【作者】 陈静；

【导师】 赵春杰；

【作者基本信息】 沈阳药科大学 ， 药物分析学， 2008， 硕士

【摘要】 随着中药事业的不断发展，中药及其产品的质量越来越引起人们的重视。但在中药材的种植中，大量应用的化学农药在土壤中长期残留以及环境的污染，使中药材中的农药残留量及重金属量超标，严重影响了中药及其产品的质量。目前，在中药中残留农药及重金属的检测和分析方面研究相对较集中，而对脱除中药中残留农药及重金属方法方面的研究相对较少。因此有效的脱除残留农药和重金属的方法，是非常有必要的。本研究建立了人参提取物中10种有机氯农药、4种有机磷农药和2种拟除虫菊酯农药残留同时测定的气相色谱分析方法。采用丙酮-正己烷（1：4，V：V）混合溶剂超声提取，再用正已烷进行液-液分配，提取液用弗罗里硅土柱净化，采用OV-1701弹性石英毛细管柱进行程序升温技术分离，用GC-ECD同时检测，用内标物进行定量分析。结果高、中、低3个水平添加标样的回收率为82．32％～115．3％，相对标准偏差为1．5％～8．7％。该方法的检出限为：有机氯农药0．005～0．007mg·kg^-1，有机磷农药0．005～0．009mg·kg^-1，拟除虫菊酯0．005～0．008mg·kg^-1。绝大多数农药达到基线分离，分离度均在1．5以上。建立了利用原子吸收仪测定人参提取物中7种重金属的方法。采用HNO₃—HClO₄混酸消化，空气-乙炔火焰及氢化物发生原子吸收光谱法测定。结果高、中、低3个水平添加标样的回收率为85．37％～120．1％，相对标准偏差为2．7％～11．4％。建立了同时测定人参提取物中人参皂苷Rg₁、Rb₁、Re的HPLC色谱法。提取方法：70％乙醇加热回流，用水饱和的正丁醇萃取，残渣用甲醇溶解。采用DiamonsilC18柱；流动相：乙腈—0．1％磷酸溶液（三乙胺调pH=5），梯度洗脱；检测波长203nm；流速0．8mL·min^-1。加样的回收率为87．02％～102．3％，相对标准偏差为1．0％～2．5％。检出限为：Rg₁0．2350～4．700μg·g^-1，Rb₁0．2300～4．600μg·g^-1，Re0．2000～4．000μg·g^-1。建立了人参提取物中残留农药和重金属的脱除方法。筛选了50种吸附树脂，以农药、重金属去除率及人参有效成份的损失率为标准，优化选出一种树脂，进行四因素三水平正交实验法。通过试验结果得到最佳条件为：A₁B₃C₃D₂，树脂用量为20g；药液流速为0．5V／0．5h；洗水用量为1V；洗水流速为1V／h。研究证实该方法简便，重现性好，可加以深入研究，进而推广用于其他中药材提取物。这对提高中药材及中成药质量，推动中药国际化发展具有重要的意义。更多还原

【Abstract】 This article discusses the current status and types of pesticide contaminants found in plant material used to make Chinese herbal medicines in China. Research on maximum residue limit （MRL） standards for pesticide and heavy metals residues in Chinese herbal medicine plant material is also discussed. Feasible suggestions are proposed for dealing with the problem of pesticide and heavy metals residues exceeding standard levels allowed in plant material used for Chinese herbal medicine.With the development of Chinese Medicines, the quality of Chinese Medicines and their products is taken seriously by People. However, in the process of planting Chinese medicinal materials, because of remained agricultural chemicals in soil due to massive and long-term application of chemistry and polluted environment, pesticide and heavy metals in traditional Chinese medicines exceed those in the allowed standard. Thus the quality of Chinese native medicine and product quality is affected seriously. Chemistry has become one of main sources of pollution to Chinese medicines.At present, the study of detection and analysis from the pesticide and heavy metals in traditional Chinese medicines was concentrated relatively, and the study of the removal from them was few. So the effective removal of pesticide residues and heavy metals in the way, it is very necessary.The research has established the method which determines 10 kinds of organophosphorus pesticide, 4 kinds of organochlorine pesticide and 2 kinds of pyrethroid pesticide residues in the extracted ginseng by GC simultaneously. Pesticide residues were extracted from the extracted with acetone and n - hexane. Liquid - liquid extraction was performed with n - hexane and the clean - up of the extracted were made with alumina neutral - florisil column. Analytical screening was determined with internal-standard method by gas chromatography using capillary column equipped with electron - capture detector. The recovery obtained from the samples of the extracted of ginseng（ n = 3） at three concentration levels was in the ranges of 82.32%～115.3% , with relative standard deviations of 1.5%～8.7%. Detection limit was from 0.005 to 0.007mg·kg^-1 for organochlorines, 0.005 to 0.009mg·kg^-1 for organophosphorus and 0.005 to 0.008mg·kg^-1 for pyrethroids, respectively.The method with determining 7 kinds of heavy metals by atomic absorption spectrophotometry was set up. The samples were digested with HNO₃-HClO₄. The determining method was acetylene-flame and hydride generation atomic absorption spectrometry. The recovery obtained from the samples was in the ranges of 85.37% -120.1%, with relative standard deviations of 2.7%-11.4%.The establishing research was determined Ginsenoside Rg₁, Rb₁ and Re in the extracted ginseng by HPLC simultaneously. Ginsenosides were extracted from the extracted with 70% alcohol. Liquid - liquid extraction was performed with H₂O saturated n BuOH and the residue was dissolved with methanol. The medthod was used the Diamonsil C₁₈ column, the acetonitrile-0.1% phosphoric acid solution as the mobile phase with gradient elution（ pH=6.0,adjusted with triethylamine）, the UV detector was set at 203 nm and the flow rate of 0.8mL·min^-1. The recovery obtained from the samples was in the ranges of 87.02%～102.3% , with relative standard deviations of 1.0%～2.5%. Detection limit was from 0.2350 to 4.700μg·g^-1 for Rg₁, 0.2300 to 4.600μg·g^-1 for Rb₁ and 0.2000 to 4.000μg·g^-1 for Re, respectively.Through near 50 kinds of macroporous resin screening, the method optimizes the removal condition of the ginseng extraction’s pesticide and heavy metals residues with orthogonal test by the loss rate of the ginseng’s effective ingredient. The optimum condition is A₁B₃C₃D₂. the resin weight is 20 gram, the extract flows 0.5V/0.5h, the washing water is 1 volume, and the washing water speeds 1V/h.The results of research show that the recommended method is simple, reproducible, and can be used in testing pesticide residues in other extracts of Chinese medicinal materials. Therefore the method will be a great benefit to enhancing the quality of Chinese medicinal materials and Chinese traditional patent medicine, as a result impelling internationalization of Chinese native medicines.更多还原