Method for removing heavy metal residues in traditional Chinese medicinal materials and application of method in preparation of fifteen-ingredient gentiana scabra bunge pills

Abstract

The invention discloses a method for removing heavy metal residues in traditional Chinese medicinal materials and application of the method in preparation of fifteen-ingredient gentiana scabra bunge pills, and relates to the technical field of heavy metal removal in traditional Chinese medicinal materials. The method comprises the following steps: (1) adding carboxymethyl chitosan and microcrystalline cellulose into a traditional Chinese medicinal material extracting solution, adjusting the pH value to 6-8, and carrying out microwave treatment to obtain a treatment solution; and (2) adjusting the pH value of the treating fluid obtained in the step (1) to 4-6, and separating the filtrate. The method has an efficient removal effect on lead (Pb), cadmium (Cd), arsenic (As), mercury (Hg) and copper (Cu), the transfer rate of effective components is high, the method can be used for preparing the fifteen-ingredient gentian flower pills, and the use safety of Tibetan medicine is improved.

Description

Technical Field

[0001] The invention relates to the technical field of heavy metal removal from traditional Chinese medicines, and in particular to a method for removing heavy metal residues from traditional Chinese medicines and application of the method in preparing fifteen-flavor gentian flower pills. Background Art

[0002] The 15-flavor gentian flower pill is made of 15 kinds of medicines, including white gentian, sandalwood, terminalia chebula, emblica, travertine, jujube clove, nutmeg, agarwood, bashaga, stemless mustard, and licorice. The Tibetan medicine name is "Bangjian Jiuer Ribu". The main effects are clearing heat and regulating the lungs, relieving cough and reducing phlegm. It is used for bronchitis and emphysema, cough and asthma, hoarseness, and has good therapeutic effects. However, medicinal plants are easily polluted by heavy metals in the environment during their growth, which poses a potential threat to human health.

[0003] Heavy metals refer to metal impurities that can react with thioacetamide or sodium sulfide to develop color under experimental conditions. Heavy metals have a significant inhibitory effect on many normal physiological functions of the human body. At the same time, excessive heavy metal content in the body can lead to the occurrence of various diseases. Lead is easy to accumulate and poison in the human body. When the content reaches 12g / L or more, functional paralysis and encephalopathy may occur, directly damaging the thyroid function of humans and animals, reducing the ability of the thyroid to absorb iodine and plasma protein to bind iodine, reducing the secretion of pituitary hormones and the function of the adrenal cortex, and can also damage reproductive cells and reduce sexual function. Mercury is one of the most toxic heavy metals and can contaminate medicines through various channels. After being absorbed by the human body, mercury accumulates in the human body, affecting the central nervous system of the human body, leading to hearing loss, speech loss, limb paralysis and even dementia. Antimony and its compounds are similar to arsenic in toxicity to the human body. They mainly combine with the sulfhydryl group of the enzyme system in human cells, causing enzyme dysfunction and affecting normal cell metabolism. Tin is an essential element for the human body, but its organic compounds are highly toxic. When it exceeds 250mg / L, it can cause poisoning reactions, and severe brain edema occurs. The toxicity of cadmium to the human body is similar to that of lead. It suppresses the human immune system and causes tumors and aging. Although cadmium and copper are essential elements for the human body, hexavalent chromium is toxic and a carcinogen. It can interfere with the enzyme activity of many traditional Chinese medicines and damage the liver and kidneys. Copper has a hemolytic effect and can cause benign necrosis of the liver and kidneys. Heavy metals such as As, Hg, Pb, and Cd are all research hotspots on toxic trace elements in traditional Chinese and Tibetan medicines.

[0004] CN112973190 A discloses a method for removing heavy metals from a Chinese medicine extract, comprising the following steps: adding Chinese medicinal materials to an aqueous solution for decoction, filtering out the drug residue, and retaining the filtrate; adding water to the drug residue for decoction again, filtering out the drug residue, and retaining the filtrate; combining the two filtrates, adding a CuS@magnetic chitosan composite adsorbent, stirring, and separating to obtain a Chinese medicine extract with a low heavy metal content. The method for removing heavy metals from a Chinese medicine extract provided by the present invention has the advantages of simple process and high heavy metal removal rate. The method can simultaneously remove five heavy metal elements of lead (Pb), cadmium (Cd), arsenic (As), mercury (Hg), and copper (Cu) from the Chinese medicine extract. The preparation of the adsorbent CuS@magnetic chitosan involved in the method is relatively complicated and has a high cost.

[0005] Macroporous resin adsorption is also a treatment method for heavy metal pollution in traditional Chinese medicine. Wei Jixin et al. investigated the removal rate of heavy metal ions in Radix Isatidis extract by two chelating resins, taking the dry paste yield as an indicator, and found that the loss of dry paste yield after removing heavy metals was less than 7%. However, the adsorption effect of macroporous adsorption resin is easily affected by the adsorption environment and is relatively unstable. At the same time, it is usually difficult to determine good process conditions and the operation is complicated.

[0006] In view of this, the present invention provides a method for removing heavy metal residues in traditional Chinese medicine and its application in the preparation of Fifteen-flavor Longdanhua Pills. The process is simple and can achieve efficient removal of multiple heavy metal ions for multiple Tibetan medicinal ingredients in the Fifteen-flavor Longdanhua Pills. Summary of the invention

[0007] In view of this, the purpose of the present invention is to provide a method for removing heavy metal residues in traditional Chinese medicine and its application in the preparation of Fifteen-flavor Longdanhua Pills, which has a high efficient removal effect on lead (Pb), cadmium (Cd), arsenic (As), mercury (Hg), and copper (Cu), and has a high transfer rate of effective ingredients. It can be used in the preparation of Fifteen-flavor Longdanhua Pills to improve the safety of Tibetan medicine.

[0008] To achieve the above-mentioned object of the invention, the technical solution of the present invention is as follows:

[0009] In one aspect, the present invention provides a method for removing heavy metal residues from traditional Chinese medicine, comprising the following steps:

[0010] (1) adding carboxymethyl chitosan and microcrystalline cellulose to a Chinese medicinal material extract, adjusting the pH to 6-8, and subjecting the extract to microwave treatment to obtain a treated solution;

[0011] (2) The pH of the treated solution obtained in step (1) is adjusted to 4-6, and the filtrate is separated.

[0012] Preferably, in step (1), the mass ratio of carboxymethyl chitosan to microcrystalline cellulose is 2-5:1, more preferably 3-5:1, and most preferably 4:1.

[0013] Preferably, in step (1), the amount of carboxymethyl chitosan added is 0.5-5% of the mass of the Chinese herbal medicine extract, and the amount of microcrystalline cellulose added is 0.1-2.5% of the mass of the Chinese herbal medicine extract.

[0014] Further preferably, the amount of carboxymethyl chitosan added is 2% of the mass of the Chinese herbal medicine extract, and the amount of microcrystalline cellulose added is 0.5% of the mass of the Chinese herbal medicine extract.

[0015] Preferably, in step (1), the pH is adjusted to 7.5.

[0016] Preferably, in step (1), the microwave treatment conditions are: microwave power of 80-150 W, and treatment time of 30-60 min. Further preferably, the microwave treatment conditions are: microwave power of 120 W, and treatment time of 45 min.

[0017] Preferably, in step (1), the Chinese medicinal material extract is prepared according to the following method:

[0018] The Chinese medicinal material is decocted with water for the first time, and filtered to obtain a filter residue and a filtrate 1; the filter residue is decocted with water for the second time, and filtered to obtain a filtrate 2, and the filtrate 1 and the filtrate 2 are combined to obtain a Chinese medicinal material extract.

[0019] Further preferably, the conditions for the first decoction are: adding water 5-15 times the weight of the Chinese medicinal materials, heating to boiling, and decocting for 40-120 minutes.

[0020] Further preferably, the conditions for the second decoction are: adding 5-15 times the weight of water of the filter residue, heating to boiling, and decoct for 20-60 minutes.

[0021] Further preferably, the Chinese medicinal materials include gentiana alba, sandalwood, terminalia chebula, terminalia chebula, emblica emblica, travertine, costusroot, jujube, clove, nutmeg, smilax glabra, agarwood, baxiaga, mustard and licorice.

[0022] Further preferably, the Chinese medicinal materials include, by weight, 10-40 parts of Gentiana scabra, 10-40 parts of Santalum album, 1-20 parts of Terminalia chebula, 1-20 parts of Terminalia chebula, 1-20 parts of Phyllanthus emblica, 1-15 parts of Travertine, 1-15 parts of Aucklandia lappa, 1-15 parts of Ziziphus jujuba, 1-15 parts of Clove, 1-15 parts of Myristica fragrans, 1-15 parts of Caulis Trichosanthis, 1-15 parts of Aquilaria woods, 1-5 parts of Bashaga, 1-5 parts of Brassica juncea and 10-40 parts of Licorice.

[0023] Most preferably, the Chinese medicinal materials, in parts by weight, include 30 parts of Gentiana dahurica, 30 parts of Santalum album, 15 parts of Terminalia chebula, 10 parts of Terminalia chebula, 10 parts of Phyllanthus emblica, 10 parts of Travertine, 10 parts of Aucklandia lappa, 10 parts of Ziziphus jujuba, 12 parts of Cloves, 12 parts of Myristica fragrans, 12 parts of Caulis Trichosanthis, 10 parts of Aquilaria woods, 3 parts of Bashaga, 3 parts of Brassica juncea and 25 parts of Licorice.

[0024] Preferably, in step (2), the pH is adjusted to 5.

[0025] Preferably, in step (2), the method of separating the filtrate includes but is not limited to filtration separation, centrifugal separation, membrane separation and other conventional separation methods in the art.

[0026] On the other hand, the present invention provides the use of the above-mentioned method for removing heavy metal residues from traditional Chinese medicines in the preparation of Shiwuwei Longdanhua Pills.

[0027] As one of the implementation schemes, the application comprises the steps of:

[0028] (1) adding water to the Chinese medicinal material and boiling it for the first time, filtering to obtain filter residue 1 and filtrate 1; adding water to the filter residue and boiling it for the second time, filtering to obtain filter residue 2 and filtrate 2, combining filtrate 1 and filtrate 2 to obtain a Chinese medicinal material extract;

[0029] (2) adding carboxymethyl chitosan and microcrystalline cellulose to the Chinese medicinal material extract obtained in step (1), adjusting the pH to 6-8, and subjecting the mixture to microwave treatment to obtain a treated solution;

[0030] (3) adjusting the pH of the treated solution obtained in step (2) to 4-6, and separating the filtrate;

[0031] (4) The filtrate is concentrated and dried, and combined with the filter residue 1 and the filter residue 2 to make pills to obtain the fifteen-flavor gentian flower pills.

[0032] The beneficial effects of the present invention are:

[0033] (1) The present invention uses carboxymethyl chitosan combined with microcrystalline cellulose for combined adsorption under microwave conditions, which can effectively remove heavy metal residues in a short time and with a simple process;

[0034] (2) Targeting the various Tibetan medicinal ingredients in Shiwuwei Longdanhua Pills, the simultaneous and efficient removal of lead (Pb), cadmium (Cd), arsenic (As), mercury (Hg), and copper (Cu) was achieved;

[0035] (3) It has little impact on medicinal materials and has a high transfer rate of effective ingredients. DETAILED DESCRIPTION

[0036] In order to make the technical means, creative features, purpose and efficacy of the present invention easy to understand, the present invention is further explained in conjunction with specific embodiments below, but the following embodiments are only preferred embodiments of the present invention, not all. Based on the embodiments in the implementation mode, other embodiments obtained by those skilled in the art without creative work all belong to the protection scope of the present invention. In the following embodiments, unless otherwise specified, the operating methods used are conventional operating methods, the equipment used are conventional equipment, and the equipment materials used in each embodiment are the same.

[0037] In the following examples, the sources of raw materials are as follows:

[0038] Microcrystalline cellulose was purchased from Guangdong Dingsheng Food, and carboxymethyl chitosan was purchased from Kanghe Pharmaceutical, product number KH-SJ158, CAS: 83512-85-0.

[0039] Example 1

[0040] (1) Weigh 30 parts of Gentiana dahurica, 30 parts of Santalum album, 15 parts of Terminalia chebula, 10 parts of Terminalia chebula, 10 parts of Phyllanthus emblica, 10 parts of Travertine, 10 parts of Aucklandia lappa, 10 parts of Fructus zizyphi, 12 parts of Clove, 12 parts of Myristica fragrans, 12 parts of Caulis lappae, 10 parts of Aquilaria carmichaelii, 3 parts of Mustarda australis, and 25 parts of Licorice, mix well, add 10 times the weight of water for the first decoction, decoct for 60 minutes, filter, and obtain a residue and filtrate 1; add 12 times the weight of water for the second decoction, decoct for 40 minutes, filter, and obtain filtrate 2, and combine filtrate 1 and filtrate 2 to obtain a Chinese herbal medicine extract.

[0041] (2) adding solutions of Pb, Cd, As, Hg and Cu to the Chinese herbal medicine extract so that the mass content of each metal ion in the extract is 2.5 μg / g of lead, 0.5 μg / g of cadmium, 1 μg / g of arsenic, 0.1 μg / g of mercury and 10 μg / g of copper, and mixing well to prepare for heavy metal removal treatment: adding carboxymethyl chitosan and microcrystalline cellulose, wherein the amount of carboxymethyl chitosan added is 2% of the mass of the Chinese herbal medicine extract, and the amount of microcrystalline cellulose added is 0.5% of the mass of the Chinese herbal medicine extract, adjusting the pH to 7.5, performing microwave treatment, the microwave power is 120 W, and the treatment time is 45 min to obtain a treated solution;

[0042] (3) The treated liquid obtained in step (1) was adjusted to pH 5, allowed to stand for 5 hours, and the filtrate was separated.

[0043] Example 2

[0044] The difference from Example 1 is that the amount of carboxymethyl chitosan added is 4% of the mass of the Chinese medicinal material extract, and the amount of microcrystalline cellulose added is 1% of the mass of the Chinese medicinal material extract.

[0045] Example 3

[0046] The difference from Example 1 is that the amount of carboxymethyl chitosan added is 5% of the mass of the Chinese medicinal material extract, and the amount of microcrystalline cellulose added is 2.5% of the mass of the Chinese medicinal material extract.

[0047] Example 4

[0048] The difference from Example 1 is that the amount of carboxymethyl chitosan added is 1.5% of the mass of the Chinese medicinal material extract, and the amount of microcrystalline cellulose added is 1% of the mass of the Chinese medicinal material extract.

[0049] Example 5

[0050] The difference from Example 1 is that the amount of carboxymethyl chitosan added is 0.5% of the mass of the Chinese medicinal material extract, and the amount of microcrystalline cellulose added is 2% of the mass of the Chinese medicinal material extract.

[0051] Example 6

[0052] The difference from Example 1 is that the amount of carboxymethyl chitosan added is 8% of the mass of the Chinese medicinal material extract, and the amount of microcrystalline cellulose added is 2% of the mass of the Chinese medicinal material extract.

[0053] Example 7

[0054] Different from Example 1, the microwave treatment conditions are: microwave power is 80 W, and the treatment time is 30 min.

[0055] Example 8

[0056] Different from Example 1, the microwave treatment conditions are: microwave power is 150 W, and the treatment time is 60 min.

[0057] Comparative Example 1

[0058] (1) Step (1) is the same as in Example 1.

[0059] (2) adding solutions of Pb, Cd, As, Hg and Cu to the Chinese herbal medicine extract so that the mass content of each metal ion in the extract is 2.5 μg / g of lead, 0.5 μg / g of cadmium, 1 μg / g of arsenic, 0.1 μg / g of mercury and 10 μg / g of copper, and mixing well to prepare for heavy metal removal treatment: adding carboxymethyl chitosan and microcrystalline cellulose, wherein the amount of carboxymethyl chitosan added is 2% of the mass of the Chinese herbal medicine extract, and the amount of microcrystalline cellulose added is 0.5% of the mass of the Chinese herbal medicine extract, adjusting the pH to 7.5, and ultrasonically treating at 400 W for 45 min to obtain a treated solution;

[0060] (3) The treated liquid obtained in step (1) was adjusted to pH 5, allowed to stand for 5 hours, and the filtrate was separated.

[0061] Comparative Example 2

[0062] (1) Step (1) is the same as in Example 1.

[0063] (2) adding solutions of Pb, Cd, As, Hg and Cu to the Chinese herbal medicine extract so that the mass content of each metal ion in the extract is 2.5 μg / g of lead, 0.5 μg / g of cadmium, 1 μg / g of arsenic, 0.1 μg / g of mercury and 10 μg / g of copper, and mixing well to prepare for heavy metal removal treatment: adding carboxymethyl chitosan, wherein the amount of carboxymethyl chitosan added is 2.5% of the mass of the Chinese herbal medicine extract, adjusting the pH to 7.5, performing microwave treatment, the microwave power is 120 W, and the treatment time is 45 min to obtain a treated solution;

[0064] (3) The treated liquid obtained in step (1) was adjusted to pH 5, allowed to stand for 5 hours, and the filtrate was separated.

[0065] Comparative Example 3

[0066] (1) Step (1) is the same as in Example 1.

[0067] (2) adding solutions of Pb, Cd, As, Hg and Cu to the Chinese herbal medicine extract so that the mass content of each metal ion in the extract is 2.5 μg / g of lead, 0.5 μg / g of cadmium, 1 μg / g of arsenic, 0.1 μg / g of mercury and 10 μg / g of copper, and mixing well to prepare for heavy metal removal treatment: adding microcrystalline cellulose, wherein the amount of microcrystalline cellulose added is 2.5% of the mass of the Chinese herbal medicine extract, adjusting the pH to 7.5, performing microwave treatment, the microwave power is 120 W, and the treatment time is 45 min to obtain a treated solution;

[0068] (3) The treated liquid obtained in step (1) was adjusted to pH 5, allowed to stand for 5 hours, and the filtrate was separated.

[0069] Results

[0070] 1. Heavy metal removal rate

[0071] Detection method: Determine the heavy metal content in the traditional Chinese medicine extract according to the inductively coupled plasma mass spectrometry in 2321 Determination of Lead, Cadmium, Arsenic, Mercury and Copper in the Pharmacopoeia 2020 Edition, and calculate the heavy metal removal rate.

[0072] Heavy metal removal rate (%) = (heavy metal content of the extract before removal - heavy metal content of the extract after removal) / heavy metal content of the extract before removal × 100%.

[0073] The test results are as follows:

[0074]

[0075]

[0076] The results show that the heavy metal removal methods of Examples 1-8 can all effectively remove five heavy metal ions at the same time, among which Example 1 has the best comprehensive removal effect. Comparative Example 1 does not use microwave treatment, and the heavy metal removal effect is significantly reduced. Comparative Examples 2 and 3 add microcrystalline cellulose and carboxymethyl chitosan respectively, and the heavy metal removal effect is also significantly reduced. The above results show that the combined effect of carboxymethyl chitosan, microcrystalline cellulose and microwave treatment can significantly improve the heavy metal removal effect of the above-mentioned medicinal materials.

[0077] 2. Active ingredient transfer rate

[0078] Detection method: Referring to the high performance liquid chromatography in the "Chinese Pharmacopoeia", gentiopicroside and glycyrrhizic acid were used as test indicators. The content of active ingredients in the extract before and after the removal of heavy metals was detected by high performance liquid chromatography, and the transfer rate of active ingredients was calculated.

[0079] Active ingredient transfer rate (%) = (active ingredient content of the extract before removal - active ingredient content of the extract after removal) / active ingredient content of the extract before removal × 100%.

[0080] The results are as follows:

[0081]

[0082]

[0083] The results show that this removal method has little impact on the active ingredients and can retain more active ingredients while efficiently removing heavy metals.

[0084] The above description is only a preferred embodiment of the present invention and is not intended to limit the present invention. Any modifications, equivalent substitutions, improvements, etc. made within the spirit and principle of the present invention should be included in the protection scope of the present invention.

Claims

1. A method for removing heavy metal residues from traditional Chinese medicine, characterized in that: The following steps are involved: (1) adding carboxymethyl chitosan and microcrystalline cellulose to a Chinese medicinal material extract, adjusting the pH to 6-8, and subjecting the extract to microwave treatment to obtain a treated solution; (2) The pH of the treated liquid obtained in step (1) is adjusted to 4-6, and the filtrate is separated.

2. The removal method according to claim 1, characterized in that: In step (1), the mass ratio of carboxymethyl chitosan to microcrystalline cellulose is 2-5:

1.

3. The removal method according to claim 2, characterized in that: In step (1), the mass ratio of carboxymethyl chitosan to microcrystalline cellulose is 4:

1.

4. The removal method according to claim 1, characterized in that: In step (1), the amount of carboxymethyl chitosan added is 0.5-5% of the mass of the Chinese herbal medicine extract, and the amount of microcrystalline cellulose added is 0.1-2.5% of the mass of the Chinese herbal medicine extract.

5. The removal method according to claim 4, characterized in that: The added amount of the carboxymethyl chitosan is 2% of the mass of the Chinese herbal medicine extract, and the added amount of the microcrystalline cellulose is 0.5% of the mass of the Chinese herbal medicine extract.

6. The removal method according to claim 1, characterized in that: In step (1), the pH is adjusted to 7.

5.

7. The removal method according to claim 1, characterized in that: In step (1), the microwave treatment conditions are: microwave power is 80-150W, and the treatment time is 30-60min.

8. The removal method according to claim 7, characterized in that: The microwave treatment conditions are as follows: microwave power is 120 W, and treatment time is 45 min.

9. The removal method according to claim 1, characterized in that: In step (2), the pH is adjusted to 5.

10. Use of the method for removing heavy metal residues from traditional Chinese medicines according to any one of claims 1 to 9 in the preparation of Shiwuwei Longdanhua Pills.

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