HPLC法测定氨糖美辛肠溶片的含量

摘 要 目的：建立HPLC法测定氨糖美辛肠溶片中吲哚美辛和盐酸氨基葡萄糖含量。方法: 采用Waters BridgeC18 (250 mm×4.6 mm,5 μm)色谱柱,以磷酸二氢铵(以磷酸调节pH至3.0)（A）,乙腈(B)为流动相,梯度洗脱,流速为0.7 ml·min-1,检测波长195 nm,进样量为20 μl,柱温30℃。结果: 盐酸氨基葡萄糖在0.030 0～1.500 8 mg·ml-1（r=0.999 1）,吲哚美辛在0.010 3～0.513 0 mg·ml-1（r=0.999 9）范围内线性关系良好;平均回收率分别为98.3% （RSD=0.33%,n=6）;99.9% （RSD=0.06%,n=6）。结论: 此方法准确、快速、灵敏、专属性强,可较好地控制该产品的质量。     

HPLC-MS/MS法同时测定百蕊颗粒中紫云英苷和山奈酚的含

摘 要 目的：建立同时测定百蕊颗粒中紫云英苷和山奈酚2种有效成分含量的HPLC MS/MS检测方法。方法: 采用Ultimate XB C18 （100 mm×2.1 mm,5 μm）色谱柱;流动相为0.1%甲酸水溶液（A） 0.1%甲酸乙腈(B),梯度洗脱,流速0.3 ml·min-1;柱温为40℃;采用电喷雾离子源(ESI),以多反应监测方式(MRM)进行定量分析。紫云英苷和山奈酚在负离子模式下定量分析离子对分别为m/z 447.2→m/z 284.0和m/z 285.1→m/z 187.1。结果:紫云英苷和山奈酚的浓度分别在9.86~1 970 ng·ml-1（r=0.999 5）和8.73~437 ng·ml-1（r=0.999 6）范围内均呈良好线性关系;紫云英苷和山奈酚低、中、高平均加样回收率分别为99.23%、99.65%、99.23%和98.24%、99.13%、99.69%,RSD分别为1.84%、1.37%、1.21%和1.38%、0.96%、1.47%（n=6）。结论:本文方法简便可靠,重复性好,可同时测定百蕊颗粒中紫云英苷和山奈酚的含量,适用于百蕊颗粒质量控制。     

HPLC-MS/MS法测定人血清中异帕米星的浓度

摘 要 目的：建立测定人血清中异帕米星的高效液相色谱 串联质谱（HPLC-MS/MS）方法。 方法: 色谱柱为Agilent Poroshell120 HILIC Z柱(100 mm×2.1 mm,2.7 μm),流动相为水溶液（100 mmol·L-1醋酸铵+1%甲酸） 乙腈（1%甲酸）,梯度洗脱。以阿米卡星为内标,电喷雾离子源,多反应离子监测模式,正离子模式检测。异帕米星定量离子通道为570.2/411.4,定性离子通道为570.2/250.3。 结果: 异帕米星在0.78～25.00 μg·ml-1范围内线性关系良好（r=0.998 7）,回收率为93.22%~101.96%。 结论: 本方法简单、快速、准确,适用于临床患者人血清异帕米星浓度分析测定。     

HPLC法同时测定根管消毒糊剂中3种成分的含量

摘 要 目的：建立高效液相色谱法（HPLC）同时测定根管消毒糊剂中多西环素、甲氧苄啶和醋酸地塞米松的含量。 方法: 色谱柱为Wonda Cract C18（250 mm×4.6 mm,5 μm）,流动相为甲醇 0.005 mol·L-1庚烷磺酸钠缓冲溶液（内含0.1%三乙胺）（梯度洗脱）,流速1.0 ml·min-1,检测波长240 nm,柱温25℃,进样量20 μl。 结果: 多西环素、甲氧苄啶和醋酸地塞米松的质量浓度分别在61 ~ 1 214 μg·ml-1（r=0.999 5）、57 ~ 1 137 μg·ml-1（r=0.999 7）和2~9 μg·ml-1（r=0.999 2）范围内与峰面积呈良好的线性关系;平均加样回收率及相应RSD分别为99.5%（RSD=1.21%）、100.4%（RSD=1.23%）和100.1%（RSD=1.20%）（n=9）。 结论: 该方法准确度好,精密度高,可用于多西环素、甲氧苄啶和醋酸地塞米松的同时测定。     

HPLC法测定人血清中百草枯含量

摘 要 目的：建立HPLC法测定人血清中百草枯含量。方法: 色谱柱：Kromasil C18柱（200 mm×4.6 mm,5 μm）,流动相：乙腈 水（含0.03 mol·L-1庚烷磺酸钠,0.24 mol·L-1磷酸）=3〖KG*9〗∶〖KG-*2〗97（用三乙胺调pH至2.0）;检测波长258 nm;柱温25℃;进样体积20 μl;流速0.8 ml·min-1。结果: 百草枯在0.106~10.6 mg·L-1浓度范围内线性关系良好( r=0.999 3),最低检出浓度为0.065 mg·L-1。高、中、低3种浓度样品绝对回收率＞89.4%,方法回收率＞94.4%,日内精密度RSD在0.12%～1.74%之间,日间精密度RSD在0.44%～2.89%之间。结论: 该方法操作简便易行、灵敏度高、专属性强,适用于百草枯的人体血清浓度测定。     

GC法同时测定肚痛丸中6 种有效成分的含量

摘 要 目的：建立同时测定肚痛丸中6种成分含量的气相色谱方法。方法: 色谱柱为 HP 5柱 (30 m×0.32 mm,0.25 μm);采取程序升温,载气为氮气,流速为2.0 ml·min-1,进样量为1 μl,分流比为5∶1,进样口温度为280 ℃,检测器（FID）温度为300 ℃。结果:桂皮醛、乙酸龙脑酯、木香烃内酯、去氢木香内酯、厚朴酚、和厚朴酚分别在32.28~516.40 μg·ml-1（r=0.999 3）、27.06~433.00 μg·ml-1（r=0.999 2）、25.65~410.40 μg·ml-1（r=0.999 3）、26.10~417.60 μg·ml-1（r=0.999 3）、24.01~384.20 μg·ml-1（r=0.999 0）、18.32~293.10 μg·ml-1（r=0.999 4）范围内呈良好的线性关系;平均加样回收率分别为99.71%（RSD=0.67%）、99.34%（RSD=1.18%）、100.16%（RSD=0.34%）、100.40%（RSD=0.39%）、99.32%（RSD=1.22%）、99.58%（RSD=0.58%)(n=6）。结论:该方法操作简便,灵敏度高,准确度好,可为控制该制剂的质量提供依据。     

HPLC法同时测定参莲胶囊中7种生物碱成分的含量

摘 要 目的：建立RP HPLC双波长法同时测定参莲胶囊中氧化苦参碱、槐定碱、氧化槐果碱、苦参碱、槐果碱、粉防己碱、防己诺林碱7种生物碱含量。 方法: 采用Venusil XBP NH2（250 mm×4.6 mm,5 μm）色谱柱,以乙腈 0.01%醋酸铵水溶液为流动相梯度洗脱,流速为1.0 ml·min-1,检测波长为210 nm、280 nm。 结果: 氧化苦参碱、槐定碱、氧化槐果碱、苦参碱、槐果碱、粉防己碱、防己诺林碱线性范围分别为32.07～513.07 μg·ml-1（r=0.998 8）、37.90～606.40 μg·ml-1（r=0.999 2）、23.07～369.07 μg·ml-1（r=0.999 2）、52.37～837.87 μg·ml-1（r=0.999 7）、17.63～282.13 μg·ml-1（r=0.999 1）、5.30～84.80 μg·ml-1（r=0.999 5）、8.87～141.87 μg·ml-1（r=0.999 7）;平均加样回收率（n=9）为100.16%~102.84%（RSD≤2.0%）。5批样品中氧化苦参碱、槐定碱、氧化槐果碱、苦参碱、槐果碱、粉防己碱、防己诺林碱含量依次为9.18~9.69 mg·g-1、9.35~11.74 mg·g-1、6.73~7.09 mg·g-1、15.17~15.96 mg·g-1、5.03~5.33 mg·g-1、1.23~1.97 mg·g-1、2.48~2.74 mg·g-1。 结论: 所建立的多成分分析方法可用于参莲胶囊中7个生物碱成分的含量测定。     

QuEChERS-GC-MS/MS测定蚓激酶原料药中41种农药残留量

摘 要 目的：建立QuEChERS (quick, easy, cheap, effective, rugged and safe)快速样品前处理技术结合气相色谱串联质谱法(GC-MS/MS)同时测定蚓激酶原料药中41种农药残留的方法。 方法: 采用GC-MS/MS法测定蚓激酶原料药中41种农药残留量。色谱柱为HP 5ms ultla Lert弹性石英毛细管柱（30.0 m×0.25 mm,0.25 μm）,检测器为质谱检测器,进样口温度为240℃;检测器温度为280℃,程序升温,载气为高纯氦气,隔垫吹扫为5 ml· min-1,柱流速为2.0 ml·min-1,进样量为1.0 μl,进样方式为不分流。质谱检测器离子源为电子轰击离子源,离子源温度为230℃,碰撞气为高纯氩气,灯丝电压为70 eV,传输线温度为280℃,积分延时为4 min。 结果: 41种农药检测质量浓度线性范围均为100～500 μg·L-1（r≥0.995 0）;检测限为1.5～3.8 μg·L-1;定量限为5.0~12.5 μg·L-1;精密度的RSD均<8%（n=6）、重复性与稳定性试验的RSD均<6%(n=6);蚓激酶原料药样品加样平均回收率均为70.47%～105.66%。 结论: 该方法简便、准确、高效,可用于判断蚓激酶原料药是否有农药残留。     

八珍丸HPLC特征指纹图谱研究及多成分定量分析

摘 要 目的：建立八珍丸HPLC指纹图谱,并进行多成分定量分析,为八珍丸的质量控制提供可靠依据。方法: 采用SHIMADZU VP ODS (250 mm×4.6 mm,5 μm)色谱柱,以乙腈 甲醇 水（60 ∶〖KG-*4〗38 ∶〖KG-*4〗2）（A） 0.6%磷酸水溶液（B）作为流动相进行梯度洗脱,流速1.0 ml·min-1,柱温35 ℃,检测波长230 nm、320 nm、220 nm。结果: 利用《中药色谱指纹图谱相似度评价系统2004A版》进行分析,共确定八珍丸HPLC指纹图谱17个共有峰,通过与混合对照品比较指认其中6个指标成分分别是：芍药苷(4号峰)、毛蕊花糖苷(6号峰)、阿魏酸(8号峰)、甘草苷(9号峰)、白术内酯Ⅰ(13峰)和白术内酯Ⅲ(17号峰)。对12批样品的指纹图谱进行相似度分析,各批样品相似度均在0.9以上。芍药苷、毛蕊花糖苷、阿魏酸、甘草苷、白术内酯Ⅰ和白术内酯Ⅲ线性范围分别为0.010～0.250 μg（r=0.999 7）、0.124～3.100 μg（r=0.999 1）、0.058～1.450 μg（r=0.999 5）、0.069～1.475 μg（r=0.999 0）、0.032～0.800 μg（r=0.999 8）和0.027～0.675 μg（r=0.999 3）。12批八珍丸中芍药苷、毛蕊花糖苷、阿魏酸、甘草苷、白术内酯Ⅰ和白术内酯Ⅲ含量分别为0.099～0.118 mg·g-1、1.383～1.449 mg·g-1、0.300～0.395 mg·g-1、0.504～0.604 mg·g-1、1.013～1.080 mg·g-1和0.205～0.299 mg·g-1。结论: 所建立的八珍丸HPLC指纹图谱检测和定量测定分析方法快速、准确、专属性强、灵敏度高,可以用于评价该制剂的质量。     

离子色谱-电感耦合等离子体质谱联用测定琥珀酸亚铁片中三价铁和二价铁含量

摘 要 目的：建立测定琥珀酸亚铁片中三价铁和二价铁含量的方法。方法: 采用Dionex RFICTM保护柱(4mm×50mm),Dionex RFICM Ion PacRCS5A分析柱(4 mm×250 mm), 淋洗液：7 mmol·K^-1 吡啶二羧酸、66 mmol·K^-1氢氧化钾、5.6 mmol·K^-1硫酸二氢钾和74 mmol·K^-1甲酸的混合溶液;流速：1.5 ml·min^-1;柱温：30.0℃;进样体积：1.3 μl。结果: Fe³+在0.5～15 μg·ml^-1范围内线性良好（r=1.000 0）;Fe²+在25～200 μg·ml^-1范围内线性良好（r=1.000 0）; Fe³+的平均回收率为103.6%（RSD=2.7%, n=9）;Fe²+的平均回收率为98.3%（RSD=1.9%, n=9）。结论:该方法简便可靠,结果准确,可用于琥珀酸亚铁片的含量测定。     

API-ionspray MS and MS/MS study on the structural characterization of bisbenzylisoquinoline alkaloids

API-ionspray MS and MS/MS techniques have been utilized to elucidate the structures of 20 bisbenzylisoquinoline alkaloids, consisting of 17 diether and three monoether links of two benzyltetrahydroisoquinoline units, which were isolated and identified previously from a variety of Thalictrum sp. (Ranunculaceae family). Apparent protonated molecular ions ([M+H](+)) and very intense doubly-protonated molecular ion ([M+2H](++), 100% of relative abundance) in Q1 Scan MS spectra and prominent as well as diagnostic product ions for the structural information in MS/MS spectra were observed in nanogram quantities for all investigated alkaloids.     

LC/MS/MS的多反应监测方法定量测定灯盏乙素

目的：建立一种可靠的灯盏乙素定量分析方法。方法：用三级四极串联质谱(MS/MS)作为HPLC的检测器,其中MS/MS使用了多反应监测(MRM)扫描方式。选择母→子离子对m/z -461→m/z -285作为MRM监测的离子对;HPLC流动相为100％甲醇,流速0.9 mL.min^-1,色谱柱Beckman ODS-1。以测定短葶飞蓬提取物的灯盏乙素含量为例,对此方法进行了应用。结果：灯盏乙素在短葶飞蓬提取物中含量为6.98%。方法线性范围20～160 ng.mL^-1 (γ=0.999);加入灯盏乙素标准品20,60和160 ng的加样回收率分别为：96.5%,97.4%和97.3%。检测限为1 ng,每个样品的分析时间为4 min。结论：此法灵敏、快速、准确,可应用于灯盏乙素的各种药剂、药代的研究。     

System suitability in bioanalytical LC/MS/MS

System suitability is widely recognized as a critical component of bioanalysis. This paper discusses a generic system suitability test that monitors instrument performance throughout a run when used for liquid chromatography tandem mass spectrometry (LC/MS/MS) in bioanalysis. This system suitability process is designed to ensure that the LC/MS/MS system is performing in a manner that leads to the production of accurate and reproducible data that can be submitted with confidence to regulatory agencies. This process contains tests for signal stability, carryover, and instrument response. This approach is integrated throughout an analytical run and has been used in the analysis of over 25,000 batches of clinical samples. Two case studies are presented in which quality control samples and standards meet all acceptance criteria (based on Standard Operating Procedures and the Food and Drug Administration's recommendations for bioanalytical method validation) but failed the proposed system suitability test, and thus were rejected. In these case studies, the concentrations of a significant number of clinical samples (over 35%) were affected, resulting in changes of more than 15% when the samples were reanalyzed. These data indicate that the poor performance of an LC/MS/MS system could adversely affect the calculated concentrations of unknown samples even though the results for quality control samples appear to be acceptable.     

LC/MS/MS与GC/MS法分析鉴定小鼠尿中沙美特罗的代谢产物

目的:鉴定沙美特罗在小鼠尿中的主要代谢产物.方法:ig给药后,收集小鼠尿液,经固相提取,葡萄糖醛酸酶水解,进行LC/MS/MS分析和硅烷化后进行GC/MS分析同时分离鉴定沙美特罗代谢产物.结果和结论:在给药后尿样中发现沙美特罗原型和4种代谢产物M1～M4,其结构推测为19-羟基沙美特罗(M1)、2-羰基沙美特罗(M2)、19-羰基沙美特罗(M3)和19-羟基-8-甲氧基沙美特罗(M4).     

Analysis of 'SHENMAI' injection by HPLC/MS/MS

An HPLC/MS/MS method was developed for the analysis of 'SHENMAI' injection, composed of red ginseng and ophiopogon. The constituents of 'SHENMAI' were found to be similar with those of ginseng and 39 ginsenosides were detected. By the studies of MS and MS/MS spectra and the comparison with literature data, most of these ginsenosides were identified. Based on this study, suggestions were put forward to improve the quality control system of 'SHENMAI' injection.     

液相色谱-串联质谱法快速测定人血浆中伊曲康唑

目的:建立灵敏、快速的液相色谱-串联质谱法测定人血浆中伊曲康唑,并用于药代动力学研究。方法:血浆样品经乙腈沉淀蛋白后,以乙腈-水-甲酸(80:20:0.2,v/v/v)为流动相,流速0.50 mL·min~(-1),Zorbax sB C_(18)柱分离,采用电喷雾电离源,以选择反应监测(SRM)方式进行正离子检测。用于定量分析的离子反应分别为 m/z 705→m/z(392 432)(伊曲康唑)和m/z 256→m/z 167(内标,苯海拉明)。结果:测定血浆中伊曲康唑的线性范围为1.00～1000 ng·mL~(-1),定量下限为1.00 ng·mL~(-1)。日内、日间精密度(RSD)均小于7.2%,准确度(RE)在±3.0%以内。应用本法测得20名健康受试者单剂量口服200mg 伊曲康唑胶囊后的主要药动学参数为:T_(max)(4.25±1.02)h,C_(max)(155.5±73.3)ng·mL~(-1),t_(1/2)(20.4±11.4)h;用梯形法计算,AUC_(0-84h)(2257±1168)ng·h·mL~(-1),AUC_(0-∞)(237.1±1207)ng·h·mL~(-1)。结论:该法选择性强、灵敏度高、操作简便,适用于伊曲康唑的临床药代动力学研究。     

Determination of a selection of synthetic cannabinoids and metabolites in urine by UHPSFC‐MS/MS and by UHPLC‐MS/MS

Two different analytical techniques, ultra‐high performance supercritical fluid chromatography‐tandem mass spectrometry (UHPSFC‐MS/MS) and reversed phase ultra‐high performance liquid chromatography‐tandem mass spectrometry (UHPLC‐MS/MS), were used for the determination of two synthetic cannabinoids and eleven metabolites in urine; AM‐2201 N‐4‐OH‐pentyl, AM‐2233, JWH‐018 N‐5‐OH‐pentyl, JWH‐018 N‐pentanoic acid, JWH‐073 N‐4‐OH‐butyl, JWH‐073 N‐butanoic acid, JWH‐122 N‐5‐OH‐pentyl, MAM‐2201, MAM‐2201 N‐4‐OH‐pentyl, RCS‐4 N‐5‐OH‐pentyl, UR‐144 degradant N‐pentanoic acid, UR‐144 N‐4‐OH‐pentyl, and UR‐144 N‐pentanoic acid. Sample preparation included a liquid‐liquid extraction after deconjugation with ß‐glucuronidase. The UHPSFC‐MS/MS method used an Acquity UPC^{2 TM} BEH column with a mobile phase consisting of CO₂ and 0.3% ammonia in methanol, while the UHPLC‐MS/MS method used an Acquity UPLC® BEH C₁₈ column with a mobile phase consisting of 5 mM ammonium formate (pH 10.2) and methanol. MS/MS detection was performed with positive electrospray ionization and two multiple reaction monitoring transitions. Deuterated internal standards were used for six of the compounds. Limits of quantification (LOQs) were between 0.04 and 0.4 µg/L. Between‐day relative standard deviations at concentrations ≥ LOQ were ≤20%, with biases within ±19%. Recoveries ranged from 40 to 90%. Corrected matrix effects were within 100 ± 10%, except for MAM‐2201 with UHPSFC‐MS/MS, and for UR‐144 N‐pentanoic acid and MAM‐2201 N‐4‐OH‐pentyl with UHPLC‐MS/MS. Elution order obtained by UHPSFC‐MS/MS was almost opposite to that obtained by UHPLC‐MS/MS, making this instrument setup an interesting combination for screening and confirmation analyses in forensic cases. The UHPLC‐MS/MS method has, since August 2014, been successfully used for confirmation of synthetic cannabinoids in urine samples revealing a positive immunoassay screening result. Copyright © 2015 John Wiley & Sons, Ltd.     

快速液相色谱联用质谱法测定人血浆氟伏沙明的药物浓度

摘 要 目的：建立快速液相串联质谱方法,测定人血浆中氟伏沙明的药物浓度。方法: 色谱柱为Inertsil ODS SP （100 mm×2.1mm, 3 μm）,流动相为乙腈:2 mmol·L^-1醋酸铵缓冲液（含0.3%甲酸）=40∶60 (v/v),流速为0.3 ml·min^-1,兰索拉唑为内标。采用电喷雾离子源,以多反应监测（MRM）方式进行正离子检测。用于定量分析的离子分别为m/z 319.1→m/z 69.8（氟伏沙明）和m/z 370.2→m/z 252.1 （兰索拉唑,内标）。 结果: 氟伏沙明的血浆浓度在1~100 μg·L^-1范围内线性良好,定量下限为1 SymbolmA@g· L^-1,日内精密度<5%,日间精密度<10%,回收率为85%~95%。结论: 该法操作简单,灵敏,准确,重现性好,适用于氟伏沙明人体药动学及生物等效性研究。     

超高压液相/电喷雾-LTQ-Orbitrap质谱联用技术分析三七根中皂苷类成分

建立三七药材的UPLC-ESI-HRMS定性分析方法。采用Kinetics色谱柱,梯度洗脱,经DAD检测器后采用ESI-LTQ-Orbitrap质谱负离子模式采集,三七成分的一级全扫描离子在离子阱内进行CID多级质谱,FT检测高分辨质谱数据进行分析。结果表明三七皂苷成分分离良好,根据多级质谱碎片信息和精确相对分子质量信息,结合文献,从三七中鉴定分析了43个成分,并首次从三七中检测到新型的三七皂苷母核和乙酰取代皂苷成分。本方法分离度良好、灵敏度高,可用于三七药材的定性分析,并有助于对三七进行进一步的活性成分研究和质量控制。