高效液相色谱-串联质谱法测定食用植物油中4-壬基酚的含量

采用高效液相色谱-串联质谱法测定食用植物油中4-壬基酚的含量。食用植物油样品用乙酸乙酯-环己烷(1+1)混合液溶解,以凝胶渗透色谱净化,在线收集14.0~17.0min的馏分,于30℃浓缩至近干,加甲醇1.0 mL溶解残余物。在高效液相色谱分离中,以Agilent Poroshell120ec-C_(18)色谱柱为分离柱,以不同体积比的甲醇和0.1%(质量分数)氨水溶液的混合液为流动相进行梯度洗脱。在串联质谱分析中,采用电喷雾负离子源和多反应监测模式检测。所用内标物为4-n-NP-D4,以空白玉米油为基质。4-壬基酚的线性范围为0.25~160μg·kg~(-1),方法的检出限(3S/N)为1.00μg·kg~(-1)。在2.00,5.00,10.00μg·kg~(-1)等3个浓度水平进行加标回收试验,测得回收率为99.0%~115%,测定值的相对标准偏差(n=6)为4.3%~8.1%。     

凝胶渗透色谱净化-液相色谱-同位素稀释串联质谱法测定肉及肉制品中的甲萘威残留

称取试样约5g(精确至0.01g),加入1.000 mg·L~(-1)甲萘威-D7同位素内标溶液50μL,加入适量水(肉样加水1.5mL,肉制品加水3mL),加40mL丙酮,均质1min,加氯化钠6g,充分摇匀,再加30mL石油醚,振摇30min,静置30min。取有机层上清液,经无水硫酸钠过滤,旋转蒸发浓缩至约1mL,加2mL乙酸乙酯-环己烷(1+1)混合液,再浓缩至约1mL,如此重复3次。用乙酸乙酯-环己烷(1+1)溶液定容至10.0mL,经0.22μm滤膜过滤,进行凝胶色谱(GPC)净化。GPC条件如下:Bio Beads S-X3凝胶色谱净化柱(400mm×30mm),乙酸乙酯-环己烷(1+1)混合液为流动相,馏分收集段10.0～15.0min,在线浓缩加热温度45℃,真空度2.0×10~4Pa。以乙腈为替换溶剂替换两次后将净化液定容至1.0mL,进行液相色谱-串联质谱分析。采用HSS T3色谱柱(100mm×2.1mm,1.7μm)进行分离,以0.1%(体积分数)甲酸溶液-乙腈(6+4)为流动相,质谱分析中采用电喷雾正离子源和多反应监测模式。甲萘威的质量浓度在0.010～0.500mg·L~(-1)内和其峰面积与内标峰面积之比呈线性关系,测定下限(10S/N)为0.005mg·kg~(-1)。加标回收率在81.0%～105%之间,测定值的相对标准偏差(n=6)在3.8%～16%之间。     

固相萃取-液相色谱-串联质谱法测定动植物油脂中胆固醇

采用固相萃取-液相色谱-串联质谱法测定动植物油脂中胆固醇的含量。样品在无水乙醇和氢氧化钾溶液中皂化,用石油醚-乙醚(1+1)混合液提取,经硅胶固相萃取柱净化。以Zorbox SB C_(18)色谱柱为分离柱,以不同体积比的5mmol·L~(-1)乙酸铵溶液和乙腈-甲醇(1+1)溶液的混合液为流动相进行梯度洗脱,采用电喷雾正离子源和多反应监测模式检测。采用内标法定量,胆固醇的质量浓度在0.1~5.0mg·L~(-1)内与其对应的峰面积呈线性关系,胆固醇在植物油脂和动物油脂中的检出限(3S/N)分别为0.02,0.2mg·kg~(-1)。在0.5,1.0,5.0mg·kg~(-1)等3个浓度水平进行加标回收试验,回收率为85.2%~92.0%,测定值的相对标准偏差(n=6)为3.6%~9.4%。     

高效液相色谱-串联质谱法测定化妆品中壬基苯酚

提出了高效液相色谱-串联质谱法测定化妆品中壬基苯酚含量的方法。化妆品试液用甲醇-二氯甲烷（8+2）混合溶液超声提取30 min[唇膏类试样用无水乙醇-二氯甲烷（8+2）混合溶液],离心分离取上清液过Oasis HLB固相萃取柱净化。从SPE净化柱所得淋出液,以WatersXBridge C₁₈色谱柱（2.1 mm×150 mm,3.5μm）为固定相分离,以不同体积比的甲醇和氨水（0.1+99.9）溶液为流动相梯度洗脱,串联质谱进行测定。采用电喷雾负离子模式多反应监测,内标法定量。壬基苯酚的线性范围为10～500μg·L^-1,测定下限（10S/N）为0.2 mg·kg。方法用于分析4种类型化妆品样品,回收率在83.1%～103.0%之间,相对标准偏差（n=6）在2.75%～9.24%之间。     

高效液相色谱-串联质谱法测定工业废水中尼古丁含量

通过采用液相色谱-电喷雾串联质谱法测定工业废水中尼古丁的方式,从排污口取得的废水,过滤后采用反相C18色谱柱(150mm×4.6mm,5μm)分离,以甲醇-水(95+5)溶液为流动相,电喷雾串联质谱正离子模式下监测,测定尼古丁特征离子碎片m/z 130.1。结果发现:方法的线性范围为0.80～80.0μg.L-1,检出限(3S/N)为0.05μg.L-1,加标回收率为96.0%～97.9%。     

固相萃取纯化-高效液相色谱-串联质谱法测定尿液中痕量雷公藤红素

提出了尿液中雷公藤红素的高效液相色谱-串联质谱测定方法。尿液样品经Waters Oasis HLB固相萃取柱富集、净化后,以XDB C18反相色谱柱(150 mm×4.6 mm,5μm)为分离柱,以0.5 g.L-1乙酸-乙腈(25+75)混合溶液为流动相,以氢化可的松为内标,采用负离子模式大气压化学电离源在多反应监测模式下进行检测,雷公藤红素和内标的定量离子对分别为m/z449/405和m/z419/329。线性范围为0.2~50.0μg.L-1,检出限(3S/N)为0.07μg.L-1。日内精密度(n=6)和日间精密度(n=15)分别小于9.3%和11.4%。     

超高效液相色谱-串联质谱法快速测定吸烟者尿液中尼古丁和可替宁

吸烟者尿液样品用自主研究开发设计的前处理萃取瓶处理,采用超高效液相色谱-串联质谱法快速测定萃取液中尼古丁和可替宁的含量。以Waters ACQUITY UPLC BEHHILIC色谱柱(50mm×2.1mm,1.7μm)为固定相,以含0.1%(质量分数)氨水的甲醇(6+4)溶液为流动相,串联质谱中采用正离子模式监测。以D4-尼古丁和D3-可替宁为内标物,尼古丁和可替宁的线性范围均为20.0～2 000μg·L~(-1),检出限(3S/N)依次为5.7,3.7μg·L~(-1)。在2.0,4.0,8.0μg等3个浓度水平进行加标回收试验,回收率为93.6%～112%,测定值的日内相对标准偏差(n=7)为2.9%～3.4%,日间相对标准偏差(n=7)为3.2%～3.6%。     

高效液相色谱法测定食品添加剂中水杨酸

提出了高效液相色谱法测定食品添加剂中水杨酸含量的方法。样品采用含0.1%(体积分数)甲酸的甲醇-水(9+1)混合溶剂溶解,超声提取后经0.22μm滤膜过滤,滤液供高效液相色谱荧光仪测定。采用ZORBAX SB-C18色谱柱(4.6mm×250mm,3.5μm)分离,用不同配比的(A)甲酸-乙腈(0.1+99.9)和(B)甲酸-水(0.1+99.9)的混合溶液为流动相梯度洗脱,在激发波长为290nm、发射波长为400nm处检测。水杨酸的质量浓度在41.60～1 664μg·L-1范围内与其对应的峰面积呈线性关系,检出限(3S/N)为1.55μg·L-1,方法的回收率在90.4%～101.7%。     

固相萃取净化/超高效液相色谱-串联质谱法测定养殖环境中地西泮及其代谢物

建立了固相萃取净化/超高效液相色谱-串联质谱(SPE/UPLC-MS/MS)同时测定养殖水和沉积物样品中地西泮及其3种代谢物的分析方法。水样经0.45μm玻璃纤维膜过滤,沉积物采用1%氨水-乙酸乙酯提取后,均通过混合型阳离子交换固相萃取(MCX SPE)柱富集净化。目标物用5%氨水-乙腈溶液洗脱后吹干,1 mL 40%乙腈水溶液溶解残渣,UPLC-MS/MS测定。经Phenomenex Kinetex C₁₈(100 mm×2.1 mm,1.7μm)色谱柱分离,乙腈和0.1%甲酸水溶液为流动相进行梯度洗脱。采用电喷雾正离子电离,多反应监测(MRM)模式下测定,内标法定量。4种目标物在0.1～100μg/L范围内的线性关系良好,相关系数(r²)大于0.999。水体和沉积物中的方法检出限分别为1.0～2.0 ng/L和0.02～0.05μg/kg,定量下限分别为2.0～5.0 ng/L和0.05～0.1μg/kg;平均加标回收率为90.2%～115%,相对标准偏差(RSD,n=6)为2.1%～9.6%。该方法灵敏度高,实用性强,可满足养殖环境中地...     

高效液相色谱法测定化妆品中黄芩甙

采用高效液相色谱法测定化妆品中黄芩甙含量。样品经乙醇-水(75+25)溶液萃取,用ZORBAX SB C18色谱柱(4.6 mm×25 cm,5μm)分离,用乙腈与磷酸(0.1+99.9)溶液以体积比22比78组成的混合溶液为流动相进行洗脱,在波长276 nm处检测。黄芩甙的质量浓度在100.0 mg.L-1以内与其峰面积呈线性关系,方法的检出限(3S/N)为4.5 mg.kg-1。方法用于化妆品中黄芩甙的测定,加标回收率在76.8%～104.9%之间。     

Rapid liquid chromatography-tandem mass spectrometry method for quantification of ziprasidone in human plasma

A liquid chromatography-tandem mass spectrometry (LC-MS/MS) method for the determination of ziprasidone (ZIP) in human plasma was developed. ZIP and N-methyl ziprasidone as internal standard (IS) were extracted from alkalinized plasma using tert- butyl methyl ether. Separation was performed isocratically on a C8 column with 90% acetonitrile containing 2 mmol/L ammonium acetate as a mobile phase with a total run time of 2.5 min. MS/MS transitions of m/z 413 --> 194 and m/z 427 --> 177 of the analyte and internal standard were used for quantification. Confirmatory ions of m/z 413 --> 177 and m/z 427 --> 180 were collected as well. The calibration curve based on peak-area ratio was linear up to at least 200 ng/mL with a detection limit of 0.1 ng/mL. The method showed satisfactory reproducibility with a coefficient of variation of less than 5%. The method was successfully applied to the analysis of ZIP in spiked human plasma.     

Determination of Penicillium griseofulvum‐oriented pyripyropene A,a selective inhibitor of acyl‐coenzyme A:cholesterol acyltransferase 2, in mouse plasma using liquid chromatography–tandem mass spectrometry and its application to pharmacokinetic studies

In this study, we developed a method for the determination of Penicillium griseofulvum‐oriented pyripyropene A (PPPA), a selective inhibitor of acyl‐coenzyme A:cholesterol acyltransferase 2, in mouse and human plasma and validated it using liquid chromatography–tandem mass spectrometry. Pyripyropene A (PPPA) and an internal standard, carbamazepine, were separated using a Xterra MS C18 column with a mixture of acetonitrile and 0.1% formic acid as the mobile phase. The ion transitions monitored in positive‐ion mode [M + H]⁺ of multiple‐reaction monitoring (MRM) were m/z 148.0 from m/z 584.0 for PPPA and m/z 194.0 from m/z 237.0 for the internal standard. The detector response was specific and linear for PPPA at concentrations within the range from 1 to 5,000 ng/mL. The intra?/inter‐day precision and accuracy of the method was acceptable by the criteria for assay validation. The matrix effects of PPPA ranged from 97.6 to 104.2% and from 93.3 to 105.3% in post‐preparative mouse and human plasma samples, respectively. PPPA was also stable under various processing and/or handling conditions. Finally, PPPA concentrations in the mouse plasma samples could be measured after intravenous, intraperitoneal, or oral administration of PPPA, suggesting that the assay is useful for pharmacokinetic studies on mice and applicable to human studies.     

固相萃取-气相色谱-质谱联用检测地沟油中胆固醇

建立了固相萃取-气相色谱-质谱联用(SPE-GC-MS)检测地沟油样品中胆固醇的分析方法。样品用硅胶固相萃取小柱前处理净化,先用20 mL含0.6%乙醚的正己烷溶液淋洗,再用10 mL含15%乙醚的正己烷溶液洗脱,胆固醇萃取率达97%。净化后的样品用配备电子轰击离子源的气相色谱-质谱联用仪进行测定,以保留时间和特征碎片离子定性,在选择离子监测模式下用外标法定量,选择离子为m/z 213、275、301、368、386,目标离子为m/z 386,参考离子为m/z 213和275。不同加标水平下的加标回收率为91.7%～101%,相对标准偏差(RSD)小于6%,检出限为0.01 mg/L。胆固醇质量浓度在0.24~6.0 mg/L范围内有良好的线性关系(相关系数为0.9996)。该法可精确检测油脂中胆固醇的含量,检测结果可作为判断其中是否掺有地沟油的依据之一。     

High-performance liquid chromatography/tandem mass spectrometry method for the determination of arbidol in human plasma

An HPLC/MS/MS method for the determination of arbidol in human plasma was developed. Arbidol and internal standard (loratadine) were extracted from alkaline plasma with tert-butyl methyl ether and analyzed on a Zorbax SB C18 column (30 x 2.1 mm id, 3.5 microm particle size). The detection was by monitoring arbidol at m/z 479.1 --> 434.1 and the internal standard at m/z 383.2 --> 337.2. The method was validated according to U.S. Food and Drug Administration guidelines. The calibration curve was linear over the range of 0.5-500 ng/mL using a 100 microL sample volume. The intraday and interday precisions were less than 6.5%, and acceptable values were obtained for accuracy, recovery, and sensitivity. The developed method was selective, simple, sensitive, and easily applicable.     

Rapid and highly sensitive liquid chromatography/electrospray ionization tandem mass spectrometry method for the quantitation of buspirone in human plasma: application to a pharmacokinetic study

A rapid and sensitive method for the quantitation of buspirone in human plasma by liquid chromatography/electrospray ionization tandem mass spectrometry (LC/ESI-MS/MS) was developed. Plasma samples were treated by liquid-liquid extraction with methyl tert-butyl ether (MTBE). The chromatographic separation was performed isocratically on a reversed-phase Shiseido C18 column (50 mm x 2.0 mm, 3 microm) with a mobile phase of acetonitrile/0.1% acetic acid (1:1, v/v). The acquisition was performed in multiple reaction monitoring (MRM) mode, monitoring the transitions m/z 386 --> 122 for buspirone and m/z 409 --> 238 for amlodipine (the internal standard). The method was validated to determine its specificity, recovery, limit of quantitation, accuracy and precision. The lower limit of quantitation was 0.02 ng/mL with a relative standard deviation of less than 10%. The present method provides an accurate, precise and sensitive tool for buspirone and was successfully applied to a pharmacokinetic study in eight subjects.     

Determination of M+4 stable isotope labeled cortisone and cortisol in human plasma by microElution solid-phase extraction and liquid chromatography/tandem mass spectrometry

A sensitive microElution solid-phase extraction (SPE) liquid chromatography/tandem mass spectrometry (LC/MS/MS) method has been developed and validated for the determination of M+4 stable isotope labeled cortisone and cortisol in human plasma. In this method, M+4 cortisone and M+4 cortisol were extracted from 0.3 mL of human plasma samples using a Waters Oasis HLB 96-well microElution SPE plate using 70 microL methanol as the elution solvent, and chromatographed on a Waters Symmetry C18 column (4.6 x 50 mm, 3.5 microm). M+9 cortisone and M+9 cortisol were used as the internal standards. A PE Sciex API 4000 tandem mass spectrometer interfaced with the liquid chromatograph via a turboionspray source was used for mass analysis and detection. The selected reaction monitoring (SRM) of precursor --> product ion transitions were monitored at m/z 365.2 [M+H](+) --> 167.0 and at m/z 367.3 [M+H](+) --> 125.1 for M+4 cortisone and M+4 cortisol, respectively. The lower limit of quantitation was 0.1 ng mL(-1) and the linear calibration range was from 0.1 to 100 ng mL(-1) for both analytes. This method demonstrated to be very reproducible and reliable.     

Quantification of zolpidem in human plasma by liquid chromatography-electrospray ionization tandem mass spectrometry

A simple and robust method for quantification of zolpidem in human plasma has been established using liquid chromatography-electrospray ionization tandem mass spectrometry (LC-ESI MS/MS). Es-citalopram was used as an internal standard. Zolpidem and internal standard in plasma sample were extracted using solid-phase extraction cartridges (Oasis HLB, 1 cm3/30 mg). The samples were injected into a C8 reversed-phase column and the mobile phase used was acetonitrile-ammonium acetate (pH 4.6; 10 mm) (80:20, v/v) at a flow rate of 0.7 mL/min. Using MS/MS in the selected reaction-monitoring (SRM) mode, zolpidem and Es-citalopram were detected without any interference from human plasma matrix. Zolpidem produced a protonated precursor ion ([M+H]+) at m/z 308.1 and a corresponding product ion at m/z 235.1. The internal standard produced a protonated precursor ion ([M+H]+) at m/z 325.1 and a corresponding product ion at m/z 262.1. Detection of zolpidem in human plasma by the LC-ESI MS/MS method was accurate and precise with a quantification limit of 2.5 ng/mL. The proposed method was validated in the linear range 2.5-300 ng/mL. Reproducibility, recovery and stability of the method were evaluated. The method has been successfully applied to bioequivalence studies of zolpidem.     

Determination and pharmacokinetics of manidipine in human plasma by HPLC/ESIMS

A sensitive HPLC/ESIMS method was established for the determination of manidipine in human plasma and pharmacokinetics study. After basified plasma with ammonia, manidipine and the internal standard (IS) (felodipine) were extracted with n-hexane and separated on a Hypersil ODS2 column with a mobile phase of methanol-5 mm ammonium acetate solution containing 0.1% acetic acid (85:15, v/v). MS determination was performed by electrospray ionization in the selected ion monitoring mode. Manidipine was monitored at m/z 611.4 and IS at m/z 384. The assay had a calibration range from 0.2 to 20 ng/mL and a lower limit of quantification of 0.1 ng/mL. The method has been successfully applied to the pharmacokinetic study in healthy volunteers.     

Tenax采样管富集气相色谱-质谱法测定空气中的痕量酚类化合物

建立了Tenax采样管富集气相色谱-质谱测定空气中痕量酚类化合物的方法。用Tenax采样管吸附环境空气中的痕量酚类化合物,用甲醇淋洗解吸酚类化合物,洗脱液加入萘-D8作为内标,利用气相色谱-选择离子监测质谱(GC-MS/SIM)进行检测,内标法定量。该方法定性、定量准确,线性响应良好,回归曲线的线性相关系数均大于0.999,平均回收率为92.4%～102%,测定干扰小,检测灵敏度高,按采样10 L计算,空气中最低检测浓度可达0.001 mg/m3。用于实际样品测定,完全能满足环境空气中痕量酚类化合物监测的要求。     

固相萃取-气相色谱-质谱法测定利多卡因代谢物单乙基甘氨酰二甲苯胺的血药浓度

建立了固相萃取-气相色谱-质谱(GC-MS)测定利多卡因代谢物单乙基甘氨酰二甲苯胺(MEGX)血药浓度的方法。血清中的MEGX采用固相萃取小柱萃取、GC-MS测定。色谱条件为：HP-5MS毛细管柱(15 m×0.25 mm×0.1 μm),初始柱温100 ℃,保持1 min后以40 ℃/min速率升温至200 ℃,保持0.5 min;进样口温度250 ℃;分流进样,分流比1∶1,进样量2 μL;载气为氦气,流量为1.0 mL/min。质谱条件为:离子源温度230 ℃,电子轰击电离,电子能量70 eV,选择离子检测（m/z 58(MEGX)、 m/z 86(普鲁卡因,内标)）。结果表明,MEGX在血清中的浓度在1.562～25 ng/mL范围内的线性关系良好,相关系数0.9981,最低检测限为0.5 ng/mL,不同浓度MEGX的萃取回收率在80.1%～85.7%之间。实验证明该方法快速、准确,选择性好,灵敏度高,适合用于血清中微量MEGX的测定。