液相色谱-串联质谱法测定饲料中的游离棉酚

建立了高效液相色谱-串联质谱法(LC-MS/MS)定量测定饲料中棉酚残留的分析方法。待测物经丙酮-水(7∶3)混合溶液振荡提取,C18色谱柱(100 mm×2.1 mm,3.5μm)分离,以乙腈和0.1%甲酸为流动相进行梯度洗脱,串联质谱测定,外标法定量。方法的定量下限(S/N10)为1 mg/kg;棉酚在10~100μg/L质量浓度范围内,线性相关系数为0.993。以1、20、40 mg/kg浓度进行加标后测得平均回收率为83.8%~97.5%,相对标准偏差为1.3%~5.2%。该方法操作简单、回收率稳定,可用于饲料中棉酚残留的快速确证及定量分析。     

液相色谱-串联质谱法测定食用植物油中的棉酚

建立了食用植物油中棉酚的液相色谱-串联质谱（LC-MS/MS）分析方法。待测物经无水乙醇涡旋振荡提取,C18色谱柱分离,以乙腈和0.1%（v/v）甲酸水溶液为流动相进行梯度洗脱,LC-MS/MS测定,外标法定量。方法的测定低限（S/N>10）为1 mg/kg;在添加浓度为1、2和200 mg/kg水平下,棉酚的加标回收率为87.4%~100%,相对标准偏差为3.9%~12.2%。结果表明,本方法灵敏度高,测定结果准确,回收率稳定,可用于食用植物油中棉酚残留的确证检测。     

液相色谱串联质谱法测定水果中复硝酚钠残留量

以甲醇提取样品,采用超高效液相色谱串联质谱法(UPLC–MS/MS)测定水果中复硝酚钠的残留量。以甲醇–10 mmol/L乙酸铵水溶液(体积比为60∶40)为流动相,质谱采用电喷雾负离子MRM检测模式。对硝基苯酚钠和5-硝基愈创木酚钠的线性范围为0.05~2.00 mg/L,检出限为0.01 mg/kg,邻硝基苯酚钠的线性范围为2.5~100.0 mg/L,检出限为0.5 mg/kg,线性相关系数均大于0.995。实际样品中对硝基苯酚钠、邻硝基苯酚钠和5-硝基愈创木酚钠的加标回收率分别为83.0%~93.4%,81.0%~87.4%,83.0%~91.8%,测定结果的相对标准偏差小于7%(n=6)。该法操作简单、快捷,精密度、准确度高,适用于水果中复硝酚钠的残留分析。     

高效液相色谱法同时测定血清和尿中厚朴酚与和厚朴酚

 建立了大鼠服用厚朴提取物后的血清中及尿中厚朴酚与和厚朴酚的高效液相色谱测定法。色谱柱填料为SpherisorbC18,流动相为甲醇-水-冰醋酸(体积比为70∶30∶1),UV检测波长为294nm,灵敏度0.005AUFS。样品用甲醇沉淀蛋白,上清液酸化后用乙酸乙酯-乙醚萃取,然后测定其中的药物浓度。血清和尿中的药物浓度与峰面积的线性关系良好,线性范围分别为0.05～2mg/L(厚朴酚)、0.025～1mg/L(和厚朴酚);精密度和重现性良好。血清中厚朴酚与和厚朴酚的平均加样回收率分别为95.6%(RSD=3.85%)和93.8%(RSD=3.95%),尿中分别为96.0%(RSD=3.83%)和94.9%(RSD=3.54%)。     

反相高效液相色谱法对秦岭21种蕨类植物中槲皮素与山柰酚含量的测定

运用反相高效液相色谱(RP/HPLC)法对21种蕨类植物中槲皮素、山柰酚的含量进行测定。使用Shimadzu C18(250 mm×4.6 mm,5μm)色谱柱,以甲醇-水溶液为流动相进行等度洗脱,流速1.0 mL/min,检测波长360 nm,进样量20μL,柱温28℃。各对照品的质量浓度与色谱峰面积线性关系良好,具有较好的精确度和重复性,槲皮素、山柰酚的加标回收率分别为93%和95%。采用该方法分别对采自秦岭的21种蕨类植物的地上和地下部分进行测定,地上部分有19种含槲皮素、15种含山柰酚,其中毡毛石韦中槲皮素含量最高(2.11 mg/g),蜈蚣草中山柰酚含量最高(19.80 mg/g);而地下部分除有边瓦韦、大瓦韦含槲皮素(含量分别为0.11、0.12 mg/g)外,其余根状茎中几乎没有这两种黄酮类化合物;表明槲皮素与山柰酚在蕨类植物的地上部分广泛存在。     

超高效液相色谱-串联质谱法同时测定食用油中痕量的δ-9-四氢大麻酚、大麻酚和大麻二酚

建立了超高效液相色谱-串联质谱(UPLC-MS/MS)同时测定食用油中δ-9-四氢大麻酚(THC)、大麻酚(CBN)和大麻二酚(CBD)的方法。目标分析物经甲醇提取、中性氧化铝固相萃取柱净化后,采用UPLC-MS/MS分离和检测。实验以氘代四氢大麻酚(THC-D3)为内标物,采用同位素内标法定量。在3个添加水平下,目标物的平均回收率为68.0%～101.6%,相对标准偏差为7.0%～20.1%。方法检出限为0.06～0.17μg/kg,定量限为0.20～0.52μg/kg。该方法能够满足食用油中痕量四氢大麻酚、大麻酚和大麻二酚检测的需要。     

高效液相色谱-内标法测定碘硝酚原料及其注射液中碘硝酚的含量

建立了碘硝酚的高效液相色谱(HPLC)-内标法检测方法。用甲醇将样品配制成测试浓度后过滤,经依利特Sino Chrom C_(18)(4.6 mm×200 mm,5μm)色谱分析柱进行色谱分离,流动相为0.02 mol/L磷酸二氢钾溶液(pH 2.6)-甲醇(30∶70),流速为1 mL/min,紫外检测波长为235 nm,柱温为30℃,内标物为硝氯酚,进样量为20μL。结果表明,碘硝酚的质量浓度在20~120 mg/L范围内呈线性关系,相关系数(r)为0.999 6;在3个不同浓度(64、80、96 mg/L)加标水平下,平均回收率为90.4%~98.2%,相对标准偏差(RSD)为0.18%~0.72%;检出限(LOD,S/N=3)为0.15 mg/L,定量下限(LOQ,S/N=10)为1.5 mg/L。该方法的精密度、稳定性以及重复性良好,且操作简便,结果准确,可用于碘硝酚原料药及注射液的含量测定。     

祛痘化妆品中苯海拉明的高效液相色谱检测及质谱确证

建立了祛痘化妆品中苯海拉明的高效液相色谱(HPLC)分析方法及液相色谱-串联质谱(LC-MS/MS)确证方法。水剂类和膏霜类祛痘化妆品样品分别采用适宜提取溶剂超声提取,提取液离心处理后,以HPLC测定。选用Waters XTerra MS C18色谱柱(250×4.6mm,5μm),以甲醇-10mmol/L碳酸氢铵缓冲溶液(体积比78∶22,氨水调节pH至10)为流动相,等度洗脱,流速1.0mL/min,检测波长218nm,外标法定量。阳性样品采用LC-MS/MS进行确证。苯海拉明的定量限为1.0mg/kg,在低、中、高添加水平的平均回收率为88.2%~105.0%,相对标准偏差在2.8%~7.9%之间。该方法简便、准确、灵敏度高,适用于祛痘化妆品中苯海拉明的测定。     

超高效液相色谱-串联质谱法同时测定食用油中痕量的δ-9-四氢大麻酚、大麻酚和大麻二酚

建立了超高效液相色谱-串联质谱(UPLC-MS/MS)同时测定食用油中δ-9-四氢大麻酚(THC)、大麻酚(CBN)和大麻二酚(CBD)的方法。目标分析物经甲醇提取、中性氧化铝固相萃取柱净化后,采用UPLC-MS/MS分离和检测。实验以氘代四氢大麻酚(THC-D3)为内标物,采用同位素内标法定量。在3个添加水平下,目标物的平均回收率为68.0%～101.6%,相对标准偏差为7.0%～20.1%。方法检出限为0.06～0.17 μg/kg,定量限为0.20～0.52 μg/kg。该方法能够满足食用油中痕量四氢大麻酚、大麻酚和大麻二酚检测的需要。     

高效液相色谱法测定化妆品中4种禁用醛酮化合物

建立了同时测定化妆品中4种禁用醛酮化合物(巴豆醛、苯乙酮、2,4-二羟基-3-甲基苯甲醛和2-亚戊基环己酮)的高效液相色谱(HPLC)分析方法。样品使用50%乙腈(体积比)溶液提取,经AQ-C18(4.6 mm×150 mm,5μm)色谱柱分离后,高效液相色谱/二极管阵列检测器检测,以保留时间和紫外吸收光谱定性,外标法定量,高效液相色谱-质谱/质谱法确证。结果表明,4种醛酮化合物在0.05~2.0 mg/L质量浓度范围内呈良好的线性关系,相关系数均不小于0.999 9;方法检出限和定量下限分别为0.5~1.0 mg/kg和1.5~3.0 mg/kg。样品加标回收率为89.0%~106.7%,相对标准偏差(RSDs,n=6)为2.0%~6.9%。该方法准确可靠,适用于化妆品中4种禁用醛酮化合物的测定。     

Simultaneous quantitative and qualitative analysis of bioactive phenols in Dendrobium aurantiacum var. denneanum by high-performance liquid chromatography coupled with mass spectrometry and diode array detection

A novel high-performance liquid chromatographic method with mass spectrometry and diode array detection method for the simultaneous qualitative and quantitative analysis of bioactive phenols was developed. In total, nine chemically diverse phenols including five bibenzyls, three phenanthrenes and a coumarin were unambiguously identified in Dendrobium aurantiacum var. denneanum by comparison with the available references or reported data according to their retention behaviors, UV spectra and fragmentations of ESI-MS. The contents of the four main phenolic compounds, moscatilin, gigantol, moscatin and coumarin, in D. aurantiacum var. denneanum from the wild and various cultivated populations were determined by HPLC-UV. The sample preparation involved a rapid and simple procedure based on solid-phase extraction using a C(18) reversed-phase cartridge. The quantitative analysis was performed on a Beckman Coulter ODS column (5 microm, 250 x 4.6 mm) using a linear gradient elution system of acetonitrile-0.5% formic acid. The method was validated for linearity, limits of detection (LOD) and quantification (LOQ), precision and accuracy. Good results were obtained with respect to the overall intra- and inter-day variations (RSD less than 3.22%) and the percentage recoveries (ranging from 90.50 to 99.22%). Notable differences in the contents of phenols were observed among different cultivated populations. The samples colleted in April and May (spring), or October and November (autumn) accumulated much higher contents of phenols than those collected in other seasons.     

Quality evaluation of Rhizoma Belamcandae (Belamcanda chinensis (L.) DC.) by using high-performance liquid chromatography coupled with diode array detector and mass spectrometry

A high-performance liquid chromatography coupled with diode array detector and mass spectrometry (HPLC-DAD-MS) method was developed to evaluate the quality of Rhizoma Belamcandae (Belamcanda chinensis (L.) DC.) through establishing chromatographic fingerprint and simultaneous determination of seven phenolic compounds. The analysis was achieved on an Alltima C(18) analytical column (250 mm x 4.6 mm i.d. 5 microm) using linear gradient elution of acetonitrile-0.1% trifluoroacetic acid. The correlation coefficients of similarity were determined from the HPLC fingerprints, and they shared a close similarity. By using an online APCI-MS/MS, twenty phenols were identified. In addition, seven of these phenols including mangiferin, 7-O-methylmangiferin, tectoridin, resveratrol, tectorigenin, irigenin and irisflorentin were quantified by the validated HPLC-DAD method. These phenols are considered to be major constituents in Rhizoma Belamcandae, and are generally regarded as the index for quality assessment of this herb. This developed method by having a combination of chromatographic fingerprint and quantification analysis could be applied to the quality control of Rhizoma Belamcandae.     

高效液相色谱-电喷雾离子阱质谱法测定红葡萄酒中酚类物质

建立了高效液相色谱-质谱联用(HPLC-MS)技术检测葡萄酒中酚类物质的方法,并评价其定量分析的准确性、线性、重复性和检出限,结果显示:16种酚类物质除芦丁和白藜芦醇糖苷外,平均加标回收率大于78%;相关系数R2>0.999,线性关系良好;保留时间和峰面积在日内(n=10)与日间(n=6)重复性的相对标准偏差(RSD)均分别低于2.0%和5.0%;检出限为0.05~1.0 mg/L。利用该方法对6个红葡萄酒中16种酚类物质进行了定性定量分析,其相对标准偏差(CV%)均小于5.0%,说明本方法简便、准确、灵敏、重现性好,可用于葡萄酒产品质量监控。     

Characterization and identification of multiple constituents in Yinhuang granules by high-performance liquid chromatography with diode-array and time-of-flight mass spectrometry detection

A fast high-performance liquid chromatography (HPLC) method with diode-array detection (DAD) and time-of-flight mass spectrometry (TOF/MS) has been developed for the analysis of multi-constituent in Yinhuang granules, a well-known combined herbal remedy prepared from the extract mixtures of Flos Lonicerae and Radix Scutellariae. The fast HPLC analysis was performed on an Agilent ZorBax SB-C(18) column (4.6×50 mm, 1.8 μm) and 0.2% aqueous formic acid and acetonitrile was the optimum mobile phase for gradient elution in 17 min, which is five times faster than the performance of conventional columns packed with 5.0 μm particles. With various fragmentor voltages in TOF/MS, accurate mass measurements (<5 ppm error) for molecular ions and characteristic fragment ions represented reliable identification criteria for different constituents. A total of 28 compounds, including nine phenolic acids, three iridoid glycosides and nine saponins from Flos Lonicerae and seven flavonoids from Radix Scutellariae, were identified or tentatively characterized in the extract of Yinhuang granules. The established fast HPLC-DAD-TOF/MS method turns out to be useful and efficient for quality control of this commonly used Chinese herbal preparation.     

Identification of the metabolites of gigantol in rat urine by ultra‐performance liquid chromatography combined with electrospray ionization quadrupole time‐of‐flight tandem mass spectrometry

Gigantol is a typical bibenzyl compound isolated from Dendrobii Caulis that has been widely used as a medicinal herb in China for the treatment of diabetic cataract, cancer and arteriosclerosis obliterans and as a tonic for stomach nourishment, saliva secretion promotion and fever reduction. However, few studies have been carried out on its in vivo metabolism. In the present study, a rapid and sensitive method based on ultra‐performance liquid chromatography/electrospray ionization quadrupole time‐of‐flight tandem mass spectrometry (UPLC‐Q/TOF‐MS) in positive ion mode was developed and applied to identify the metabolites of gigantol in rat urine after a single oral dose (100 mg/kg). Chromatographic separation was performed on an Acquity UPLC HSS T3 column (100 × 2.1 mm i. d., 1.8 µm) using acetonitrile and 0.1% aqueous formic acid as mobile phases. A total of 11 metabolites were detected and identified as all phase II metabolites. The structures of the metabolites were identified based on the characteristics of their MS, MS² data and chromatographic retention times. The results showed that glucuronidation is the principal metabolic pathway of gigantol in rats. The newly identified metabolites are useful to understand the mechanism of elimination of gigantol and, in turn, its effectiveness and toxicity. As far as we know, this is the first attempt to investigate the metabolic fate of gigantol in vivo. Copyright © 2014 John Wiley & Sons, Ltd.     

超高效液相色谱/串联质谱法分析水中的微囊藻毒素

建立了超高效液相色谱/质谱快速、准确、高灵敏度地测定水体中痕量微囊藻毒素（MCYST）的分析方法,并用于实 际样品的分析。采用固相萃取法富集净化样品。该法在5 min内即可完成4种MCYST（LR、RR、LW、LF）的分离及检测;LR 、RR、LW、LF的定量检测限、回收率分别为1.3～6.0 ng/L、91.1%～111%;工作曲线的线性相关系数大于0.99,线性范 围达3个数量级。实际样品分析表明,在所测定的水库水样中均检出了LR和RR,其质量浓度分别为0.0447～2.73 μg/L和0.0208～1.36 μg/L;而在所有的检测样品中均未检出LW和LF。     

Comparison of Phenolic Profile of Balsamic Vinegars Determined Using Liquid and Gas Chromatography Coupled with Mass Spectrometry

Balsamic vinegar is one of the best known and most popular types of vinegar, and it is a rich source of polyphenolic compounds. The quality of balsamic vinegar as well as the content of phenolic substances vary depending on the production method. In the present work, we have developed a method for comprehensive characterization of the content of phenolic compounds in balsamic vinegars based on the combination of gas chromatography (GC) and high-performance liquid chromatography (HPLC) coupled with mass spectrometric detection in single mode (MS) and tandem mode (MS/MS). In total, 14 samples of different types of balsamic vinegar were analyzed without difficulty in sample preparation. The separation conditions and detection parameters of HPLC-MS/MS were optimized and used for the determination of 29 phenolic compounds and 6 phenolic acids. The profile of phenolic compounds was completed by semi-quantitative analysis of volatile organic compounds using GC-MS after optimized headspace solid-phase microextraction. Gallic acid, protocatechuic acid, caffeic acid, and p-coumaric acid have been identified as the major phenolic compounds in balsamic vinegars.     

Identification and determination of the major constituents in Kai‐Xin‐San by UPLC‐Q/TOF MS and UFLC‐MS/MS method

In order to have overall chemical material information of Kai‐Xin‐San (KXS), the reliable ultra‐high‐performance liquid chromatography quadrupole time‐of‐flight mass spectrometer (UHPLC–Q‐TOF‐MS) and ultra‐fast liquid chromatography mass spectrometer (UFLC‐MS/MS) methods were developed for the identification and determination of the major constituents in KXS. Moreover, the UHPLC–Q‐TOF‐MS method was also applied to screen for multiple absorbed components in rat plasma after oral administration of KXS. The UHPLC–Q‐TOF‐MS method was achieved on Agilent 6520 Q‐TOF mass and operated in the negative ion mode. Good separation was performed on a ZORBAX Eclipse Plus C18 column with a gradient elution at a flow rate of 0.2 ml/min. A total of 92 compounds in KXS were identified or tentatively characterized based on their exact molecular weights, fragmentation patterns, and literature data. A total of 26 compounds including 23 prototype components and three metabolites were identified in rat plasma after oral administration of KXS. Then, 16 major bioactive constituents were chosen as the benchmark substances to evaluate the quality of KXS. Their quantitative analyses were performed by a triple quadrupole tandem mass spectrometer (MS/MS) operating in multiple‐reaction monitoring mode(MRM). The analysis was completed with a gradient elution at a flow rate of 0.4 ml/min within 35 min. The simple and fast method was validated and showed good linearity, precision, and recovery. Furthermore, the method was successful applied for the determination of 16 compounds in KXS. All results would provide essential data for identification and quality control of active chemical constituents in KXS. Copyright © 2016 John Wiley & Sons, Ltd.     

高效液相色谱-串联质谱法测定粮谷中9种氨基甲酸酯类农药残留

本研究采用了高效液相色谱-串联质谱联用(HPLC-MS/MS)技术,建立了高灵敏度的同时检测粮谷中9种氨基甲酸酯类农药残留量的方法。样品经乙腈提取,中性氧化铝填充柱净化,然后采用HPLC-ESI( )-MS/MS测定。对液-质分离条件和样品前处理条件进行了优化。9种氨基甲酸酯类农药在0.1~100μg/L范围内线性良好,相关系数为0.9986~0.9998。在0.001~0.05mg/kg浓度范围内,平均加标回收率在73.40%~102.01%之间;相对标准偏差为1.25%~9.94%。该方法简便、快速、灵敏、净化效果好。可同时满足进、出口粮谷中多种氨基甲酸酯类农药残留量的检验工作需要。