.6% for C(max), 87.7-99.8% for AUC(last) and 88.1-99.7% for AUC(0-infinity). Since the 90% CI for the above-mentioned parameters were included in the 80-125% interval proposed by the US Food and Drug Administration, the two formulations were considered bioequivalent in terms of both rate and extent of absorption.     

Sensitive method for determination of methyl tert-butyl ether (MTBE) in water by use of headspace-SPME/GC-MS

A simple and rapid method for the determination of methyl tert-butyl ether (MTBE) in water by headspace-solid-phase microextraction (headspace-SPME) at sub-microg/L concentrations is described. On using a cooled SPME fiber coated with a 75-microm layer of poly(dimethylsiloxane)/carboxene and heating the sample to 35 degrees C, about 4 times more MTBE is extracted compared to SPME extraction with the fiber placed in the water sample. Stable analytical conditions with a detection limit of 10 ng/L are achieved. By use of a sample volume of 4 mL in a 10 mL vial, a sodium chloride content of 10% (w/w), and an extraction time of 30 min, the total time of an analytical cycle was optimized to 39 min. Precise linearity of R2>0.9991 and R2>0.9916 in the calibration range of 20-5000 ng/L and 20-100 ng/L, both in addition to blanks, respectively, and relative standard deviations of 10% (100 ng/L, long-term) and 11% (20 ng/L, short-term) are presented. The recovery is well within the accepted limits of 83-118% at a concentration of 100 ng/L and even close thereto at trace levels of 20 ng/L (96-125%). The data presented for a concentration of 100 ng/L are examined by statistical methods and show results for the T test at the 95% confidence level. Due to the large concentration range covered, the method is well suited for the monitoring of MTBE in the aquatic environment.     

Simultaneous determination of a selected group of cytostatic drugs in water using high-performance liquid chromatography-triple-quadrupole mass spectrometry

In recent years, an increasing concern has risen about the presence of pharmaceuticals in the aquatic environment. Despite their toxicity, increasing consumption and release into the municipal sewage, only a few studies have been focused on cytostatic drugs, mainly due to the lack of methods for their simultaneous analysis. In this work, a method, based on solid-phase extraction prior to high-performance liquid chromatography-triple quadrupole mass spectrometry determination, was optimized and validated for the simultaneous determination of some (14) of the most widely used cytostatic drugs in river water, influent and effluent wastewater. Process efficiency was in the range between 41 and 99% in real samples, except for cytarabine (24%), docetaxel (17%) and methotrexate (30%), due to suppression effects; precision values were <11%, except for gemcitabine (up to 19%); and detection limits were in the range between 0.1 and 38 ng/L. Cytarabine, doxorubicin, etoposide, gemcitabine, iphosphamide and vinorelbine were found at concentration levels up to 14 ng/L in influent and effluent wastewater, showing an insignificant decrease during sewage treatment; cytarabine and gemcitabine were found in effluent wastewater and were also detected in river water associated with effluent discharges.     

UPLC-MS/MS法快速筛查尿液中30种滥用药物

基于超高液相色谱-串联四极杆/线性离子阱质谱(QTRAP UPLC-MS/MS),建立了尿液中30种滥用药物的筛查方法。采用蛋白沉淀法处理尿液样品,实现对多类别滥用药物的高效提取。采用分段多反应监测(s MRM)联合信息依赖性采集(IDA)与增强离子扫描(EPI)模式,结合EPI谱库检索匹配确证检出物信息,并引入内标辅助定量。30种滥用药物质量浓度在0.5~50 ng/mL范围内线性关系良好(R²> 0.99);检出限为0.01~0.25 ng/mL,定量限为0.1~0.4 ng/mL;加标回收率为76.2%~112.5%,相对标准偏差为3.1%~12%。该方法适用于实际尿样中痕量滥用药物的定性与定量分析。     

Simultaneous determination of rofecoxib and celecoxib in human plasma by high-performance liquid chromatography

An innovative reversed-phase high-performance liquid chromatographic method is validated for the simultaneous determination of rofecoxib and celecoxib in human plasma. The internal standard is 4-n-pentyl-phenyl-acetic acid. Good chromatographic separation is achieved using a Zorbax SB-CN (5 microm) analytical column operated at room temperature and mobile phase consisting of acetonitrile and water containing 0.1M potassium dihydrogen orthophosphate buffer adjusted to pH 2.4 with 85% orthophosphoric acid (42:58, v/v). UV detection is performed at 254 nm, and the flow rate is maintained at 1.0 mL/min. Plasma samples are extracted into an organic solvent (1-chlorobutane) and evaporated under an air flow. The calibration curve for rofecoxib is linear over the range of 10 to 500 microg/L, and the celecoxib calibration curve is linear over the range of 20 to 2000 microg/L. The lower limit of quantitation for rofecoxib and celecoxib is 10 and 20 microg/L, respectively, using 1.0 mL of human plasma. The validation data show that the assay is sensitive, accurate, specific, and reproducible for the determination of rofecoxib and celecoxib. This method is therefore appropriate for pharmacokinetic studies to quantitate these therapeutic agents in patients with arthritis conditions.     

Analysis of pharmaceuticals in indirect potable reuse systems using solid-phase extraction and liquid chromatography–tandem mass spectrometry

A solid-phase extraction (SPE) LC–MS/MS method for 18 commercial drugs in secondary wastewater and product water from water recycling plants using microfiltration (MF) and reverse osmosis (RO) has been developed, optimised and validated. The method incorporates a range of multi-class pharmaceuticals including lipid lowering agents, analgesics, antipyretics, non-steroidal anti-inflammatory drugs, antidepressants, anticoagulants, tranquilizers, cytostatic agents, and antiepileptics. Method limits of quantitation (MLQs) in secondary wastewater ranged from 15 to 250 ng/L, while MLQs in post-RO water ranged from 1 to 25 ng/L. Results from analysis of secondary wastewater from Western Australia are presented, and represent the largest survey of non-antibiotic pharmaceuticals within Australia to date. Analysis of post-RO water from two MF/RO water recycling facilities also demonstrate that MF/RO treatment removes most pharmaceuticals to below the analytical limits of detection, and more importantly, up to seven orders of magnitude below health-based guideline values.     

顶空气相色谱质谱联用测定厄贝沙坦中遗传毒性杂质N-亚硝基二甲胺和N-亚硝基二乙胺

采用顶空进样气相色谱-质谱联用法,对厄贝沙坦原料药中的遗传毒性杂质N-亚硝基二甲胺(NDMA)和N-亚硝基二乙胺(NDEA)进行同时测定。采用岛津SH-Rtx-Wax气相色谱柱程序升温进行分离,电子轰击电离源(EI)电离,选择离子监测(SIM)模式检测。结果表明NDMA和NDEA在10~500 ng/mL浓度范围内线性关系良好,检出限(LOD)分别为1.7 ng/mL和4.5 ng/mL,峰面积相对标准偏差(RSD)均小于2.4%。阴性及阳性样品加标回收率为100.6%~108.7%。该方法能够有效地检测原料药厄贝沙坦中NDMA和NDEA的含量。     

液相色谱-串联质谱法测定污水处理厂水样中双酚A、四溴双酚A及烷基酚类化合物

近年来,双酚A、四溴双酚A及烷基酚类化合物由于其对水生生物的内分泌干扰作用受到越来越广泛的关注。污水处理厂是处理这类化合物的重要途径,研究目标物在其中的浓度分布对于探明此类物质在环境中的暴露水平具有重要意义,而建立相应的分析测定方法则是开展上述研究的基础。本研究建立了同时测定污水处理厂水样中双酚A、四溴双酚A及6种烷基酚类化合物的反相液相色谱-电喷雾串联质谱分析方法。结果发现,以ZORBAX Eclipse Plus C18色谱柱（150 mm×2.1 mm,3.5 μm）为分离柱,乙腈和0.02%（v/v）氨水溶液为梯度洗脱的流动相,电喷雾质谱负离子模式下目标化合物在11 min内分离;在1~100 μg/L范围内,双酚A、四溴双酚A及6种烷基酚类化合物的峰面积与质量浓度的线性关系良好（R²≥0.998）,方法定量限为2.0~20 ng/L;添加水平分别为0.2、2、20 μg/L时,目标化合物的平均回收率分别为64.3%~118.0%、65.9%~100.5%、70.3%~102.7%,相对标准偏差均小于7.1%。基于上述方法,对江苏省某工业园区污水处理厂水样中相关物质进行检测,出水中检出5种目标化合物,质量浓度范围为11.9~3015.3 ng/L。结果表明,该方法准确可靠、灵敏度高,适用于污水处理厂水样中相关烷基酚类化合物的检测。