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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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> Hg>Pb >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,通心络稀释若干倍铜的测定湿法消解测定值0.9μg. g-1高于干法灰化0.69μg.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0.91μg.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,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25°C,洗脱剂用量为9倍量体积的树脂效果最好。
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 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, circulation 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 severity is Cd> Hg> Pb> As> Cu; Cd's 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 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 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 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 of copper in a number of times the measured value of the wet digestion 0.9μg. g-1 higher than the dry ashing 0.69μg.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, determination of lead is 365 ng.g-1 did not decrease, the determination of the value of copper has increased 0.91μg.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 dry 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 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 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 2001 formulated the《Import and 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 the determination of wet digestion of copper measured values 0.9μg/g higher than the dry Ashing 0.69μg/g; Lead determination dry ashing 358ng/g measured value is higher than the wet digestion using PTEE 305 ng/g; dissolved in nitric acid with 10% of dry ash digestion , Determination of lead is 365 ng/g did not decrease, the determination of the value of copper has increased 0.91μg/g; choose dry ashing, acid method is more suitable for Copper, Lead and Cadmium in Chinese atomic absorption spectrometry determination of prior treatment. Determination of cadmium values measured with dry 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 .
High content of selected heavy metals Tongxinluo capsule technology as an inorganic ion resin rid study Tongxinluo capsule Yiqihuoxue, Tongluozhitong effect, is commonly used in clinical cardiovascular and cerebrovascular diseases effective drugs; for Coronary Heart Disease angina, myocardial infarction, arrhythmia, myocardial ischemia diseases have a good effect; for cerebral infarction, cerebral ischemia, cerebral hemorrhage, stroke sequelae have a significant effect.
HPLC method was established to determine the medicine Tongxinluo Paeoniflorin capsules, the USP using 70% methanol into a non-toxic ultrasonic treatment of 70% ethanol. Through the study found that the method is accurate, reliable, fast, easy, and determined by the method of Tongxinluo in paeoniflorin.
Resin with inorganic ions in the copper Tongxinluo get rid of lead and cadmium in the experiment, to find an effective way to get rid of heavy metals: The TXL treated samples of inorganic ions on the resin column, the column before and after the determination of heavy metals and the active ingredients of these three Calculation of paeoniflorin Copper, Lead and cadmium content of the active ingredients drive out rate and recovery of paeoniflorin, the test found that the yield of the three resins paeoniflorin in excess of 95%, SIB-1 resin> SICu resin> SI-2 resin. SIB-1 resin, which after recovery 101.04%, SICu resin rid of 100% copper, is a valid drive out of copper material. SIB-1 resin is better than SI-2 resin, two resin rid of lead in more than 95%. Get rid of the three resin effects of cadmium is not good ,were below 85%. SIB-1 resin as the recovery and removal of paeoniflorin significant effect of lead, get rid of the resin for the three heavy metals of factors: alcohol eluant, temperature, PH value, eluent flow rate and other factors were investigated . The results showed that 70% ethanol, 1.5mL/min flow rate, 1.7 times the amount of resin, PH 6, temperature 25°C, the amount of eluent volume was 9 times the amount of resin was the best.
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> Hg>Pb >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,通心络稀释若干倍铜的测定湿法消解测定值0.9μg. g-1高于干法灰化0.69μg.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0.91μg.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,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25°C,洗脱剂用量为9倍量体积的树脂效果最好。
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 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, circulation 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 severity is Cd> Hg> Pb> As> Cu; Cd's 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 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 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 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 of copper in a number of times the measured value of the wet digestion 0.9μg. g-1 higher than the dry ashing 0.69μg.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, determination of lead is 365 ng.g-1 did not decrease, the determination of the value of copper has increased 0.91μg.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 dry 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 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 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 2001 formulated the《Import and 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 the determination of wet digestion of copper measured values 0.9μg/g higher than the dry Ashing 0.69μg/g; Lead determination dry ashing 358ng/g measured value is higher than the wet digestion using PTEE 305 ng/g; dissolved in nitric acid with 10% of dry ash digestion , Determination of lead is 365 ng/g did not decrease, the determination of the value of copper has increased 0.91μg/g; choose dry ashing, acid method is more suitable for Copper, Lead and Cadmium in Chinese atomic absorption spectrometry determination of prior treatment. Determination of cadmium values measured with dry 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 .
High content of selected heavy metals Tongxinluo capsule technology as an inorganic ion resin rid study Tongxinluo capsule Yiqihuoxue, Tongluozhitong effect, is commonly used in clinical cardiovascular and cerebrovascular diseases effective drugs; for Coronary Heart Disease angina, myocardial infarction, arrhythmia, myocardial ischemia diseases have a good effect; for cerebral infarction, cerebral ischemia, cerebral hemorrhage, stroke sequelae have a significant effect.
HPLC method was established to determine the medicine Tongxinluo Paeoniflorin capsules, the USP using 70% methanol into a non-toxic ultrasonic treatment of 70% ethanol. Through the study found that the method is accurate, reliable, fast, easy, and determined by the method of Tongxinluo in paeoniflorin.
Resin with inorganic ions in the copper Tongxinluo get rid of lead and cadmium in the experiment, to find an effective way to get rid of heavy metals: The TXL treated samples of inorganic ions on the resin column, the column before and after the determination of heavy metals and the active ingredients of these three Calculation of paeoniflorin Copper, Lead and cadmium content of the active ingredients drive out rate and recovery of paeoniflorin, the test found that the yield of the three resins paeoniflorin in excess of 95%, SIB-1 resin> SICu resin> SI-2 resin. SIB-1 resin, which after recovery 101.04%, SICu resin rid of 100% copper, is a valid drive out of copper material. SIB-1 resin is better than SI-2 resin, two resin rid of lead in more than 95%. Get rid of the three resin effects of cadmium is not good ,were below 85%. SIB-1 resin as the recovery and removal of paeoniflorin significant effect of lead, get rid of the resin for the three heavy metals of factors: alcohol eluant, temperature, PH value, eluent flow rate and other factors were investigated . The results showed that 70% ethanol, 1.5mL/min flow rate, 1.7 times the amount of resin, PH 6, temperature 25°C, the amount of eluent volume was 9 times the amount of resin was the best.
引文
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