齊魯藥事 Qilu Pharmaceutical Affairs2005Vol.24N.7馬藺子素中殘留乙醇、乙酸乙酯的測定豐宇勝邢玉君1孫愛永(山東新華制藥股份有限公司淄博2550051.淄博醫(yī)藥站淄博255005)摘要淚目的應(yīng)用頂空氣相色譜法對馬藺子素中的殘留溶劑乙醇和乙酸乙酯進(jìn)行測定。方法采用固定相為94%二甲基聚硅氧烷-6%氰丙基苯基θ.53mm×30m膜厚3.0m的色譜柱以氮氣為載氣FI檢測器通過外標(biāo)法計算殘留溶劑的含量。結(jié)果馬藺子素中有乙醇檢出乙酸乙酯未檢岀。乙酸乙酯的線性范圍2.22~-6664r=0.9999乙醇的線性范圍:4,84-4844r=0.998)定量限乙醇為4.8pm乙酸乙酯為2.2pmn檢測限乙醇為0.5pm乙酸乙酯為0.4pp。平均回收率乙醇為105.2%乙酸乙酯為95.2%。結(jié)論本方法簡便、靈敏度高、重復(fù)性好結(jié)果準(zhǔn)確關(guān)鍵詞馮馬藺子素氣相色譜法頂空進(jìn)樣毛細(xì)管柱中圖分類號πTα460.7文獻(xiàn)標(biāo)識碼A文章編號:1672-7738205)7-0411-02Determination of ethanol and ethyl acetate remained in IrisquinoneFeng Yu-sheng Xing Yu-jun Sun Ai-yongShandong Xinhua Pharmaceutical Share Limited Corporation Zibo 255005'1.Zibo Purchase and Supply Station Zibo 255005)Abstract Objective A gas chromatograph with a headspace sampler was used to determine ethanol and ethyl acetate ofisquinone. Methods The solid phase is 6%cyanopropylphenyl-94% dimethylpolysiloxane 0. 53mm X 30m ,thickness is 3. 0 mcarrier gas is N, detector is FID, ISTD method is used to determine the assay. Results In the sample of Irisquinone the ethanol isdetected and ethyl acetate is not detected. The linearity range of ethyl acetate is 2. 22-666ug( r=0. 9999). The linearity range ofethanol is 4.84-484u r=0. 9998),the LOQ of ethanol is 4.8ppm ,the LoQ of ethyl acetate is 2.2ppm ,the LOD of ethanol is0. 5ppm the LOd of ethyl acetate is 0. 4ppm the average recovery of ethanol is 105.2% that of ethyl acetate is 95.2%. ConclusionThe method is simple sensitive exactive and has good repeatabilityKey words Irisquinone XC headspace capillary馬藺子素是抗腫瘤增效劑其生產(chǎn)工藝過程中使用了乙1.4自動頂空進(jìn)樣器條件爐溫$℃計溫ν℃;傳輸線醇和乙酸乙酯為測定其溶劑殘留筆者使用配置有頂空進(jìn)溫度:00℃加熱時間min加壓時間.2min進(jìn)樣體積樣器的氣相色譜儀對馬藺子素中殘留乙醇、乙酸乙酯進(jìn)行測1ml定本文建立的方法與曾經(jīng)報道的頂空氣相色譜法均具有圖譜靈敏可靠、重復(fù)性好、結(jié)果準(zhǔn)確、操作簡便的特點1。適用于馬藺子素中殘留乙醇、乙酸乙酯的測定。l儀器及色譜條件1.1儀器氣相色譜儀 Agilent6890)自動頂空進(jìn)樣器(Ag.iminilent 7694 b樣品(乙醉保留時間:1.475min)1.2試劑無水乙醇(AR)乙酸乙酯(AR)二甲基甲酰胺( DMFXAR)超純水、馬藺子素山東新華制藥股份有限公1,473乙醇司1.3色譜條件色譜柱:HP-624(30m×0.53mm,膜厚3.0;m固定液巧%氰丙基苯基-94%二甲基聚硅氧烷)柱溫斗0℃保持6min,然后以120℃·min1升溫至240℃并保齊魯藥事 Qilu Pharmaceutical Affairs2005vl.24No.72溶液和樣品配制線噪音的3.8倍。則乙醇的檢測限為0.5pm乙酸乙酯的2.1空白溶液移取5.0ml水、1.0 mI DMF于20ml頂空瓶檢測限為0.4pm中密封。醇回收率2.2標(biāo)準(zhǔn)溶液取無水乙醇約0.25mW=0.2002g)乙酸對照品中乙醇的重量(g)乙酯約20y(W=0.0183g)于已加入少量去有機(jī)物水的溶液100ml容量瓶中再加入去有機(jī)物水至刻度搖勻得溶液A樣品乙醇加入g)38.76135.7取A液1.0m用去有機(jī)物水稀釋至20oml得溶液B。取乙醇的測得量g)142.1回收率%)107.2液5.0ml于20ml頂空瓶中加入1.0 mI DMF密封。同法平均回收率%)105.2制得6個標(biāo)準(zhǔn)溶液瓶。表乙酸乙酩回收率2.3樣品配制精稱樣品約100ng于20ml頂空瓶中加入1.0 mI DMF溶解然后加入5.0m水密封。對照品中乙酸乙酯的重氬四)2.4依次將6個標(biāo)準(zhǔn)溶液瓶、空白溶液瓶、樣品溶液瓶放入溶液樣品乙酸乙酯加入量g)17.7622.2062.16頂空進(jìn)樣器中在80℃下平衡60min乙酸乙酯的測得量四)16.6821,1160.113測定回收率(%)93,995.196.73.1系統(tǒng)適應(yīng)性試驗標(biāo)準(zhǔn)溶液連續(xù)6次進(jìn)樣乙醇峰面積平均回收率%)95.2的RSD=2.2%Z酸乙酯峰面積的RSD=2.1%z醇與3.4檢測限、定量限的測定乙酸乙酯的分離度R=12。系統(tǒng)適應(yīng)性試驗符合要求23.4.1配制相當(dāng)于樣品中含乙醇1pm乙酸乙酯0.4pm的3.2線性及線性范圍取無水乙醇約0.25ml(W水溶液取線性及線性范圍項下C液稀釋100000倍)移取0.1938g)z酸乙酯約10W=0.088g)已加入少量超.0ml于20m頂空瓶中加入1.mDMF密封后于8o℃純水的100ml容量瓶中加入超純水至刻度搖勻得溶液A,烘6min取1.0ml氣體頂空進(jìn)樣,記錄得色譜圖。色譜圖將溶液A以超純水稀釋成一系列濃度的線性測試淑(乙醇中乙醇峰高約為基線噪音的4.3倍乙酸乙酯的峰高約為基的量依次為4.8419.496.919439A84gz酸乙酯的量線噪音的3.8倍。則乙醇的檢測限為0.5pm乙酸乙酯的依次為228.8844.488.815522144669g)然后各檢測限為0.4pm取5.0ml于20ml頂空瓶中分別各加入1.0mDMF密封后3.4.2配制相當(dāng)于樣品中含乙醇4.8pm、乙酸乙酯2.2pp在80℃恒溫平衡6min。分別進(jìn)樣1.om記錄色譜圖。以的水溶液取線性及線性范圍項下C液稀釋2000倍)移取峰面穊Y劂溶液濃度Ⅹ進(jìn)行線性回歸乙醇、乙酸乙酯的5.0ml于20m頂空瓶中加入1.0mDMF,同法配置-空線性回歸方程分別為:Y=2.30x-0.7478;Y=16.93X白密封后于80℃烘60min取lml氣體頂空進(jìn)樣記錄得色11.2035。相關(guān)系數(shù)r分別為0.99980.999ν線性范圍分譜圖。色譜圖中乙醇的峰高約為基線嗓音的14倍乙酸乙別為484-48412.22pga酯的峰高約為基線噪音的18倍。則乙醇的定量限為3.3回收率測定分別取線性測試項下溶液A0.4ml、4.8pm乙酸乙酯的定量限為2.2ppm0.5m、1.4ml,以超純水稀釋成100ml的測試液得溶液14樣品的測定(含乙醇38.76g相當(dāng)于387.6pm浛含乙酸乙酯17.76,利用上述色譜條件對5批馬藺子素樣品進(jìn)行殘留溶劑相當(dāng)于177.6pm)溶液2(含乙醇48.45g,相當(dāng)于的測定結(jié)果見表3484.5pm含乙酸乙酯22.20g相當(dāng)于22.0pm)溶液3表3樣品中殘留溶劑的測定結(jié)果(含乙醇135.7相當(dāng)于1357pm含乙酸乙酯62.161g相批號乙pm)乙酸乙醌ppm)當(dāng)于621.6pm)然后各取50m于20ml頂空瓶中各加0304001未檢出入0.1g樣鼠(批號0304004廂和1.0mDMF密封。再按照0304002未檢出2.3項樣品的制備方法制備1份樣品做為空白樣品液。將3040034.5未檢出以上溶液依次放入自動頂空進(jìn)樣器中在80℃下平衡60min0304004未檢出03040054.0未檢出后分別取1.0ml進(jìn)樣分別記錄色圖譜。以RSD測試項下對照溶液為標(biāo)準(zhǔn)計算加樣品的溶液1溶液2和溶液3的乙5討論醇和乙酸乙酯回收率乙醇平均回收率為105.2%(表1)之乙中國藥典殘留溶劑的測定采用填充杜2多采用溶液法酸乙酯平均回收率為95.2%表2)直接進(jìn)樣靈敏度較低本方法采用頂空進(jìn)樣技術(shù)相當(dāng)于對3.4檢測限、定量限的測定溶液中的殘留溶劑具有富集作用又采用殘留溶劑測定專用3.4.1配制相當(dāng)于樣品中含乙醇1pm乙酸乙酯0.4pm的的色譜柱HP-624檢測靈敏度明顯提高水溶液取線性及線性范圍項下C液稀釋1000倍)移取參考文獻(xiàn)5.0ml于20m頂空瓶中,加入1. OmI dme,密封后于80℃[1唐慶華.頂空氣相色譜法測定依莫法宗中溶劑殘留.國外分析