《中藥中吡咯里西啶類生物堿檢測(cè)液相色譜-串聯(lián)質(zhì)譜法》本標(biāo)準(zhǔn)采用超高效液相色譜-串聯(lián)質(zhì)譜法（HPLC-MS/MS）方法對(duì)藥材及飲片建立藥材及飲片（植物類）中27種吡咯里西啶類生物堿的種類判定和含量英文通用名中文別名CAS登記號(hào)分子式分子量Echimidine藍(lán)薊定520-68-3C20H31NO7397.46EchimidineN-oxide藍(lán)薊定氧化物41093-89-4C20H31NO8413.46ErucifolineN-oxide芝麻菜葉千里光堿氧化物123864-94-8C18H23NO7365.38Europine歐天芥菜堿570-19-4C16H27NO6329.39EuropineN-oxide歐天芥菜堿氧化物65582-53-8C16H27NO7345.39Heliotrine天芥菜堿303-33-3C16H27NO5313.39HeliotrineN-oxide天芥菜堿氧化物6209-65-0C16H27NO6329.39Intermedine印美定10285-06-0C15H25NO5299.36Intermedine-N-oxide印美定氧化物95462-14-9C15H25NO6315.36Jacobine千里光堿6870-67-3C18H25NO6351.39JacobineN-oxide千里光堿氧化物38710-25-7C18H25NO7367.39Lasiocarpine毛果天芥菜堿303-34-4C21H33NO7411.49LasiocarpineN-oxide毛果天芥菜堿氧化物127-30-0C21H33NO8427.49Lycopsamine石松胺10285-07-1C15H25NO5299.36Lycopsamine-N-oxide石松胺氧化物95462-15-0C15H25NO6315.36Monocrotaline野百合堿315-22-0C16H23NO6325.36Monocrotaline-N-oxide野百合堿氧化物35337-98-5C16H23NO7341.36Retrorsine倒千里光堿480-54-6C15H25NO6351.40Retrorsine-N-oxide倒千里光堿氧化物15503-86-3C18H25NO7367.39Senecionine千里光寧130-01-8C18H25NO5335.39SenecionineN-oxide千里光寧氧化物13268-67-2C18H25NO6351.39Seneciophylline千里光菲靈堿480-81-9C18H23NO5333.39SeneciophyllineN-oxide千里光菲靈堿氧化物38710-26-8C18H23NO6349.39Senecivernine春光千里堿72755-25-0C18H25NO5335.39SenecivernineN-oxide春千里光堿氧化物101687-28-9C18H25NO6351.39Senkirkine克氏千里光堿2318-18-5C19H27NO6365.43Trichodesmine毛束草堿548-90-3C18H27NO6353.41質(zhì)譜儀檢測(cè)；離子源為電噴霧（ESI）離子源，正離子掃描模式，利用多反應(yīng)監(jiān)對(duì)照品的監(jiān)測(cè)離子對(duì)峰面積比一致(相對(duì)比例>50%，允許±20%偏差；相對(duì)比例>20%~50%，允許±25%偏差；相對(duì)比例>10%~20%，允許±30%偏差；相對(duì)比例xi=································（1）Ci-------從標(biāo)準(zhǔn)曲線上得到的待測(cè)溶液中吡咯里西啶類生混合對(duì)照品溶液的制備精密量取各對(duì)照品貯備溶液適量，用甲醇制成濃度），鐘，放至室溫，再稱定重量，用0.05mol/L硫酸溶液補(bǔ)足減失的重量，離心5方法準(zhǔn)確度溶液的配制取供試品粉末（過三號(hào)篩取約3.0g（9份液相色譜條件色譜柱：用十八烷基硅烷鍵合核殼硅膠為填充劑(Agilent表2梯度洗脫程序時(shí)間(分鐘)流動(dòng)相A(%)流動(dòng)相B(%)0~592→905~5.190→825.1~1882→7918→2118~2179→4021→6021~244060串聯(lián)質(zhì)譜參考條件以三重四極桿串聯(lián)質(zhì)譜儀檢測(cè)；離子源為電噴霧(ESI)離子源，正離子掃描模式。監(jiān)測(cè)模式為多反應(yīng)監(jiān)測(cè)(MRM)，各化合物參考保留時(shí)表3各化合物保留時(shí)間、監(jiān)測(cè)離子對(duì)及碰撞電壓(CE)參考值編號(hào)中文名英文名保留時(shí)間母離子子離子CE1藍(lán)薊定Echimidine20.9398.1120.2220.2238.12藍(lán)薊定N-氧化物EchimidineN-oxide21.1414.0254.0352.13芝麻菜葉千里光堿-氮氧化物ErucifolineN-oxide7.1366.0119.2136.14歐天芥菜堿Europine7.2330.2138.0156.040405歐天芥菜堿N-氧化物EuropineN-oxide7.8346.3111.1172.1108.2406天芥菜堿Heliotrine314.3120.2138.27天芥菜堿N-氧化物HeliotrineN-oxide330.1156.1153.1181.1458印美定Intermedine7.1300.1207.1120.2138.1156.19印美定N-氧化物Intermedine-N-ox8.3316.2138.2172.1162.2千里光堿千里光堿N-Jacobine7.0352.1105.2120.2155.1162.2190.1氧化物JacobineN-oxide7.6367.9249.0毛果天芥菜堿Lasiocarpine21.9412.0120.1220.1238.145毛果天芥菜堿N-氧化物L(fēng)asiocarpineN-oxide22.3410.0106.2120.2136.1石松胺Lycopsamine7.3300.0120.2138.1石松胺N-氧化物L(fēng)ycopsamine-N-ox8.7316.2156.1138.2172.1野百合堿Monocrotaline3.8326.1121.2164.1194.1野百合堿N-氧化物Monocrotaline-N-oxide6.5342.1119.2137.1236.1倒千里光堿倒千里光堿RetrorsineRetrorsine-Noxid9.7324.1120.1138.1136.340N-氧化物e368.1248.9156.0108.2120.1千里光寧千里光寧N-SenecionineSenecionine336.2138.1156.0118.1氧化物N-oxide352.1136.1220.1千里光菲靈堿Seneciophylline334.1105.2120.2138.228千里光菲靈Seneciophylline120.1252312.4350.1堿N-氧化物N-oxide136.130154.125108.125120.22524春光千里堿Senecivernine14.4336.1156.040春千里光堿Senecivernine91.0402516.2352.4N-氧化物N-oxide252.115克氏千里光26Senkirkine20.1366.0150.125堿168.12527毛束草堿Trichodesmine7.8354.0208.125222.126純；氨水：分析純；0.05mol/L硫酸溶液：取硫酸3mL，緩50mL，緩緩注入適量水中，冷卻至室溫，加水稀釋至100mL，搖勻。0.05%甲酸）：心機(jī)；分析天平：感量0.1mg；量瓶：5mL；微量移液器：100-1000μL量程、取系列混合對(duì)照品溶液，以各分析物的質(zhì)量定量離子對(duì)峰面積為縱坐標(biāo)（Y繪制標(biāo)準(zhǔn)曲線。以分析物定性離子對(duì)的3倍表427種吡咯里西啶類生物堿的線性關(guān)系考察結(jié)果編號(hào)英文名稱線性范圍/線性方程rLODng/mLLOQng/mL1Lycopsamine5-100Y=8925.44*X+1359.620.99990.20.52Intermedine3HeliotrineIntermedine4N-oxideLycopsamine5N-oxide6Moncrotaline7HeliotrineN-oxide8Europine9Seneciophylline10Senecivernine11SenecionineMoncrotalineN-oxide13EuropineN-oxideSeneciophyllineN-oxide15JacobineSeneionineN-oxide17RetrorsineSenecivernineN-oxide19TrichodemineY=30358.1*X+5-100-8904.99Y=88646.3*X+5-10044484.1Y=27778.4*X+5-100-22227.3Y=9676.53*X+5-100-5282Y=4071.07*X+5-100-4137.35Y=43427.3*X+5-100-31973Y=3359.56*X+5-1002972.03Y=12772.3*X+5-100-4308.39Y=8731.13*X+5-100-8069.62Y=22458.1*X+5-100-17521Y=9280.24*X+5-100-7781.51Y=16228.6*X+5-1005853.58Y=2672.79*X+5-100-491.336Y=8533.62*X+5-1001571.64Y=2016.97*X+5-100703.21Y=2267.38*X+5-100-1934.18Y=1094.69*X+5-100-697.939Y=16086.4*X+5-100-24053.1Erucifoline20N-oxide21Erucifoline20N-oxide21Senkirkine22JacobineN-oxide23RetrorsineN-oxide5-1005-100Y=32745.8*X+-902.3945-1005-100Y=9094.39*X+-9718.955-1005-100Y=3998.06*X+764.2355-1000.200.9990.210.200.9990.290.9990.290.200.9990.270.9990.250.9990.290.9990.390.9990.290.9990.290.9990.290.9990.250.9990.250.9990.260.9990.290.9990.280.9990.290.9990.190.9990.290.9990.280.50.50.50.50.50.50.50.50.510.50.50.50.50.50.50.50.50.50.30.50.5Y=52005.3*X+0.99924Echimidine5-1000.20.512281.2Y=51243.5*X+60.99925Lasiocarpine5-1000.20.544462.77Echimid