中药铜铅镉含量测定与无机离子树脂驱除技术研究

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1、 I摘 要 中药是中华民族的瑰宝,在预防、保健、调节人体机能等方面,有合成药物无可替代的作用,据世界卫生组织统计全世界有 80%的人口在使用中药。然而,重金属污染问题成为中药走向国际市场的严重障碍,阻碍了中药事业的发展。 重金属可引起神经系统、消化系统、呼吸系统、循化系统毒性;我们国家对铅、镉、铜、 砷、 汞等重金属总量规定了限定标准。 通过查阅文献统计了当前重金属的污染现状,发现:大部分中药都含有一定量的重金属,有些超标还比较严重;超标严重程度为 Cd HgPb As Cu;Cd 的超标率高达 26.3%。 重金属的驱除方法目前主要有超临界 CO2萃取法,大孔树脂螯合技术,絮凝法等。至今还未

2、见无机离子树脂用于中药重金属污染驱除的文献报道。 为了解市售中药的重金属污染情况,筛选了 15 种常用中成药,采用石墨炉原子吸收法测定了铅和镉的含量, 火焰原子吸收法测定铜的含量。 通过测试结果分析我们得到:通心络的铜的含量为 32.25mg.kg- 1,铅的含量为 16.937 mg.kg- 1,镉的含量为 0.589 mg.kg- 1;桑菊感冒片中镉的含量为 0.3685 mg.kg- 1。这些均超出了我国 2001 年对外贸易合作部制订的 药用植物及制剂进出口绿色行业标准 。参照药典的基础上建立了 15种中成药铜铅镉含量测定的方法,通过比较湿法消解和干法灰化法处理的样品发现,通心络稀释若

3、干倍铜的测定湿法消解测定值 0.9g. g- 1高于干法灰化 0.69g.g- 1;铅的干法灰化测定是 358ng.g- 1测定值高于湿法使用 PTEE 消解 305 ng.g- 1;加入 10%的硝酸溶解干法消解的灰烬,铅的测定值为 365 ng.g- 1没有减少,铜的测定值 0.91g.g- 1有提高;选择干法灰化,酸溶法更适合中药铜铅镉原子吸收法含量测定的前处理。镉的测定值也有干法灰化测的值 9.7ppb,加入 10%的硝酸溶解得到结果 10.6 ppb,选择干法灰化,酸溶法更适合中药铜铅镉原子吸收法含量测定的前处理。 选择了重金属含量较高的通心络胶囊作为无机离子树脂驱除技术研究对象,

4、通心络胶囊具有益气活血,通络止痛功效,是临床常用于心脑血管疾病的有效药物;对于冠心病心绞痛、心肌梗死、心律失常、心肌缺血疾病有很好疗效;对于脑梗死、脑缺血、脑出血、中风后遗症有明显的疗效。 建立了 HPLC 法,测定了中药通心络胶囊中芍药苷的含量,把药典中用 70%甲醇超II 声处理改成了无毒的 70%乙醇。通过研究发现表明该方法准确、可靠、快捷、操作方便,并用该方法测定了通心络中芍药苷的含量。 采用无机离子树脂驱除通心络中铜铅镉的实验,找到了一种有效驱除重金属的方法:将通心络样品经处理后上无机离子树脂柱,测定上柱前后这三种重金属和有效成分芍药苷含量变化,计算铜铅镉的驱除率和有效成分芍药苷的回

5、收率,通过测试发现三种树脂芍药苷的收率都超过了 95%:SIB- 1 树脂 SICu 树脂 SI- 2 树脂,其中 SIB- 1 树脂处理后回收率高达 101.04%,SICu 树脂对铜的驱除率达 100%,是一种驱除铜的有效材料。SIB- 1 树脂优于 SI- 2 树脂,两种树脂对铅的驱除率达 95%以上。三种树脂对镉的驱除效果不够理想最高为 85%。由于 SIB- 1 树脂芍药苷的回收率和驱除铅的效果显著,对于该树脂驱除三种重金属的影响因素:洗脱剂的醇度、温度、PH 值、洗脱剂流速等因素进行了考察。结果表明 70%乙醇,1.5mL/min 流速,1.7 倍量的树脂,PH 为 6,温度25C

6、,洗脱剂用量为 9 倍量体积的树脂效果最好。 关键词:铜、铅、镉、含量测定、无机离子树脂、重金属脱除IIIABSTRACT Chinese medicine is a treasure of Chinese nation, in the prevention, care, regulate body functions, etc., there is no substitute for the role of synthetic drugs. According to the World Health Organization, 80% of the population around the

7、 world in the use of traditional Chinese medicine, However, heavy metal pollution in recent years, traditional Chinese medicine to the international market as a serious obstacle to the development of Chinese medicine. Heavy metals can cause nervous system, digestive system, respiratory system, circu

8、lation system toxicity; our country on the lead, cadmium, copper, arsenic, mercury and other heavy metals provided the total limit standard.Statistics of the current status of pollution and found that: most Chinese have a certain amount of heavy metals, some quite serious overweight; excessive sever

9、ity is Cd Hg Pb As Cu; Cds excessive rate of 26.3%. Get rid of heavy metals are present method of supercritical CO2 extraction, macroporous resin sequestration technologies, flocculation method.Inorganic ions has not yet been found in resins used in Chinese medicine get rid of heavy metals reported

10、in the literature. To understand the commercial heavy metal pollution in Chinese medicine, screening for 15 commonly used Chinese medicine, the use of graphite furnace atomic absorption spectrometry of lead and cadmium by flame atomic absorption determination of copper content. Analysis of the test

11、results we get: Tongxinluo copper content of 32.25mg.kg- 1, lead content of 16.937 mg.kg- 1, cadmium content of 0.589 mg.kg- 1; Sang Ju cold tablets of cadmium The content of 0.3685 mg.kg- 1. These are beyond China in 2001 formulated by the Ministry of Foreign Trade and Cooperation, “the import and

12、export of medicinal plants and preparation of green industry standards.“ Pharmacopoeia reference to the basis of the establishment of 15 Chinese herbs Copper, Lead and cadmium content of the method, by comparing the wet digestion and dry ashing sample treatment found that TXL dilution determination

13、of copper in a number of times the measured value of the wet digestion 0.9g. g- 1 higher than the dry ashing 0.69g.g- 1; Lead Determination dry ashing 358ng.g- 1 measured value is higher than the wet digestion using PTEE 305 ng.g- 1; adding 10% nitric acid dissolution of dry ash digestion, determina

14、tion of lead is 365 ng.g- 1 did not decrease, the determination of the value of IV copper has increased 0.91g.g- 1; choose dry ashing, acid method is more suitable for Copper, Lead and Cadmium Atomic medicine Determination of absorption pre- treatment. Determination of cadmium values measured with d

15、ry ash values 9.7ppb, adding 10% nitric acid solution by the results of 10.6 ppb., Select the dry ashing, acid method is more suitable for Chinese Copper, Lead and Cadmium by Atomic Absorption Spectrometry Determination of the pre- treatment . To understand the commercial heavy metal pollution in Ch

16、inese medicine, screening for 15 commonly used Chinese medicine, the use of graphite furnace atomic absorption spectrometry of lead and cadmium by flame atomic absorption determination of copper content. Analysis of the test results we get: Tongxinluo copper content of 32.25mg.kg- 1, lead content of 16.937mg/kg of cadmium content of 0.589 mg/kg; SangJu cold tablets of cadmium content of 0.3685. These values are beyond the cooperation of the Ministry of Foreign Trade in

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