固相萃取-超高效液相色谱串联质谱法测定饮用水中15种邻苯二甲酸酯

建立了饮用水中15种邻苯二甲酸酯的固相萃取超高效液相色谱串联质谱测定方法。样品经C18固相萃取柱富集,以苯基柱分离,以甲醇和水为流动相进行梯度洗脱,正离子模式下质谱多反应监测(MRM)模式检测,外标法定量。结果表明,邻苯二甲酸二丁酯在0.63~1000μg/L,其余14种邻苯二甲酸酯在0.002~500μg/L范围内线性关系良好,相关系数均大于0.9970。本方法对15种邻苯二甲酸酯的定量限为2.2~632 ng/L,回收率在81.3%~109%之间,RSD<14%。     

固相萃取-超高效液相色谱-串联质谱法同时测定大气降水中9种全氟化合物前体物质

采用固相萃取-超高效液相色谱-电喷雾串联三重四极杆质谱联用技术,建立了大气降水中9种全氟化合物前体物质的高通量检测方法。使用HLB固相萃取柱富集和净化降水样品中的目标化合物,以HSS T_3色谱柱(100mm×2.1 mm,1.7μm)为分析柱,甲醇和水作为流动相进行梯度洗脱。质谱以电喷雾负离子电离,采用多反应监测模式检测。9种目标化合物在0.05~5.00μg/L、0.5~50.0μg/L或5.00~500μg/L浓度范围内线性良好,相关系数为0.992 1~0.999 5,方法的检出限为0.05~7.9 ng/L;高、中、低3个添加水平的回收率为76.0%~106%,相对标准偏差为0.72%~13.7%。实验结果表明,该方法灵敏、准确,且具有检测范围广、分析速度快等特点,是一种适用于大气降水样品中全氟化合物前体物质检测分析的方法。     

固相萃取-超高效液相色谱-三重四级杆串联质谱法测定水中4种杀菌剂

建立了固相萃取-超高效液相色谱-三重四级杆串联质谱方法检测水中4种杀菌剂(嘧菌酯、戊唑醇、吡唑醚菌酯、肟菌酯). 水样中的杀菌剂经HLB固相萃取柱富集后,使用C18色谱柱分离,以高效液相色谱-串联质谱(HPLC-MS/MS)外标法定量分析. 同时考察pH值、洗脱溶剂、洗脱量等对杀菌剂萃取效果的影响. 试验结果表明,4种化合物在0.10~50.0 μg/L浓度范围内具有较好的线性关系,检出限在0.004~0.095 μg/L之间,回收率为68.7%~95.4%,相对标准偏差(n=5)低于10%. 方法操作简单、快速、准确、灵敏度高,适用于水中4种杀菌剂的定量分析.     

固相萃取–气相色谱法测定饮用水中5种有机磷农药

建立了固相萃取–气相色谱法测定饮用水中敌敌畏、乐果、甲基对硫磷、马拉硫磷及对硫磷的方法。采用Cleanert PEP–SPE固相萃取柱,以二氯甲烷、乙酸乙酯、甲醇及纯水活化固相萃取柱,以5 m L/min流量富集水样,然后用二氯甲烷及乙酸乙酯洗脱浓缩后进行气相色谱分析。5种有机磷农药线性相关系数均大于0.995,方法测定下限为0.16~0.80μg/L,加标回收率为59.8%~109.0%,测定结果的相对标准偏差小于16%(n=6)。该方法灵敏度高,准确度好,适用于饮用水中5种有机磷农药的检测。     

高效液相色谱-串联质谱法同时测定水体和沉积物中12种有机磷酸酯类化合物

建立了高效液相色谱-质谱联用技术结合固相萃取和液液萃取方法检测水体和沉积物中12种磷酸酯类(OPEs)化合物残留的方法.水样样品经HLB固相萃取柱富集,乙酸乙酯洗脱两次,沉积物样品以乙腈超声萃取,旋转蒸发至干,用超纯水稀释后重复水样处理步骤,采用ZORBAX Eclipse Plus C18色谱柱(150 mm×2.1 mm, 3.5 μm)进行分离,以0.2%甲酸-甲醇作为流动相进行梯度洗脱,采用正离子MRM监测模式,外标法定量分析.水样中,12种OPEs在0.05、0.10和0.50 μg/L加标水平下,除TMP (28.5%~47.8%)和TEHP (22.4%~73.8%) 外,其余目标化合物的平均回收率为66.4%~115.0%,相对标准偏差为0.5%~9.1%,方法定量限(MOQ)为0.001~0.050 μg/L;沉积物中,在5、10和50 μg/kg加标水平下,除TMP(35.7%~44.9%)、TCEP (31.2%~48.9%)外,其余目标化合物的平均回收率为65.9%~120.0%,相对标准偏差为0.01%~9.5%,方法定量限(MOQ)为0.02~2.0 μg/kg(dw).基于上述方法对太湖水样和沉积物样品中目标化合物定量检测分析,∑OPEs含量分别为0.1~1.7 μg/L和8.1~420 μg/kg dw.     

在线固相萃取净化-液相色谱-串联质谱法测定猪肉中10种大环内酯类抗生素

建立了在线固相萃取净化-液相色谱-串联质谱检测猪肉中10种大环内酯类抗生素残留的方法。样品经过乙腈提取,提取液40℃旋蒸至干后,分析物用2 mL磷酸盐缓冲液溶解,溶解液经在线固相萃取柱(HLB柱)富集净化,甲醇洗脱,然后转移至XBridge BEH C18色谱柱上,以10 mmol/L乙酸铵水溶液和乙腈溶液为流动相进行分离,最后用串联四极杆质谱检测。结果表明,10种大环内酯类抗生素在0.1~200μg/L范围内呈现良好的线性关系,相关系数均大于0.990。方法的检出限范围为0.05~0.30μg/kg,定量限范围为0.10~1.00μg/kg;添加水平为0.10~10.0μg/kg时,方法回收率为69.6%~115.2%,相对标准偏差(RSD)10%。该方法可以作为猪肉中大环内酯类抗生素的检测方法。     

硅胶固相萃取净化/高效液相色谱-串联质谱法测定海洋生物体中六溴环十二烷

建立了海洋生物体中六溴环十二烷(HBCDs)的硅胶固相萃取净化/液相色谱-串联质谱法。样品采用正己烷提取,经硅胶固相萃取柱净化,液相色谱-串联质谱分析。根据硅胶固相萃取柱的使用特性,对洗脱条件进行优化。在ACQUITY UPLC BEH C18色谱柱上进行分离,流动相为水和甲醇乙腈(V甲醇∶V乙腈=4∶6)混合溶液,梯度洗脱。质谱采用电喷雾负离子电离,多反应监测模式,内标法定量。六溴环十二烷在0.50~100.0μg/L范围内线性关系良好,相关系数(r2)大于0.995,定量下限为0.20μg/kg,回收率为85.6%~97.3%,相对标准偏差为3.9%~8.8%。该方法基质干扰小、重复性好,适用于海洋生物中六溴环十二烷的测定。     

固相萃取–气相色谱–质谱法测定地表水中的三氯苯

建立固相萃取–气相色谱–质谱联用法测定地表水中三氯苯的方法,对固相萃取柱、洗脱剂、甲醇用量进行优化试验。在200 m L水样中加入20 m L甲醇,采用C18固相萃取柱,以正己烷为洗脱溶剂萃取水中的三氯苯,用气相色谱–质谱法测定。结果表明,三氯苯的三种同分异构体分离良好,1,2,3-三氯苯、1,2,4-三氯苯、1,3,5-三氯苯的质量浓度在2.0~100μg/L范围内与其色谱峰面积均呈良好的线性,线性相关系数分别为0.999 1,0.999 4,0.999 2,检出限分别为0.004,0.005,0.005μg/L,加标回收率为90.3%~96.5%,测定结果的相对标准偏差均小于2%(n=7)。该方法操作简便、快速,定性定量准确,有机试剂用量少,适用于地表水中三氯苯的检测。     

动物尿液中盐酸克伦特罗的分子印迹固相萃取-气相色谱-质谱法研究

采用分子印迹聚合物(MIP)固相萃取小柱提取、净化并富集猪尿液中的盐酸克伦特罗分子,用N,O-双三甲基硅基三氟乙酰胺(BSTFA)衍生化,毛细管气相色谱-质谱联用(选择离子模式,选择离子为277、262、243和86)对衍生物分析。优化了MIP固相萃取柱的淋洗条件,考察了MIP固相萃取柱的净化效果和消除基体干扰能力,建立了对动物尿液中盐酸克伦特罗的定性、定量分析的方法。在优化条件下,本法检出限(LOD)为0.51μg/L,定量限(LOQ)为1.00μg/L;不同盐酸克伦特罗加入量的回收率为71.0%~89.3%;相对标准偏差为3.2%~9.7%。将该方法与农业行业标准方法比较,结果吻合较好。但该方法灵敏度和精密度高,操作更为简单、快捷。     

固相萃取-顺序注射分光光度法快速测定微生物菌落中的麦白霉素

在顺序注射系统中引入C18固相萃取柱进行生米卡链霉菌菌落样品的纯化富集,建立了快速测定菌落中麦白霉素的分光光度法。用超声波破碎菌落细胞后,将样品溶液通过固相萃取柱,用少量甲醇洗脱吸附在C18微珠上的麦白霉素,232 nm检测。进样量为2 ml,洗脱液体积为100μL,麦白霉素的富集倍率为14;线性范围为0.1~10μg/mL,检出限为0.02μg/mL,RSD为2.5%(0.5μg/mL,n=7)。菌落样品中麦白霉素的加标回收率为96%~100%。     

Determination of (fluoro)quinolones in environmental water using online preconcentration with column switching linked to large sample volumes and fluorescence detection

An analytical method based on online enrichment using coupled-column liquid chromatography with fluorescence detection has been developed to determine marbofloxacin, ciprofloxacin, danofloxacin, enrofloxacin, norfloxacin, lomefloxacin, oxolinic acid, and nalidixic acid at trace levels in surface water. The sample containing the pharmaceuticals was pumped through a short C18 column in such a way that the analytes were retained on the column, whereas polar interferences, eluting at the first of the chromatogram, were discarded to waste. Then, the analytes were transferred by the chromatographic mobile phase to a second C18 analytical column, where they were separated following a conventional chromatography. The optimized approach allowed to preconcentrate 15 mL of sample volume adjusted at acid pH with phosphoric acid and modified with 5% of methanol, at a flow rate of 1.5 mL/min in 10 min. R(2) values were between 0.994 and 0.998, detection and quantitation limits ranged between 0.001 and 0.080 and between 0.002 and 0.100 μg/L, respectively, and the interday precision was below 9.8%. Recoveries in three different surface water samples, spiked at concentration levels between 0.002 and 0.500 μg/L (n = 3 for each spiking level), ranged from 82.1 to 125.8% with the relative standard deviation lower than 12%.     

改进QuEChERS法结合超高效液相色谱-串联质谱法同时测定冷冻食品中7种季铵盐化合物

近年来,季铵盐类消毒剂的广泛使用,导致其残留在食品或环境中,并经食物链进入人体,引起呼吸系统和生殖系统的不良反应,威胁人类身体健康。为此,建立了QuEChERS-超高效液相色谱-串联质谱(QuEChERS-UPLC-MS/MS)同时测定冷冻食品中6种常规季铵盐化合物和1种新型季铵盐化合物残留的分析方法。对样品前处理方法进行改良,色谱条件进行优化,样品经20 mL 90%甲醇水溶液(含0.5%甲酸)涡旋提取20 min后,超声10 min, 10000 r/min离心10 min,取1 mL上清液放入装有100 mg PSA净化剂的15 mL离心管中净化,涡旋1 min后,10000 r/min离心5 min,取上清液直接上机测定。以甲醇与5 mmol/L乙酸铵溶液作为流动相进行梯度洗脱,采用ACQUITY UPLC BEH C₈色谱柱(50 mm×2.1 mm, 1.7 μm)分离,在ESI⁺模式,多反应监测(MRM)方式下采集数据,基质匹配曲线外标法定量。结果表明,7种待测物在C₈色谱柱上完全基线分离,在0.1~100.0 μg/L的范围内线性关系良好,相关系数(r²)为0.9971~0.9983,该方法的检出限(LOD)为0.5~1.0 μg/kg,定量限(LOQ)为1.5~3.0 μg/kg。以阴性三文鱼、鸡肉为基质样品,在低、中、高3个水平(3.0、10.0、100.0 μg/kg)下进行加标回收试验,各待测物的平均回收率为65.4%~101%,相对标准偏差(RSD)为0.64%~16.8%。该检测方法灵敏度高,选择性强,稳定性好,结果准确可靠,适用于冷冻食品中7种季铵盐化合物的批量快速测定,同时,弥补了新型季铵盐化合物检测方法的空白。     

QuEChERS/超高效液相色谱-串联质谱法测定土壤中31种磺酰脲类除草剂残留

建立了一种基于QuEChERS前处理技术和超高效液相色谱-串联质谱(UHPLC-MS/MS)同时测定土壤中31种磺酰脲类除草剂残留的方法。通过对色谱条件、提取溶剂、净化剂等进行优化,确定以甲醇和0.1%甲酸+5 mmol/L乙酸铵为流动相,1%(体积分数)乙酸-乙腈为提取溶剂,C18(25.00 mg/mL)为净化剂。31种磺酰脲类除草剂的线性关系良好,相关系数(r2)均不小于0.998 0,定量下限(S/N=10)为0.012~2.321μg/kg。3个加标水平(10、100、400μg/kg)下的平均回收率为71.8%~119%,相对标准偏差(RSD)为0.62%~13%。除烟嘧磺隆、三氟啶磺隆钠、玉嘧磺隆、啶嘧磺隆、氯吡嘧磺隆为中等强度基质效应外,其余待测物均表现为弱基质效应。该方法简便易操作,具有较好的灵敏度和准确度,适用于土壤中31种磺酰脲类除草剂残留的同时检测。     

Simultaneous determination of cyadox and its metabolites in plasma by high‐performance liquid chromatography tandem mass spectrometry

Cyadox is a novel antimicrobial growth‐promoter of the quinoxalines. For food safety and pharmacokinetic studies, a convenient, sensitive and reproducible LC‐ESI‐MS/MS method was developed for the simultaneous determination of cyadox and its major metabolites, quinoxaline‐2‐carboxylic acid, 1,4‐bisdesoxycyadox, cyadox‐1‐monoxide and cyadox‐4‐monoxide in chicken plasma. Plasma sample was subjected to a simple deproteinisation with acetonitrile. Analysis was performed on a C₁₈ column by detection with mass spectrometry in multiple reaction monitoring mode. A gradient elution program with 0.2% formic acid, methanol and acetonitrile was performed at a flow rate of 0.2 mL/min. The decision limits (CCαs) of five analytes in plasma ranged from 1.0 to 4.0 μg/L, and the detection capabilities (CCβs) were <10 μg/L. Acceptable precision and accuracy were obtained for concentrations over the standard curve range. The extraction recoveries of five analytes were between 87.4 and 93.9% in plasma at the spiked levels of 5 (10)–200 μg/L with the relative standard deviations <10% for each analyte. The developed method demonstrated a satisfactory applicability in real plasma samples.     

Simultaneous determination of three organophosphorus pesticides in different food commodities by gas chromatography with mass spectrometry

A sensitive and selective gas chromatography with mass spectrometry method was developed for the simultaneous determination of three organophosphorus pesticides, namely, chlorpyrifos, malathion, and diazinon in three different food commodities (milk, apples, and drinking water) employing solid‐phase extraction for sample pretreatment. Pesticide extraction from different sample matrices was carried out on Chromabond C₁₈ cartridges using 3.0 mL of methanol and 3.0 mL of a mixture of dichloromethane/acetonitrile (1:1 v/v) as the eluting solvent. Analysis was carried out by gas chromatography coupled with mass spectrometry using selected‐ion monitoring mode. Good linear relationships were obtained in the range of 0.1–50 μg/L for chlorpyrifos, and 0.05–50 μg/L for both malathion and diazinon pesticides. Good repeatability and recoveries were obtained in the range of 78.54–86.73% for three pesticides under the optimized experimental conditions. The limit of detection ranged from 0.02 to 0.03 μg/L, and the limit of quantification ranged from 0.05 to 0.1 μg/L for all three pesticides. Finally, the developed method was successfully applied for the determination of three targeted pesticides in milk, apples, and drinking water samples each in triplicate. No pesticide was found in apple and milk samples, but chlorpyrifos was found in one drinking water sample below the quantification level.     

Liquid chromatography–tandem mass spectrometry method for simultaneous determination of cyclosporine A and its three metabolites AM1, AM9 and AM4N in whole blood and isolated lymphocytes in renal transplant patients

A LC‐MS/MS method was developed and validated for the determination of cyclosporine A (CsA) and its three phase 1 metabolites AM1, AM9, and AM4N in whole blood and lymphocytes isolated on the Histopaque gradient. 200 μL of whole blood was precipitated with 10 mol/L zinc sulfate in acetonitrile/methanol (40:60, v/v) and lymphocytes isolated from 1.5 mL blood were extracted with acetonitrile/methanol (40:60, v/v). The analytes and internal standard cyclosporine D were separated on RP column BEH C18, 2.1×50 mm, 1.7 μm using gradient LC‐MS/MS analysis in positive electrospray mode. Time of analysis was 5 min. Linearity in blood was 5–2000 μg/L for CsA, AM1, and AM9; 2–500 μg/L for AM4N; and 2–500 μg/L for all substances in lymphocytes. Coefficient of variations was 1.8–9.8% and recovery was 92.0–110.0%. The method was used in early and chronic renal transplant patients for therapeutic drug monitoring of CsA to compare either its share in lymphocytes as target organ or binding to one lymphocyte. The same parameters were calculated for all metabolites tested.     

悬浮固化-分散液液微萃取-液相色谱-串联质谱测定纺织废水中磷系阻燃剂

建立了悬浮固化-分散液液微萃取结合液相色谱-串联质谱测定纺织废水中5种痕量磷系阻燃剂的方法。通过对萃取过程中萃取剂、分散剂的种类与体积、盐浓度、溶液pH值等对萃取效率的影响因素优化,确立了最佳萃取条件。采用了密度小于水的十一烷醇（400 μL）为萃取剂,甲醇（300 μL）为分散剂,控制溶液pH值在6~9之间,NaCl添加量为2 g,萃取时间为涡旋2 min。在优化的萃取条件下,该方法在2~100 μg/L均有良好的线性关系,相关系数大于0.995,除二（2,3-二溴丙基）磷酸酯（BIS）的检出限为5 μg/L外,三（2-氯乙基）磷酸酯（TCEP）、三（1,3-二氯-异丙基）磷酸酯（TDCP）、三（1-氮丙啶基）氧化膦（TEPA）和三（2,3-二溴丙基）磷酸酯（TRIS）的检出限均为2 μg/L。后整理、染色和印花等实际废水样品加标试验表明,方法的平均回收率为71.6%~114.5%,RSD为2.7%~11.2%（n=6）。对11个样品进行检测,其中3个废水样品检出TCEP与TDCP化合物,含量为2.6~3.4 μg/L。本方法简单,快速,灵敏度好且环保绿色,能够对纺织废水中的5种痕量磷系阻燃剂进行准确的定性与定量检测。     

固相萃取-超高效液相色谱-串联质谱法测定人尿中苯氧乙酸除草剂和有机磷、拟除虫菊酯农药代谢物北大核心CSCD

基于96孔固相萃取-超高效液相色谱-串联质谱法,建立了人尿中2种苯氧乙酸除草剂、2种有机磷农药代谢物和4种拟除虫菊酯农药代谢物的测定方法。通过对液相色谱条件、质谱条件和样品前处理过程的系统优化,实现了在16 min内对8种目标分析物的分析测定。具体方法:1 mL尿液经β-葡萄糖醛酸酶酶解过夜,Oasis HLB 96孔固相萃取进行目标分析物的提取净化,甲醇洗脱;以0.1%(体积分数)乙酸乙腈和0.1%(体积分数)乙酸水作为流动相,Acquity BEH C_(18)作为分析柱进行色谱分离;负离子电喷雾(ESI-)多反应监测(MRM)模式下检测目标化合物,同位素内标法定量。2,4-二氯苯氧乙酸(2,4-D)、2,4,5-三氯苯氧乙酸(2,4,5-T)2种苯氧乙酸除草剂和3-苯氧基苯甲酸(3-PBA)、4-氟-3-苯氧基苯甲酸(4F-3PBA)、反式二氯乙烯基二甲基环丙烷羧酸(trans-DCCA)3种拟除虫菊酯农药代谢物在0.1~100μg/L内、对硝基苯酚(PNP)、3,5,6-三氯-2-吡啶酚(TCPY)2种有机磷农药代谢物、顺式二氯乙烯基二甲基环丙烷羧酸(cis-DCCA)1种拟除虫菊酯代谢物在0.2~100μg/L内线性关系良好,相关系数均大于0.9993;方法检出限为0.02~0.07μg/L,方法定量限为0.08~0.2μg/L;低、中、高3个水平下的加标回收率为91.1%~110.5%,日内精密度为2.9%~7.8%,日间精密度为6.2%~10%。应用该方法测定了214份尿液样本。结果显示除2,4,5-T外,其余7种目标分析物均有检出。TCPY、PNP、3-PBA、4F-3PBA、trans-DCCA、cis-DCCA、2,4-D的检出率为2.8%~99.1%。检出浓度(中位值)由高到低分别是2.0μg/L(TCPY)、1.8μg/L(PNP)、0.99μg/L(trans-DCCA)、0.81μg/L(3-PBA)、0.44μg/L(cis-DCCA)、0.35μg/L(2,4-D)和未检出(4F-3PBA)。该方法操作简便,定量准确,灵敏度高,每批次可完成96个样品测定,适用于人尿中多种农药及农药代谢物的批量分析测定。     

毛细管电泳用于中药白鲜皮中生物碱的分析

建立了毛细管电泳同时分离白鲜皮中3种生物碱(胡芦巴碱、白鲜碱和胆碱)的的定量分析方法.以缓冲液H3BO3—Na2B4O7(pH=8.4,5 mmol/L)、添加剂3 mmol/L SDS和0.1%triton X-100为电泳运行液,24 kV为分离电压,分离在5 min内就可以快速完成.在230 nm检测波长处,3种组分的线性范围为:胡芦巴碱5～100μg/mL、白鲜碱5～75μg/mL、胆碱50～300μg/mL,检测限分别为1.4、1.4和16.0μg/mL.方法用于白鲜皮实际样品的测定,回收率范围在92.0%～101.0%之间。     

分散液液微萃取-气相色谱法快速测定水中15种硝基苯类物质

建立了分散液液微萃取-气相色谱电子捕获检测器测定水中15种硝基苯类物质的方法.筛选出了具有高密度且能够适用于电子捕获检测器的萃取剂.优化了色谱条件,对萃取剂种类及用量、分散剂种类及用量、萃取时间、萃取温度等条件进行了优化.DB-35毛细管柱对15种硝基苯类物质具有最好的分离效果.使用程序升温,初始80℃ 保持2 min,以5℃/min速率升温至180℃,可以在22 min内完成分离.以100μL氯苯作为萃取剂、400μL甲醇作为分散剂,对5.00 mL水样在室温下进行萃取,仅需30 s即可达到萃取平衡,15种目标物的萃取率均可达到90%以上,富集倍数达到45.0~48.8.离心分离,取下层沉积相进行气相色谱测定,使用电子捕获检测器检测,方法的定量限为0.03~0.15μg/L,线性范围为0.20~50.0μg/L,相关系数不低于0.998.方法的相对标准偏差在3.3%~8.9%之间,加标回收率在86.0%~103.5%之间.