青黛的质量考察与掺伪研究
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摘要
随着中医药现代化的推进,中医中药越来越多地被人们接受,近年来中药材的使用量也急剧增加。但常见有报道以次充好、以伪充真、掺伪染色中药材的现象。因此,我们收集药材,考察其质量,研究其掺伪方法以提供检测手段。本文对收集于全国各地的38批青黛或伪品青黛进行了研究,研究主要情况如下：
通过市场调查,发现青黛的造假严重,伪品较多,于是中国生物制品研究所、四川、重庆、广西等药检所收集了全国各地38批青黛样品,对此进行了质量考察与掺伪研究。
参考《中国药典》2010年版一部青黛项下的各项指标对38批青黛样品进行了火烧试验、浓硝酸试验、水溶性色素检查、薄层鉴别、水分测定、靛蓝、靛玉红的含量测定,结果发现38批样品中合格的仅有10批,劣等青黛4批,伪品青黛2/1批。伪品青黛占收集样品总量的63.16%,表明市场上假青黛太多,有必要对假青黛作进一步研究以便更好的进行控制。
首先,我们对假青黛的染色物质进行了研究。利用三氯甲烷、甲醇、水为溶剂对假青黛的染色剂进行溶出试验,发现共有15批假青黛的染色剂为蓝色,溶于甲醇或三氯甲烷,15批中有1批假青黛的蓝色素溶于水；无其他颜色的染色剂。对这15批假青黛色素的甲醇溶液进行薄层鉴别,发现其主要有2类色素,其中一类有8批样品,另一类有7批样品。这说明市场上用染色剂制造假青黛的主要色素是这2种色素。
接下来我们对这2种色素进行查找,主要用了2种方法：一,在市场上买一些常见的蓝色素,用薄层色谱的方法进行对比查找；二,对色素进行分离纯化,然后对纯化物进行波谱解析。结果：薄层对比市场上常见的分散蓝、还原蓝、酸性蓝、碱性蓝等几十种蓝色素,无一种能与这两种相同；对分离纯化的色素进行紫外分析、质谱解析、红外分析,发现其中一种色素为孔雀石绿。
然后以孔雀石绿标准品为对照,对8批疑含有孔雀石绿的样品进行薄层验证、高效液相色谱验证、液相色谱-质谱验证,结果证明了这些样品含有孔雀石绿。同时,利用验证过程的数据建立了药材中孔雀石绿、结晶紫的通用检测方法。针对青黛用孔雀石绿造假泛滥的情况,建立了青黛中孔雀石绿的高效液相色谱测定方法。对8批假青黛检测的结果为：孔雀石绿最低0.0144 mg·g-1,最高0.5658mg·g-1,平均0.2126 mg·g-1
最后,对比假青黛、青黛、熟石灰、泥土的灰分和钙含量,发现假青黛的酸不溶性灰分高达40%左右,钙含量为10%以下,与泥土的酸不溶性灰分和钙含量差不多,发现假青黛可能是用泥土为基质进行掺伪的。由于伪品青黛中有机成分不含有靛蓝、靛玉红等,而主要有孔雀石绿,证实了青黛是用孔雀石绿和泥土混合染色而成的。用泥土和孔雀石绿进行破解实验,得到的自制样品和假青黛样品相似。破解了伪品青黛造假的方法。
With the advancement of modernization of Chinese medicine, Chinese medicine is increasingly being accepted, and the use of Chinese herbal medicines also increased dramatically in recent years. But the most commonly been reported is the phenomenon of shoddy, pseudo charge true, adulteration of Chinese herbal medicines. Therefore, we collect medicinal herbs, examine its quality, study ways of adulteration for detection means.In this paper, we collected 38 batches of indigo throughout the country, the indigo has been studied to obtain the following results:
Through market surveys, found lots of counterfeit indigo. So the NIFDC, Sichuan, Chongqing, Guangxi Institute for Drug Control collected 38 batches of indigo.We checked their quality and researched the fake one.
Reference to the indicators of "Chinese Pharmacopoeia" a 2010 edition, We conducted a series of tests of 38 batches of samples:fire test, concentrated nitric acid test, check water-soluble pigment, TLC, moisture content, indigo, indirubin determination, and found that 10 of 38 batches were qualified,4 batches were inferior indigo,24 batches were counterfeit. Counterfeit indigo accounted 63.16% of total samples collected, indicating that the markets are too many fake indigo, fake indigo is necessary for further research to better control.
First of all, the dyeing substances in fake indigo were studied. Using chloroform, methanol and water as the solvent for dissolution test, there are a total of 15 batches of fake blue indigo dye, which soluble in methanol or chloroform, a batch of 15 batches of fake indigo's Blue pigment soluble in water; no other color dye. With TLC testing of those pigment in 15 batches of fake indigo and found that there are two main pigments, one have 8 batches of samples, and the other have 7 batches of samples. This shows that the dyeing color in fake indigo is the two kinds of pigment.
Next we look for these two kinds of pigment, mainly used 2 methods: first, we bought some of the common blue pigment in the market, and compared the bought one with the target pigment; Second, isolated and purified the pigments for spectral analysis. Results:The TLC comparing method don't found the pigments, but the other way found that a pigment is malachite green.
Then using malachite green as standard substance, verified that the 8 batches of samples contain malachite green by TLC, HPLC, HPLC-MS. At the same time, the general detection method of malachite green, crystal violet in Chinese herbal medicines have been established.8 batches of test results as fake indigo:malachite green minimum 0.0144 mg·g-1, the highest 0.5658 mg·g-1, an average of 0.2126 mg·g-1
Finally, comparison of ash content and calcium content, found fake indigo's acid insoluble ash content is as high as 40%, calcium content is under 10%, and it's similar to the soil. Therefore, we concluded that the Indigo may be maked up of soil. Since fake Indigo's components do not contain Indigo, indirubin, but contained only malachite green, etc. Initially speculated that part of the fake Indigo is made up of malachite green and clay. And using malachite green and clay to experiment to get the home-made samples,found that the home-made one is similar with fake indigo. thus we break the counterfeit methods of fake indigo.
通过市场调查,发现青黛的造假严重,伪品较多,于是中国生物制品研究所、四川、重庆、广西等药检所收集了全国各地38批青黛样品,对此进行了质量考察与掺伪研究。
参考《中国药典》2010年版一部青黛项下的各项指标对38批青黛样品进行了火烧试验、浓硝酸试验、水溶性色素检查、薄层鉴别、水分测定、靛蓝、靛玉红的含量测定,结果发现38批样品中合格的仅有10批,劣等青黛4批,伪品青黛2/1批。伪品青黛占收集样品总量的63.16%,表明市场上假青黛太多,有必要对假青黛作进一步研究以便更好的进行控制。
首先,我们对假青黛的染色物质进行了研究。利用三氯甲烷、甲醇、水为溶剂对假青黛的染色剂进行溶出试验,发现共有15批假青黛的染色剂为蓝色,溶于甲醇或三氯甲烷,15批中有1批假青黛的蓝色素溶于水；无其他颜色的染色剂。对这15批假青黛色素的甲醇溶液进行薄层鉴别,发现其主要有2类色素,其中一类有8批样品,另一类有7批样品。这说明市场上用染色剂制造假青黛的主要色素是这2种色素。
接下来我们对这2种色素进行查找,主要用了2种方法：一,在市场上买一些常见的蓝色素,用薄层色谱的方法进行对比查找；二,对色素进行分离纯化,然后对纯化物进行波谱解析。结果：薄层对比市场上常见的分散蓝、还原蓝、酸性蓝、碱性蓝等几十种蓝色素,无一种能与这两种相同；对分离纯化的色素进行紫外分析、质谱解析、红外分析,发现其中一种色素为孔雀石绿。
然后以孔雀石绿标准品为对照,对8批疑含有孔雀石绿的样品进行薄层验证、高效液相色谱验证、液相色谱-质谱验证,结果证明了这些样品含有孔雀石绿。同时,利用验证过程的数据建立了药材中孔雀石绿、结晶紫的通用检测方法。针对青黛用孔雀石绿造假泛滥的情况,建立了青黛中孔雀石绿的高效液相色谱测定方法。对8批假青黛检测的结果为：孔雀石绿最低0.0144 mg·g-1,最高0.5658mg·g-1,平均0.2126 mg·g-1
最后,对比假青黛、青黛、熟石灰、泥土的灰分和钙含量,发现假青黛的酸不溶性灰分高达40%左右,钙含量为10%以下,与泥土的酸不溶性灰分和钙含量差不多,发现假青黛可能是用泥土为基质进行掺伪的。由于伪品青黛中有机成分不含有靛蓝、靛玉红等,而主要有孔雀石绿,证实了青黛是用孔雀石绿和泥土混合染色而成的。用泥土和孔雀石绿进行破解实验,得到的自制样品和假青黛样品相似。破解了伪品青黛造假的方法。
With the advancement of modernization of Chinese medicine, Chinese medicine is increasingly being accepted, and the use of Chinese herbal medicines also increased dramatically in recent years. But the most commonly been reported is the phenomenon of shoddy, pseudo charge true, adulteration of Chinese herbal medicines. Therefore, we collect medicinal herbs, examine its quality, study ways of adulteration for detection means.In this paper, we collected 38 batches of indigo throughout the country, the indigo has been studied to obtain the following results:
Through market surveys, found lots of counterfeit indigo. So the NIFDC, Sichuan, Chongqing, Guangxi Institute for Drug Control collected 38 batches of indigo.We checked their quality and researched the fake one.
Reference to the indicators of "Chinese Pharmacopoeia" a 2010 edition, We conducted a series of tests of 38 batches of samples:fire test, concentrated nitric acid test, check water-soluble pigment, TLC, moisture content, indigo, indirubin determination, and found that 10 of 38 batches were qualified,4 batches were inferior indigo,24 batches were counterfeit. Counterfeit indigo accounted 63.16% of total samples collected, indicating that the markets are too many fake indigo, fake indigo is necessary for further research to better control.
First of all, the dyeing substances in fake indigo were studied. Using chloroform, methanol and water as the solvent for dissolution test, there are a total of 15 batches of fake blue indigo dye, which soluble in methanol or chloroform, a batch of 15 batches of fake indigo's Blue pigment soluble in water; no other color dye. With TLC testing of those pigment in 15 batches of fake indigo and found that there are two main pigments, one have 8 batches of samples, and the other have 7 batches of samples. This shows that the dyeing color in fake indigo is the two kinds of pigment.
Next we look for these two kinds of pigment, mainly used 2 methods: first, we bought some of the common blue pigment in the market, and compared the bought one with the target pigment; Second, isolated and purified the pigments for spectral analysis. Results:The TLC comparing method don't found the pigments, but the other way found that a pigment is malachite green.
Then using malachite green as standard substance, verified that the 8 batches of samples contain malachite green by TLC, HPLC, HPLC-MS. At the same time, the general detection method of malachite green, crystal violet in Chinese herbal medicines have been established.8 batches of test results as fake indigo:malachite green minimum 0.0144 mg·g-1, the highest 0.5658 mg·g-1, an average of 0.2126 mg·g-1
Finally, comparison of ash content and calcium content, found fake indigo's acid insoluble ash content is as high as 40%, calcium content is under 10%, and it's similar to the soil. Therefore, we concluded that the Indigo may be maked up of soil. Since fake Indigo's components do not contain Indigo, indirubin, but contained only malachite green, etc. Initially speculated that part of the fake Indigo is made up of malachite green and clay. And using malachite green and clay to experiment to get the home-made samples,found that the home-made one is similar with fake indigo. thus we break the counterfeit methods of fake indigo.
引文
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[2]龙国友,唐莉.青黛及其一种伪品的鉴别[J].时珍国医国药,2004,25(2):67
[3]程力惠,李晓蒙.青黛的质量鉴别[J].中医药导报,2006,12(12):77,87
[4j瞿毓秀,郭莹莹,耿霞,等.孔雀石绿的代谢机理及生物毒性研究进展[J].中国海洋大学学报,2007,37(z)27-32
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[2]杜雄心,唐晓晏.541批次不合格中药饮片、中药材质量分析[J].亚太传统医药,2010,9(6)：177-178
[3]崔晓林.京城“中药贩子”调查.中国经济周刊,www.ceweeklv.cn
[4]刘世军,熊英.西红花的真伪鉴别[J].甘肃中医,2009,22(3)：
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[2]龙国友,唐莉.青黛及其一种伪品的鉴别[J].时珍国医国药,2004,25(2):67
[3]程力惠,李晓蒙.青黛的质量鉴别[J].中医药导报,2006,12(12):77,87
[4j瞿毓秀,郭莹莹,耿霞,等.孔雀石绿的代谢机理及生物毒性研究进展[J].中国海洋大学学报,2007,37(z)27-32
[1]薛文卿,林展翼,张启甲.中药材走向世界竞争力是关键.中国质量新闻网,2011-03-11 08：18：07
[2]杜雄心,唐晓晏.541批次不合格中药饮片、中药材质量分析[J].亚太传统医药,2010,9(6)：177-178
[3]崔晓林.京城“中药贩子”调查.中国经济周刊,www.ceweeklv.cn
[4]刘世军,熊英.西红花的真伪鉴别[J].甘肃中医,2009,22(3)：
[5]王双,刘兴华,董晓光.西红花的真伪鉴别[J].时珍国医国,2006,17(2)：249
[6]黎跃成.中药材真伪鉴别彩色图谱大全[M].成都：四川科学技术出版社,1994：560
[7]胡双丰,陈军.一种西红花掺伪品鉴别[J].中南药学,2010,8(9)：686-688
[8]吴晓春.西红花伪品的鉴别[J].中成药,2005,27(7)：840-842
[9]黄海燕,钟建理,谢黔锋.冬虫夏草质量控制方法研究概况[J].中国药业,2010，19(9)：88-90
[10]金宏谟,岳东文.冬虫夏草的真伪鉴别[J].长春中医药大学学报,2008,24(2)：37
[11]白景义,邵苏燕.冬虫夏草及几种常见伪品的鉴别方法[J].辽宁中医杂志,2008,35(5)：755
[12]卓丹如.冬虫夏草及其混伪品的鉴别[J].海峡药学,2008,20(8)：77-79
[13]魏桂芳,程含芳.冬虫夏草的真伪鉴定[J].实用医技杂志,2005,12(4)：1011
[14]陈慧浓.冬虫夏草及其伪品亚香棒虫草的鉴别[J].中国药业2008,16(14)：57-58
[15]王霞玲,童树洪.冬虫夏草正品与伪品及混淆品的鉴别[J].中国药业,2009，18(18)：75-76
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