皮革及纺织品中烷基酚与烷基酚聚氧乙烯醚的液相色谱-质谱测定

建立了液相色谱-质谱法测定皮革及纺织品中辛基酚(OP)、壬基酚(NP)、辛基酚聚氧乙烯醚(OPEO)及壬基酚聚氧乙烯醚(NPEO)的分析方法。样品经超声波振荡萃取,C18反相色谱柱进行分离,甲醇-水为流动相,离子源为ESI。OP和NP采用负离子模式,定量离子分别为m/z205、219;OPEO和NPEO采用正离子模式,定量离子分别为m/z229+44nEO和m/z243+44nEO(nEO=3~16)。在优化实验条件下,方法的定量下限为0.25~2.5 mg/kg,样品加标回收率为92%~107%,相对标准偏差为5.3%~9.5%(50 mg/kg,n=6)。方法简单、快速、灵敏度高,可满足欧盟等地区对皮革及纺织品中OP、NP、OPEO、NPEO的测定要求。     

超声萃取结合超高效液相色谱法测定皮革中10种防霉剂

建立了皮革样品中10种防霉剂(氨基苯磺酰胺、苯并咪唑、BIT、MBT、IPBC、PCMC、水杨酰苯胺、OPP、TCMTB和OIT)的超高效液相色谱(UPLC)检测方法。样品经甲醇超声萃取,T3色谱柱分离后,甲醇和0.1%甲酸水为流动相梯度洗脱,二极管阵列检测器测定。在优化条件下,10种防霉剂在一定的浓度范围内线性关系良好,相关系数(r~2)均不小于0.999 3,除IPBC的方法定量下限(S/N=10)为190.0 mg/kg外,其余9种防霉剂的方法定量下限为4.0~8.0 mg/kg,平均回收率为81.3%~104.9%,相对标准偏差(RSD,n=6)为4.7%~11.2%。该方法前处理简单、分离效果好,适用于皮革样品中10种防霉剂的同时测定。     

液相色谱-串联质谱法测定淀粉及其制品中的顺丁烯二酸与顺丁烯二酸酐总含量

建立了测定淀粉及其制品中顺丁烯二酸和顺丁烯二酸酐总含量的高效液相色谱-串联质谱(HPLC-MS/MS)方法。样品经50%(v/v)甲醇提取、碱性条件下水解后,采用液相色谱-串联质谱对其进行分析,外标法定量。质谱分析采用电喷雾电离,负离子扫描,多反应监测模式。实验表明样品无明显的基质效应,添加水平为0.5~1 000mg/kg时,回收率为80.2%~115.3%,相对标准偏差(n=6)小于12%;方法检出限(LOD)为0.1 mg/kg,定量限(LOQ)为0.5 mg/kg。该方法提取效果好,具有良好的灵敏度、回收率和重复性,已被成功用于实际样品中顺丁烯二酸和顺丁烯二酸酐总含量的测定。     

气相色谱-串联质谱法测定皮革和纺织品中的富马酸二甲酯

建立了气相色谱-串联质谱(GC-MS/MS)准确、快速测定皮革和纺织品中富马酸二甲酯(DMF)的分析方法。样品经乙酸乙酯提取、浓缩及固相萃取柱净化处理,通过VF-5ms色谱柱分离、串联质谱对DMF进行定性和定量分析。实验结果表明: 优化样品预处理条件、固相萃取条件、质谱分析条件后,该方法可进一步消除杂质干扰,结果准确可靠,灵敏度、精密度、线性关系良好,回收率较高。3种浓度水平的加标回收率(n=6)保持在84%～93%之间,相对标准偏差小于7.2%;DMF在8种皮革和纺织品中的检出限 (S/N=3)为0.012～0.039 mg/kg, 0.05～100 mg/L质量浓度范围内线性相关系数为0.9990,适用于皮革和纺织品中DMF的日常检测。     

液相色谱-串联质谱法同时测定纺织品和食品包装材料中的壬基酚、辛基酚和双酚A

建立了纺织品和食品包装材料中壬基酚、辛基酚和双酚A的液相色谱-串联质谱分析方法。不同类型的纺织品和食品包装材料样品采用加速溶剂萃取法,以无水乙醇为提取剂,在10.3 MPa和120℃下静态循环提取2次,提取液经Supelclean Envi-Carb石墨化碳黑固相萃取柱净化,收集甲醇-二氯甲烷(1∶4,V/V)洗脱液,采用Waters XBridge C18色谱柱,以甲醇-0.1%氨水溶液为流动相,梯度洗脱分离后,在LC/MS/MS多反应监测模式下进行定性与定量分析。壬基酚、辛基酚和双酚A的方法检出限为0.5μg/kg,在0.5～10μg/kg的3个添加水平范围内,纺织品样品的平均回收率为86.9%～92.5%,相对标准偏差均小于9.1%;食品包装材料样品的平均回收率为87.8%～93.0%,相对标准偏差均小于8.8%。本方法准确、快速、灵敏度高,可用于纺织品和食品包装材料的实际检验。     

高效液相色谱法测定食品中丙二醛

采用高效液相色谱法测定各类食品样品中的丙二醛含量,建立了对猪肉、方便面、食用油、大白菜、婴儿配方奶粉和饼干等不同食品基质均适用的分析方法,采用样品加标的方法验证了方法的可行性。样品采用酸液恒温振荡提取,硫代巴比妥酸衍生提取液后,采用Agilent Eclipse XDB-C18色谱柱进行分离测定,以0.01 mol/L乙酸铵(A)-甲醇(B)(7+3,V/V)为流动相进行色谱等度分离,流速1.0 mL/min,柱温30℃,检测波长532nm。结果表明,丙二醛含量为0.125~2 mg/kg时线性良好,相关系数不小于0.9997。在0.1,1.0和2.5 mg/kg 3个添加水平下的回收率为61%~98%,日内精密度(相对标准偏差,RSD)小于8.3%,日间精密度小于9.2%,检测限为7.72μg/kg,方法稳定性良好。     

马铃薯中马来酰肼的高效液相色谱法测定

建立了马铃薯中马来酰肼的高效液相色谱(HPLC)检测方法.马铃薯样品经酸化甲醇提取,高速离心沉淀分离后,以甲醇-去离子水(体积比1:9,pH 2.7)为流动相,采用ZORBAX SB C18柱(250 mm×4.6 mm×5 μm)分离,在UV 205 nm检测,外标法定量.结果表明,马来酰肼提取液的线性范围为0.2 ～16.0 mg/L,回收率为82% ～94%,RSD均小于2%,马铃薯中马来酰肼的定量下限为1.0 mg/kg.     

超高效液相色谱-线性离子阱/静电场轨道阱高分辨质谱法测定纺织品中的游离态致癌芳香胺

建立了超高效液相色谱-线性离子阱/静电场轨道阱高分辨质谱(UPLC-LTQ/Orbitrap MS)同时测定纺织品中24种游离态致癌芳香胺的方法。样品经二氯甲烷超声提取并稀释后,用ZORBAX SB-C18色谱柱(150 mm×2.1mm,5μm)分离,以0.1%甲酸水溶液和甲醇为流动相,电喷雾正离子(ESI+)模式电离,以准分子离子峰的精确质量数和保留时间定性,以提取的色谱图峰面积定量。在0.5~500μg/L范围内,24种芳香胺的线性相关系数(R2)大于0.99,样品加标回收率为87.8%~105.6%,相对标准偏差为1.6%~3.4%。方法检出限为0.5~1μg/kg。应用本方法检测山东地区进出口含氨纶纺织品样品14个,在5个样品中检出游离态芳香胺4,4′-二氨基二苯甲烷,含量范围为0.21~25.6 mg/kg。     

超声提取-气相色谱/质谱法测定皮革及纺织品中18种多环芳烃

采用超声波萃取技术对样品进行提取,气相色谱联用质谱(GC-MS)选择离子监测(SIM)模式采集数据,建立了皮革及纺织品中18种多环芳烃(PAHs)的分析方法。对色谱、质谱分析条件以及样品前处理条件进行研究与优化。在最优条件下,18种PAHs浓度在一定范围内与其峰面积呈现良好的线性关系,相关系数(R²)为0.9991~0.9998,检出限为0.003~0.02 mg/kg,定量限为0.01~0.06 mg/kg,不同材质产品的3个不同加标水平下的平均加标回收率为80.1%~110.1%,相对标准偏差(RSDs)为0.1%~9.4%(n=7)。该方法可应用于皮革及纺织品等不同材质产品中PAHs的检测分析。     

液相色谱-串联质谱法测定饮料中邻苯二甲酸二(2-乙基)己酯和邻苯二甲酸二异壬酯

建立了饮料中邻苯二甲酸二(2-乙基)己酯(DEHP)和邻苯二甲酸二异壬酯(DINP)残留的液相色谱-串联质谱(LC-MS/MS)检测方法。2.0 g样品经8 mL甲醇振荡提取、定容、离心,取上清液过滤,采用LC-MS/MS电喷雾电离,多反应监测(MRM)模式对样品进行分析。DEHP在浓度范围为2～200μg/L,DINP在10～1000μg/L内线性良好,相关系数均大于0.998。实验表明:样品无明显的基质效应。样品中添加0.01～5 mg/kg的DEHP和DINP,其回收率为86.2%～111.6%;相对标准偏差(n=6)小于11%;DEHP检出限为0.008 mg/kg,定量限为0.01 mg/kg;DINP检出限为0.01 mg/kg,定量限为0.05 mg/kg。本方法提取效果好,具有良好的灵敏度、回收率和重复性,被成功用于实际饮料样品中DEHP和DINP的测定。     

凝胶渗透色谱净化-超高效液相色谱-串联质谱法测定皮革制品中7种尼泊金酯类防腐剂

利用超高效液相色谱-串联质谱(UPLC-MS/MS)结合凝胶渗透色谱(GPC)技术,建立了一种快速分离和测定皮革制品中7种尼泊金酯类防腐剂的分析方法。样品经超声提取、浓缩、GPC净化,甲醇-水溶液(1:1, v/v)溶解,采用Acquity UPLCBEH C18柱(50 mm×2.1 mm, 1.7 μm)分离,以甲醇和水为流动相,梯度洗脱,电喷雾负离子模式电离,采用多反应监测模式检测和外标法定量。该方法在0.1～1.0 mg/L范围内线性关系良好(r＞0.99);在添加量为0.5～3.0 mg/kg时,平均回收率为(79.44±5.67)%～(98.07±9.50)%,相对标准偏差(RSD)为4.24%～14.00%;方法的检出限(LOD)为4～12 μg/kg,定量限(LOQ)为13.2～39.6 μg/kg。该方法操作简便、快捷、灵敏、准确,适合皮革中多种尼泊金酯类防腐剂的确证和定量测定。     

液相色谱串联质谱测定纺织品中的四溴双酚A

采用固相萃取/超快速液相色谱-串联质谱技术(SPE/UFLC-MS/MS)建立了纺织品中四溴双酚A的测定方法。样品经甲醇超声提取,C_(18)-SPE净化后分析,在串联质谱电喷雾(ESI)离子多反应监测(MRM)模式下检测,以保留时间以及特征离子对进行定性、定量分析。实验结果表明,四溴双酚A在1.0~100.0μg/L范围内呈良好的线性关系。称样量为1.0 g时,方法的定量下限为1.0μg/kg。平均回收率为80.9%~95.3%,相对标准偏差(RSDs)为2.3%~5.9%。所建方法快速、准确、灵敏,可用于纺织中四溴双酚A的分析测定。     

Simultaneous quantification of 25 active constituents in the total flavonoids extract from Herba Desmodii Styracifolii by high‐performance liquid chromatography with electrospray ionization tandem mass spectrometry

A sensitive and selective high‐performance liquid chromatography coupled with electrospray ionization tandem mass spectrometry method has been developed and validated for the simultaneous determination of 25 active constituents, including 21 flavonoids and four phenolic acids in the total flavonoids extract from Herba Desmodii Styracifolii for the first time. Among the 25 compounds, seven compounds including caffeic acid, acacetin, genistein, genistin, diosmetin, diosmin and hesperidin were identified and quantified for the first time in Herba Desmodii Styracifolii. Chromatographic separation was accomplished on a ZORBAX SB‐C₁₈ (250 mm×4.6 mm, 5.0 μm) column using gradient elution of methanol and 0.1‰ acetic acid v/v at a flow rate of 1.0 mL/min. The identification and quantification of the analytes were achieved using negative electrospray ionization mass spectrometry in multiple‐reaction monitoring mode. The method was fully validated in terms of limits of detection and quantification, linearity, precision and accuracy. The results indicated that the developed method is simple, rapid, specific and reliable. Furthermore, the developed method was successfully applied to quantify the 25 active components in six batches of total flavonoids extract from Herba Desmodii Styracifolii.     

Determination of oxatomide in human plasma by high-performance liquid chromatography-electrospray ionization mass spectrometry

A rapid, sensitive and specific high-performance liquid chromatography-electrospray ionization mass spectrometry (LC-ESI-MS) method has been developed and validated for the determination of oxatomide in human plasma. Flunarizine hydrochloride was employed as the internal standard (IS). The analytes were chromatographically separated on a Shimadzu Shim-pack VP-ODS C18 column (250 x 2.0 mm i.d.) with a mobile phase consisting of methanol and aqueous ammonium acetate solution (10 mm, pH 4.0; 85:15, v/v). Detection was performed on a single quadrupole mass spectrometer using an electrospray ionization interface with the selected-ion monitoring (SIM) mode. The method showed excellent linearity (r = 0.9995) over the concentration range of 0.5-500 ng/mL with good accuracy and precision. The intra- and inter-batch precisions were within 10% relative standard deviation. The recoveries were more than 90%. The validated method was successfully applied to a preliminary pharmacokinetic study of oxatomide in Chinese healthy male volunteers.     

高效液相色谱-电喷雾串联质谱法快速测定纺织品中苯氧羧酸类除草剂残留量

建立了纺织品中7种苯氧羧酸类除草剂的高效液相色谱-电喷雾串联质谱(LC-ESI-MS/MS)快速检测方法.样品经甲酸酸化的丙酮溶液超声提取两次,无需其它净化过程.液相色谱使用C18反相色谱柱,流动相为醋酸铵水溶液和甲醇,在梯度条件下分析.在选择反应检测(SRM)负离子模式下进行质谱信号采集,采用两对同位素离子对进行定性和定量分析.选取3种有代表性的纺织品进行方法检出限(LOD)、定量限(LOQ)、线性、回收率和精密度的验证.方法的LOQ为 0.9～2.4 μg/kg; 回收率为85%～106%; 相对标准偏差为2%～11%.本方法简便、有效、可靠、灵敏,能够满足国际生态纺织品标准(Oeko-Tex Standard 100)的限量要求,适用于纺织品中苯氧羧酸类除草剂的日常检测及确证.     

Rapid separation and identification of phenolic and diterpenoid constituents from Radix Salvia miltiorrhizae by high-performance liquid chromatography diode-array detection, electrospray ionization time-of-flight mass spectrometry and electrospray ionization quadrupole ion trap mass spectrometry

High-performance liquid chromatography-diode array detection (HPLC-DAD), electrospray ionization time-of-flight mass spectrometry (HPLC-ESI-TOF-MS) and electrospray ionization quadrupole ion trap mass spectrometry (HPLC-ESI-MSn) were used for the isolation, identification and structural analysis of water-soluble phenolic and nonpolar diterpenoid constituents in Dan-shen (Radix Salvia miltiorrhizae) which was prepared by sonication in 70% methanol. Mass spectra were obtained by ESI-TOF-MS and electrospray ionization quadrupole ion trap mass spectrometry (ESI-QIT-MS). A formula database of known constituents in Dan-shen was established and most constituents were rapidly identified by HPLC-DAD/ESI-TOF-MS by matching their accurate molecular masses with the formulae of the compounds in the database. Compounds with the same molecular formula could not be differentiated by TOF-MS; however, QIT-MS could differentiate those compounds and elucidate their structures based on their characteristic fragmentation. HPLC-DAD, HPLC/ESI-TOF-MS and HPLC/ESI-MSn provided complementary information for the identification of the constituents in Dan-shen. Forty constituents were identified in 30 min based on their positive and negative ion ESI mass spectra and liquid chromatographic information. Thus the method described is useful for the rapid analysis of multiple constituents in Dan-shen.     

超高效液相色谱-电喷雾串联质谱法测定动物饲料中的大环内酯类和林可胺类抗生素

建立了动物饲料中竹桃霉素、红霉素、吉他霉素、交沙霉素、罗红霉素、泰乐菌素6种大环内酯和林可霉素、克林霉素2种林可胺抗生素的超高效液相色谱-电喷雾串联质谱(UPLC-ESI-MS/MS)检测方法。饲料样品采用甲醇提取,Oasis HLB固相萃取柱富集净化,Waters Acquity UPLC BEH C18色谱柱分离,以0.1%甲酸和乙腈为流动相进行梯度洗脱,流速为0.3 mL/min,正离子模式扫描,多反应监测模式检测,外标法定量。实验结果表明,8种药物在1～100 μg/L范围内具有良好的线性关系。在空白饲料样品中分别添加1、10和100 μg/kg 3个加标水平的8种药物,其平均回收率为68.6%～95.2%,相对标准偏差(RSD)为4.9%～11.8%,定量限均为1 μg/kg。结果表明,该方法简便快速、灵敏度高,适用于动物饲料中大环内酯类和林可胺类抗生素的同时检测。     

Determination of HX0969w in rabbit whole blood by liquid chromatography-tandem mass spectrometry and its application in a pharmacokinetic study

HX0969w is a novel carboxylate ester prodrug of propofol. After intravenous administration of HX0969w, the compound is rapidly hydrolyzed to its active metabolite propofol. A liquid chromatography-tandem mass spectrometry (LC-MS/MS) method with electrospray ionization has been developed for determination of HX0969w in rabbit whole blood. Protein precipitation with methanol was used for sample preparation and 7-hydroxycoumarin served as internal standard. The standard curve ranged from 50.1 to 15,030 ng mL(-1). The lower limit of quantification (LLOQ) for HX0969w was 50.1 ng mL(-1). The intra- and inter-day accuracies were within ± 10% and precisions were below 5.52%. The method was successfully applied to samples from a rabbit pharmacokinetic study.     

丹磺酰氯柱前衍生-超高效液相色谱-串联质谱法测定人体尿样中的环己胺

建立丹磺酰氯柱前衍生-超高效液相色谱-串联质谱法测定人体尿样中环己胺的方法。冷冻样品经解冻、离心后,用丹磺酰氯衍生,固相萃取小柱净化。目标化合物采用 Waters ACQUITY CSHTM C18色谱柱(50 mm×2.1 mm,1.7μm)分离,以甲醇和0.002 mol/L乙酸铵溶液为流动相梯度洗脱,采用电喷雾离子源电离、正离子多反应监测模式质谱检测。环己胺在2.5~200μg/L浓度范围内有较好的线性关系,相关系数大于0.999,回收率为98.7%~102.3%,精密度为3.1%~5.2%,检出限和定量限分别为1.0和3.0μg/L。结果表明,本方法操作简单、准确可靠,可适用于人体尿液中环己胺的定量分析。应用本方法测定200份学生尿液样品,环己胺检出率为34.5%。     

Determination of chikusetsusaponin V and chikusetsusaponin IV in rat plasma by liquid chromatography–mass spectrometry and its application to a preliminary pharmacokinetic study

A sensitive liquid chromatography–electrospray ionization–mass spectrometry method has been developed and validated for determination of two major bioactive saponins in rat plasma after oral administration of saponins extracted from Rhizoma Panacis Japonici, including chikusetsusaponin V and chikusetsusaponin IV for the first time. Akebia saponin D was used as the internal standard (IS). Plasma samples were prepared by protein precipitation with methanol. A Phenomenex C₁₈ column (150 × 4.6 mm, 4 µm) was used as the analytical column with a mobile phase of acetonitrile and 0.05% aqueous formic acid. Mass spectrometric detection was achieved by single quadrupole mass spectrometer equipped with an electrospray ionization interface operating in negative ionization mode. Calibration curves showed good linearity over the concentration range of 5–500 ng/mL for the two analytes in rat plasma. The lower limit of quantification was 5 ng/mL. The intra‐ and inter‐batch precisions were within 10.3% and accuracy ranged from ?3.9 to 5.4%. The method was validated and successfully applied to the preliminary pharmacokinetic study of chikusetsusaponin V and chikusetsusaponin IV in rat plasma after oral administration of saponins extracted from Rhizoma Panacis Japonici. Copyright © 2013 John Wiley & Sons, Ltd.