Gel Permeation Chromatography Purification and Gas Chromatography-Mass Spectrometry Detection of Multi-Pesticide Residues in Traditional Chinese Medicine

The measurement of 23 organochlorine, organophosphorus, and pyrethroid pesticides in typical traditional Chinese medicine (TCM), flos lonicerae, was made using gel permeation chromatography (GPC) purification and gas chroma- tography-mass spectrometry (GC-MS) detection. The pesticides were extracted with ultrasonic device and 5.0 mL mixture of ethyl acetate and cyclohexane (1:1, v/v). Coextractants from sample matrices which may have interfere to the qualitative and quantitative analysis, such as pigments, were removed using GPC purification. Simultaneous full scan and selective ion monitor (scan/SIM) mode for GC-MS was used for qualitative and quantitative analysis, which pro- vided retention time and characteristic fragments ratio for each pesticide so as to positively identify each analyte. Rela- tive standard deviations (RSDs) were within 7.7% (5.0 - 22.5 μg/kg, n = 3). The recoveries of pesticide standards at the spiked concentration of 5.0 - 22.5 μg/kg were between 87.1% and 110.9%. Limits of detection (LODs) for the analytes were 0.16 - 3.2 μg/kg, which could meet the demand of routine analysis and TCM quality control.

NOVEL APPROACHES FOR THE DETERMINATION OF MULTIPLE PARTICULAR PESTICIDES IN TRADITIONAL CHINESE MEDICINES WITH COMPLEX MATRICES

The pesticide contamination of Traditional Chinese Medicines(TCMs)takes different ways,which caused the complexity of pesticide residues.The effective control of pesticide residues and the establishment of relevant detection methods are very important for ensuring the safety of TCMs.Our group has been committed to the determination of pesticide residues in TCMs for years.

Safety issues and new rapid detection methods in traditional Chinese medicinal materials

The safety of traditional Chinese medicine(TCM) is a major strategic issue that involves human health. With the continuous improvement in disease prevention and treatment, the export of TCM and its related products has increased dramatically in China. However, the frequent safety issues of Chinese medicine have become the ‘bottleneck' impeding the modernization of TCM. It was proved that mycotoxins seriously affect TCM safety; the pesticide residues of TCM are a key problem in TCM international trade; adulterants have also been detected, which is related to market circulation. These three factors have greatly affected TCM safety. In this study, fast, highly effective, economically-feasible and accurate detection methods concerning TCM safety issues were reviewed, especially on the authenticity, mycotoxins and pesticide residues of medicinal materials.

9种药食两用药材中15种有机磷类农药残留分析及膳食风险评估

对9种药食两用药材进行15种有机磷类农药残留污染分析和膳食风险评估,为中药材中农药残留快筛方法的开发提供基础数据支持。农药残留采用检出率、超标率进行分析;膳食风险评估分别采用慢性膳食风险评估和急性膳食风险评估。陈皮和栀子检出农药数量最多,共检出8种农药,且3种为禁用农药;禁用农药中甲拌磷检出最多,在5种药材中检出,在当归中检出率高达100%;限用农药中毒死蜱检出最多,分别在6种中药材中检出,在金银花中检出率高达100%;禁用农药甲拌磷在当归中的超标率高达69.05%,限用农药丙溴磷在陈皮中的超标率为25.45%。9种药食两用药材中15种有机磷类农药均有不同程度检出,污染现象普遍且超标率较高,虽然目前急性与慢性膳食风险评估结果均在可接受范围内,但农残累积风险加重,势必会对中药材质量造成影响,进而危害人体健康。因此,要科学规范使用农药,并采取有利的监管手段对中药材进行质量控制。

用于中药中农药残留检测的全自动快速样品处理仪验证与评价

采用中药农药残留的样品处理方法作为验证方式,建立了全自动快速样品处理(QuEChERS)设备的验证与评价方法。验证的设备按照标准方法的步骤执行样品处理过程,对影响最终实验结果的基本性能和应用效果进行验证。验证的农药化合物在0.005~0.25μg/mL质量浓度范围内与其相应的色谱峰面积具有较好的线性关系,相关系数均大于0.99,检出限均为0.002 mg/kg。中药样品在不同浓度的加标水平下的加标平均回收率为71.6%~128.8%,相对标准偏差为0.1%~8.1%。全自动快速样品处理设备实验操作的一致性程度较高,设备在分液、移液和加盐等步骤的操作可以满足实验的要求。采用自动化样品处理方式应用于中药农药残留检测,能有效减少人为误差,提高检测的准确性、重现性和溯源性,为分析仪器的自动化和智能化技术验证提供了技术支持。

酶抑制率快速检测方法用于中药材中农药残留检测

采用酶抑制率法快速检测中药材中有机磷和氨基甲酸酯类农药残留,从而建立一种中药材中农药残留的快速检测方法。以酶抑制率为指标,分别考察了提取时间、进样量和抑制时间三个因素对检测条件的影响。确定了中药材中有机磷和氨基甲酸酯类农药的最佳检测条件为提取时间10min、进样量1.5mL、抑制时间15min。分别在不含农药的中药材(砂仁、金线莲、石橄榄、铁皮石斛和百合)中添加克百威、敌敌畏和久效磷做加标回收实验,其平均回收率在75.6~109.0%,相对标准偏差小于10%。克百威、敌敌畏、久效磷等多种农药的方法检测灵敏度为0.02~1mg/kg。样品同时用快速检测方法和传统色谱方法测定,两者的测定结果有较好的吻合度。

23种中药材中农药残留量的研究

AIM To compare the pesticide hexachlorocyclohexane (BHC), dichlorodiphenyl trichloroethane (DDT) and pentachloronitrobenzene (PCNB) contents in 23 kinds of traditional Chinese medicine with the existing limits in the world. METHODS The contents of BHC, DDT and PCNB in 23 kinds of medicinal medicines were determined according to the method given in the addenda IXQ of the Chinese Pharmacopoeia (2000). Average values and standard deviations of every pesticide in every medicinal material and 23 kinds of medicinal materials were obtained. This is the first time to use the percentile statistical technology to make statistics and get the limited values (80% value) of pesticide residues which made 80 percent samples qualified. The probable daily intake of pesticide residues from the traditional Chinese medicine by Chinese adult were calculated according to the dosage of 300 g herbal medicine every day. RESULTS Statistical results showed that the contents of total BHC, total DDT and PCNB in most samples were under the prescriptive standard of the Chinese Pharmacopoeia (2000). Total BHC and total DDT in traditional Chinese medicine with a dosage of 300 g medicinal materials were close to their intake from total food. The sums of total BHC and total DDT from the traditional Chinese medicine and total daily food intake by Chinese adult were much lower than the acceptable daily intake (ADI) values proposed by the FAO/WHO. CONCLUSION The limited standards of pesticide residues in Chinese Pharmacopoeia is reasonable and safe and also suitable for the fact of the traditional Chinese medicine in our country.

中药材中农药残留现状及控制措施评析

对中药材中常用农药的使用情况、残留现状及原因进行了归纳分析,并提出了防止中药材中农药残留超标的一些具体措施:完善法律法规,建立相应的质量标准体系;加强生物防治力度,推广使用无公害生物农药;选育抗病虫害的中药材新品种;科学规划中药材生产基地,严格按照《中药材生产质量管理规范》科学合理地使用农药等。应加速科研创新,综合采取各项措施,有效减少和控制中药材中的农药残留,保障中药材产品质量安全。

中药中有机氯农药残留量检测方法及限量标准研究

目的:运用作者所建立的中药中有机氯类农药残留量的测定方法,对11种中药材和6种中成药中六六六和DDT各四个异构体、五氯硝基苯及艾氏剂的残留量进行了测定,根据测定结果,提出了其限量标准的建议。方法:采用在线法提取,硫酸磺化后直接测定法;选用SE54和SPB1701毛细管柱,通过柱程序升温手段,对十种农药进行分离测定。结果:SPB1701柱对该十种农药的分离效果优于SE54柱;十种农药在1～100ng·ml-1的浓度范围内与峰值呈良好的线形关系,其检出限范围为0.5～1.5pg。结论:建议中药材和中成药中总六六六、总滴滴涕、五氯硝基苯和艾氏剂最大允许限量标准分别为0.1,0.1,0.1,0.02mg·kg-1。本方法快速、简便、准确、具有良好的通用性。

党参中29种有机氯农药的多残留分析

目的:建立党参药材中29种有机氯农药残留量的气相色谱分析方法。方法:样品采用乙酸乙酯提取,Florisil柱净化方式,采用GC-ECD,DB-5/1701双柱测定29种有机氯农药的残留量。结果:此方法3个水平的加样回收率分别为96.3%,98.2%,99.0%,RSD分别为8.2%,9.9%,14.3%。结论:方法简便,快捷。

中药材中有机磷类农药残留量的GC-PCI-MS法测定(Ⅰ)

采用气相色谱 -正化学电离_质谱法对中药材中有机磷农药残留进行检测方法的研究 ;应用选择离子监测 (SIM)技术 ,排除了杂质的干扰 ,提高了分析灵敏度 ;建立了有效。

中药中有机磷农药残留量的毛细管气相色谱测定方法

建立了同时测定中药中8种有机磷农药残留量的前处理及其毛细管气相色谱测定法 ,选用氮磷检测器和SPB -1701毛细管柱,以丙酮 -石油醚混合溶剂提取残留农药。结果表明 :敌百虫、敌敌畏、甲胺磷、二嗪农、乐果、马拉硫磷、甲基对硫磷和对硫磷8种农药在25min内有良好的分离 ;3个不同浓度的标准添加 ,其回收率范围为74.96 %～116.8 % ,相对标准偏差范围为0.71 %～16.91 % ;检出限范围为1.1×10-2～3.36×10-1 pg。该法具有灵敏度高、选择性强、操作简便、重现性好、适用性广等特点 ,有着良好的应用前景。

HPLC测定中药中农药灭幼脲残留量的方法研究

建立测定中药材、中成药中农药灭幼脲残留的含量。采用 RP- HPL C法 ,ODS色谱柱。流动相为甲醇-水 (75∶ 2 5 ) ,检测波长 2 5 0 nm。结果 :加样回收率 92 .6 7%～ 10 0 .2 1% ,0 .0 315～ 0 .6 3μg/m L、0 .315～ 6 .3μg/m L 时 ,r=0 .9999,线性关系良好。简便、快速 ,适合中药材。

气相色谱-串联质谱法快速筛查测定中药材中144种农药残留

利用气相色谱-串联质谱（GC—MS／MS）检测技术，采用QuEChERS法作为样品前处理方法，建立了能应用于11种叶J药材中144种农药残留的检测方法。探究了样品前处理过程中提取溶剂、缓冲盐体系、净化剂组成和用量对样晶提取、净化等方面的影响，最终确定了用乙腈提取，甲苯复溶，以混合净化剂净化，过有机膜后经GC-MS／MS测定，外标法定鼙。144种农药在10～2000μg／kg之间线性关系良好，相关系数（r2〉0．983；除乙酰甲胺磷、灭虫威、西玛津、克菌丹、异狄氏剂、异菌脲外，其余农药的定量限（LOQ）均低于20μg／kg；在20、50、200μg／kg的添加水平下，除乙酰甲胺磷、艾氏剂和双甲脒回收率偏低外，其余141种农药的平均回收率在74．3％～111．8％之间，相对标准偏差（RSD）为0．5％～14．6％。与已有的标准方法对比，此方法不仅检测结果一致，而且高效、快速，准确性好，灵敏度高，适用于中药材中144种农药残留的快速筛查与定量分析。

根茎类中药材有机氯及菊酯类农药多残留分析

目的建立测定根茎类中药材中50种有机氯及菊酯类农药多残留分析的方法。方法以乙腈为提取剂,提取液用弗罗里硅土柱净化,乙酸乙酯-正己烷(15∶85,v/v)洗脱,采用HP-5与DB1701毛细管色谱柱双柱分离,GC-ECD检测器进行检测。结果在5种根茎类中药材样品基质、3水平添加条件下,50种农药的回收率大多在70.0%～120.0%,相对标准偏差小于15%,检测限大多低于10μg/kg,符合农药多残留检测的要求。结论 本方法灵敏度高,稳定性好,可用于根茎类中药材中有机氯及拟除虫菊酯类农药多残留的检测。

中药中农药残留量研究状况及安全控制

总结了中药中农药残留量研究现状， 概述了农药的种类、提取、净化及其分析方法， 并就中药中农药残留的安全控制作了初步探讨。

中药中重金属和残留农药去除方法研究进展

目的为选择中药中重金属和残留农药的去除方法提供依据。方法根据近年的23篇文献,从去除中药中重金属技术及去除中药中残留农药技术两个方面进行综述。结果去除重金属的方法有吸附色谱分离法、吸附澄清法、超临界CO2配合萃取法;去除残留农药的方法有水洗法、炮制法、超临界CO2流体萃取法。结论色谱分离技术为很有前途的去除重金属的处理技术;超临界CO2流体萃取法对于去除中药中重金属和残留农药效果较好。

我国中药材中有机氯农药残留量的调查分析

通过查阅近年来的有关文献资料,阐述中药检测中有机氯农药残留量的一般方法,对国内已报道的80余种药材的有机氯农药残留量进行了统计分析．参照世界粮农组织(FAO)和世界卫生组织(WHO)及我国对蔬菜、茶等作物的农药允许残留量,制定出常用、大宗中药材品种的农药残留限量标准,并在此基础上初步制定了中药材农药最大允许残留量(MRL)的参考值．结果表明,80余种中药材样品中的有机氯农药残留量的测定结果显示,我国大部分中药材与中成药中总滴滴涕和六六六的含量均在0．1μg/g以下,但仍然有部分药材的农药残留水平较高,严重超过现有国家标准．建议我国中药材及中成药中的BHC、DDT、PCNB的最高残留量分别为0．1,0．12,0．02μg/g, 并能根据药材的药用部位和药材用量制定更为细致的农药残留量标准．

GC-MS法同时测定中药材中29种农药残留量

目的建立一种可同时对29种有机氯、有机磷类农药残留量进行定量检测的方法。方法利用GC-MS技术,配合负化学源检测器,采用选择离子检测法(SIM)进行定量,以石油醚-丙酮混合溶剂为洗脱溶剂,样品通过Florisil硅土柱净化,选择环氧七氯为内标物。结果对48种中药材进行了检测;除敌敌畏、杀虫脒、磷丹及三唑磷外,其余农药的检测限都在0.2～15 g.kg-1之间;以9种中药材为例检测,大部分农药的回收率在70%～120%之间。结论该方法简单、快捷、经济,分析结果达到农残分析的要求,适合大批量样品的同时检测。

果实类中药材中20种有机磷农药残留量的同时测定

建立了果实类中药材中多种有机磷农药残留同时测定的方法,并对影响提取、净化、检测效率的因素进行优化。样品用乙酸乙酯提取，凝胶渗透色谱收集9-15 min流分，ENVI-Carb固相萃取柱净化，DB-1701毛细管色谱柱分离，火焰光度检测器检测，外标法定量。在优化条件下，20种有机磷农药在0.01-2.0 mg/L 范围内具有良好的线性关系，相关系数为0.996 6-0.999 5，检出限（S/N=3）为0.66-5.78 μg/kg。3个加标水平下的平均回收率为80.2%-109.9%，相对标准偏差为2.3%-13%。该方法操作简便、准确、净化效果好，可满足果实类中药材中多种有机磷农药残留的同时测定要求。