Determination of Organophosphorus Pesticides in Seawater by GC-FPD Using Two Columns

本文提出了一种GC-FPD测定海水中28种有机磷农药残留的新方法。采用双柱法,即选用DB-1701柱进行定性、定量分析,用HP-5柱验证。既发挥了FPD检测器灵敏、定量准确的优点,又利用了双柱法的定性功能。方法对各目标物均有良好的线性关系,回收率和RSD分别在70.2%~103.2%、8.7%~17.5%之间,适合于海洋水体中痕量有机磷农药的分析。A GC method has been developed to determine 28 kinds of OPPs in seawater simultaneously by GC-FPD.The columns were DB-1701 and HP5.The column DB-1701 used for analysis and the column HP-5 used for validate.The linear dynamic ranges were well.the recovery was from70.2 %～103.2 %,the RSD was from 8.7 %～17.5 %.The method was used for the determination of trace OPPs in sea water.国家863项目(项目编号:2003AA635180

Methodologic Study of HPCE Fingerprints of Radix paeoniae Alba and Radix paeoniae Rubra

目的确定赤芍和白芍的高效毛细管电泳分析方法,建立赤芍和白芍的高效毛细管电泳法(HPCE)指纹图谱。方法HPCE工作条件:采用未涂层熔融石英毛细管(内径75μm,有效长度50 cm),分离电压为25 kV,柱温25℃,二极管阵列检测器(DAD)检测波长为220 nm,缓冲液为30 mmol/L硼砂(pH=9.0)溶液。按此条件对来自不同产地的7种赤芍样品和8种白芍样品进行了分析。结果建立了赤芍和白芍HPCE指纹图谱,采用中药指纹图谱相似度计算软件,以系统生成的对照指纹图谱为对照模板对不同样品的图谱进行相似度计算。结论该方法简捷、有效,可以用于赤芍和白芍药材的质量控制。Objective To set up a modern High Performance Capillary Electrophoresis analysis method for separating and detecting Radix paeoniae Alba and Radix paeoniae Rubra and establish their fingerprints.Methods Seven samples of Radix paeoniae Alba and eight samples of Radix paeoniae Rubra were carried out by HPCE under the following conditions: bared fused silica capillary(50 cm ×75 μm i.d.),30 mmol/L borate(pH = 9.0) as buffer,the run voltage is +25 kV,detection wavelength of UV at 220 nm,and column temperature of 25℃.Results The fingerprints were confirmed and compared by the software of the similarity evaluation system for chromatographic fingerprint.Conclusion The results showed that the method of HPCE fingerprint is reliable and accurate to control the quality of two Chinese traditional medicines.国家自然科学基金重点项目(No.20235020);; 青岛“2004将才计划”(No.04-3-JJ-11);; 青岛市崂山区科技计划项目(No.LS-05-KJZX-76

大孔吸附树脂分离纯化龙胆药材中龙胆苦苷和马钱子苷酸的研究

目的:建立利用大孔吸附树脂对龙胆药材中龙胆苦苷和马钱子苷酸进行富集和分离纯化的方法。方法:采用加速溶剂萃取法对龙胆药材中两种有效成分进行高效提取,比较了D301,AB-8,D101,XDA-1四种大孔树脂对龙胆苦苷和马钱子苷酸的吸附性能,最终确定采用D301型大孔对脂对二者进行富集吸附,对其工艺参数进行优化,全程采用高效液相色谱进行目标化合物浓度检测。结果:化优后的工艺参数为:上样浓度:0.2 g/mL,最大上样量:0.25 g龙胆药材/g树脂,最佳静态吸附时间:8 h,采用8%和55%的乙醇溶液对龙胆苦苷和马钱子苷酸分别进行洗脱;龙胆苦苷和马钱子苷酸分别富集在8%和55%的乙醇洗脱液中,洗脱液浓缩后冷冻干燥,可得到纯度分别为74.3%和80.9%的粗产物,龙胆苦苷和马钱子苷酸的回收率分别为70.11%和67.82%。结论:此法效率较高,操作简便,即可用于实验室制备少量的难以购置的标准品,也可进行放大研究,用于工业生产。国家自然科学基金重点项目(20235020);; 青岛“2004将才计划”(04-3-JJ-11);; 共建生物医药研发测试中心(LS-05-KJZX-76)资

Content of gentiopicroside and loganic acid in Radix gentianae and their fingerprints

To develop a HPLC-DAD-ESI-TOF/MS analysis method for the determination of gentiopicroside and loganic acid in Radix gentianae samples and for the research of their fingerprints.The samples were extracted using ASE for 10 min under 100 ℃ and 9.65 MPa,and divided into water phase and chloroform phase and analyzed them with HPLC-DAD-ESI-TOF/MS method respectively.Based on this method,the HPLC fingerprints of Radix gentianae were established.Comparing the spectrogram and mass spectrum of the chromatogram peak with the reference value,three compounds in water phase were identified as gentiopicroside,asafetida acid and loganic acid.There is no report of the compounds in chloroform phase.The content of gentiopicroside and loganic acid in samples of different groups were determined,separately.The fingerprints were compared by the software of the similarity evaluation system for chromatographic fingerprint.The water phase fingerprint congruence coefficients of samples from six different areas were above 0.90,however,the chloroform phase fingerprint congruence coefficients were within 0.62-0.99.This method can be used for determination of potent component in Radix gentianae and its quality control.Radix gentianae from different producing areas have the largest diversities,and the diversities embodied in the content of chloroform phase compounds.青岛“2004将才计划”(04-3-JJ-11);; 国家海洋局青年基金资助项目(2005602);; 崂山区政府区校共建生物医药研发测试中心资助(LS-05-KJZX-76)

Determination of Gentiopicroside and Loganic Acid in Radix Gentianae by MEKC and MEEKC Mode

目的建立胶束电动毛细管色谱(MEKC)和微乳液毛细管电动色谱(MEEKC)分析龙胆药材中龙胆苦苷和马钱子苷酸含量的方法。方法采用加速溶剂萃取法(ASE)对龙胆药材进行提取,萃取温度:100℃,压力:9.65MPa,萃取时间:10min。采用未涂层熔融石英毛细管(内径75μm,有效长度50cm)。分别考察了两种分离模式下电泳介质的构成和电泳过程中的各操作参数对样品分离过程的影响,优化了MEKC和MEEKC的分析条件,在各自对应的缓冲液体系下,MEKC和MEEKC分离电压分别为30和22kV,柱温均为25℃,检测波长均为238nm。结果在选定的工作条件下,龙胆苦苷和马钱子苷酸与其他组分达到了基线分离,两种成分的浓度与其响应信号值之间具有较好的线性相关性,加标回收率在96.3%～105.1%之间,检测限均低于10mg·L-1,对6处不同产地的龙胆药材进行了分析,并对测定结果进行了t检验,结果表明,两种模式下,测定结果之间不存在显著性差异,而不同产地的龙胆药材的龙胆苦苷和马钱子苷酸含量之间存在较大差异。结论本方法简便,准确,快速,重现性较好,可用于龙胆药材有效成分的含量测定和质量控制。OBJECTIVE To develop MEKC and MEEKC modes for the determination of gentiopicroside and loganic acid in extracts of Radix Gentianae. METHODS The analyte was extracted from Radix Gentianae samples by accelerated solvent extraction, and the extraction conditions were optimized. Separation and determination were carried out on a bared fused silica capillary(50 cm×75 μm) with corresponding buffer. The run voltage of MEKC and MEEKC were 30kV and 22 kV respectively. Detection wavelength of DAD was at 238 nm and column temperature was 25 ℃. RESULTS The developed ASE-HPCE method was simple and reliable for the determination of gentiopicroside and loganic acid in Radix Gentianae samples with a broad linear dynamic range, a recovery range of 96.3%～105.16%,and the detection limit was below 10 mg·L-1. The contents of gentiopicroside and loganic acid in six samples from different regions were determined by the developed method in two modes. T-test value indicated that the determined contents of gentiopicroside and loganic acid by MEKC and MEEKC were consistent. CONCLUSION The method is simple,accurate,rapid and with good reproducibility.It can be used to determine active components in Radix Gentianae.国家自然科学基金重点项目(20235020);; 青岛“2004将才计划”(04-3-JJ-11);; 崂山区校区共建生物医药研发测试中心资助(LS-05-KJZX-76

Organophosphate pesticide residue monitoring and risk assessment in the sea-water from Laizhou Bay

研究近年来莱州湾水体中有机磷农药残留情况及对环境的影响。于2005年5月采集了渤海莱州湾及其主要河口地区的水样,用气相色谱(GCFPD)测定了样品中有机磷农药的含量,并运用化学污染物风险评价公式进行了风险概率评价。结果表明,莱州湾海域水体中有机磷农药的含量范围在0.2~79.1ng/L,氧化乐果、甲胺磷、马拉硫磷、敌百虫、敌敌畏、乐果、甲基毒死蜱、甲基对硫磷等在研究海域占主要部分。对研究海域水体中有机磷农药的风险评价表明,莱州湾海域水体中的有机磷农药的含量与其他地区相比,污染水平居中,氧化乐果、甲胺磷、马拉硫磷、敌百虫、敌敌畏、乐果等农药对研究海域的生态环境安全已经构成了一定的威胁,应加强该地区该类农药的施用管理。The present paper is aimed at reporting our investigation and analysis of the current sea-water pollution situation in Laizhou Bay, Shandong, particularly, with the pollution distribution of organophosphate pesticide residues (OPs) in the waters. For the research purpose, we have worked out a GCFPD method to determine the 28 kinds of OPs in the water. With the method, we made an analysis on the OPs in the samples of Laizhou Bay of Bohai Sea collected in May, 2005. With the data detected, a preliminary risk assessment has been done by using the formula of risk assessment of chemical contamination. The results of our analysis reveal that the content of the OPs is ranging from 0.2 ng/L to 79.1 ng/L, with omethoate, methamidophos, malathion, trichlorphon, dichlorvos, dimethoate, chlorpyrifos-methyl, and parathion-methyl as the dominant components. Compared with other sea-water areas of the world, the OPs pollution level in OPs can be regarded as moderate. The risk assessment results indicate that some residues of the organic phosphorus pesticides, such as omethoate, methamidophos, malathion, trichlorphon, dichlorvos, dimethoate, have already become harmful factors as to form a threatening factor for the ecological environment. Therefore, our study likes to suggest that the degree of the content of OPs in the area has been affected by the complicated hydrological kinetics. It is just for this reason, necessary measures should be taken to control the use of organophosphate pesticides.国家“十五”863项目(2003AA635180

Analysis of Alkaloids in Semen Nelumbinis by Accelerated Solvent Extraction-High Performance Liquid Chromatography-Diode Array Detection-Electrospray Ioninztion-Time of Flight-Mass Spectrometry

建立了加速溶剂萃取-高效液相色谱-电喷雾飞行时间质谱(ASE-HPLC-DAD-ESI-TOF/MS)联用技术分析莲子心中生物碱类化合物的方法。采用ASE法对药材进行提取,萃取温度为100℃,压力为9646kPa,时间为10min。采用HPLC-DAD-ESI-TOF/MS联用技术对其中的化学成分进行了分离鉴定,HPLC采用AgilentEclipseXDB-C18色谱柱;流动相为0.1%三乙胺溶液,用氨水调pH=8.0(A),色谱纯乙腈(B),梯度洗脱;进样量为20μL,流速:1.0mL/min;检测波长:282nm。ESI-TOF/MS采用正离子电离模式,毛细管电压:4500V;喷雾气压:310.05kPa;干燥气(N2)流速:10.0L/min;干燥气温度:350℃,破碎电压:150V。鉴定了其中的6种生物碱分别为:前荷叶碱、莲心季铵碱、莲心碱、异莲心碱、荷叶碱和甲基莲心碱。An accelerated solvent extraction-high performance liquid chromatography-diode array detection-electrospray ioninztion-time of flight-mass spectrometry(ASE-HPLC-DAD-ESI-TOF/MS)analysis method was developed for the analysis of lkaloids in Semen nelumbinis.The samples were extracted using ASE for 10 min at 100 ℃ and 9646 kPa,and then analyzed by HPLC-DAD-ESI-TOF/MS.HPLC was carried out,using an Agilent Eclipse XDB-C18 column(250 mm×4.6 mm×5 μm)and acetonitrile-0.1% triethylamine(adjusted pH=8.0 with ammonia solution)as mobile phase(using gradient elution)with flow rate 1.0 mL/min and detected at 282 nm.The ESI-TOF/MS was set at the positive ion mode;capillary voltage:4500 V;pressure of spray:310.05 kPa;fiow velocity of dry gas(N2):10.0 L/min;temperature of dry gas:350 ℃;fragmentor voltage:150 V.Comparing the spectrogram and mass spectrum of the chromatogram peak with the references value,six compounds were identified as pronucifefine,lotusine,nuciferine,liensinine,isolisensinine,and neferine.国家自然科学基金重点项目(No.20235020);; 青岛“2004将才计划”(No.04-3-JJ-11);; 共建生物医药研发测试中心(No.LS-05-KJZX-76)资

Rapid determination of fatty acids in tea by GC-MS

建立了气相色谱-质谱联用技术(gC-MS)快速分析茶叶脂肪酸的新方法。对23批茶叶样品进行gC-MS分析,结合nIST 05谱库检索鉴定茶叶脂肪酸种类,并用峰面积归一化法测定其相对含量,比较不同加工方式的茶叶脂肪酸含量。结果表明,所有茶样中亚麻酸、亚油酸和棕榈酸含量最高,但绿茶和青茶脂肪酸含量高于发酵处理的红茶和黑茶。方法可以用于分析各种茶叶的脂肪酸,反映不同种类茶叶的性质差异。A new and rapid GC-MS method for fatty acids in tea was developed after optimizing the processes of extracting and detecting fatty acids in tea.The extracts in 23 samples were isolated and identified by GC-MS,and the relative contents of acidic components were determined by peak area normalization method.As a result,all the tea samples have the higher contents of Octadecatrienoic acid,Octadecadienoic acid and Hexadecanoic acid than other fatty acids,but the green and oolong teas have the higher contents of fatty acids than the black and dark tea.The results show that the method of GC-MS developed in this paper is quick,reliable, accurate and useful for the analysis of fatty acids in all kinds of tea.福建省科技厅茶叶指纹图谱质量控制研究项目(2006N0043);海洋一所基本科研业务专项(GY-022008T32;GY-022008G47)项目资

Analysis of alkaloids in Semen nelumbinis by accelerated solvent extraction-high performance liquid chromatography-diode array detection-electrospray ioninztion-time of flight-mass spectrometry

An accelerated solvent extraction-high performance liquid chromatography-diode array detection-electrospray ioninztion-time of flight-mass spectrometry (ASE-HPLC-DAD-ESI-TOF/MS) analysis method was developed for the analysis of lkaloids in Semen nelumbinis. The samples were extracted using ASE for 10 min at 100 T and 9646 kPa, and then analyzed by HPLC-DAD-ESI-TOF/MS. HPLC was carried out, using an Agilent Eclipse XDB-C-18 column(250 min x 4.6 min x 5 mu m) and acetonitrile-0.1% triethylamine (adjusted pH = 8. 0 with ammonia solution) as mobile phase ( using gradient elution) with flow rate 1.0 mL/min and detected at 282 nm. The ESI-TOF/MS was set at the positive ion mode; capillary voltage:4500 V; pressure of spray: 310.05 kPa; fiow velocity of dry gas (N-2) : 10.0 L/min; temperature of dry gas: 350 degrees C; fragmentor voltage: 150 V. Comparing the spectrogram and mass spectrum of the chromatogram peak with the references value, six compounds were identified as pronucifefine, lotusine, nuciferine, liensinine, isolisensinine, and neferine