CN112121071A - A product prepared from Ginseng radix - Google Patents

A product prepared from Ginseng radix Download PDF

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CN112121071A
CN112121071A CN202011047127.0A CN202011047127A CN112121071A CN 112121071 A CN112121071 A CN 112121071A CN 202011047127 A CN202011047127 A CN 202011047127A CN 112121071 A CN112121071 A CN 112121071A
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ginsenoside
rare
ginseng
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金永日
李绪文
桂明玉
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Jilin Ruinuo Technology Co ltd
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Abstract

The invention relates to a product rich in rare ginsenoside, a preparation method and application. The product has high content of rare ginsenoside, and is substantially free of common ginsenoside. The preparation method is simple, does not need to use organic solvent and has no solvent residue. Also provides a rare ginsenoside composition with excellent anti-tumor effect.

Description

A product prepared from Ginseng radix
Technical Field
The invention relates to a product prepared by taking ginseng as a raw material, in particular to a ginseng product rich in rare ginsenoside.
Background
The ginseng is the dry root and rhizome of the ginseng of the panax of the Araliaceae, and the traditional commonly used rare Chinese medicinal materials in China are known as 'Baicaowang', have the advantages of mild nature, sweet taste, slight bitterness and slight temperature, have the efficacies of invigorating primordial qi, recovering pulse, relieving depletion, promoting the production of body fluid, quenching thirst, tonifying spleen, benefiting lung, calming the nerves, benefiting intelligence and the like, always occupy an extremely important position in the scientific research field and the traditional Chinese medicine market, and have considerable value in the aspects of medicine and health preservation.
The ginsenoside is a tetracyclic triterpene saponin extracted from plants (radix Panacis Quinquefolii, Ginseng radix, Notoginseng radix, etc.) of Panax of Araliaceae, rhizoma Panacis Japonici, and Vietnamese Ginseng radix. In the 60 s of the 20 th century, researches show that ginsenoside has anticancer activity, and the ginsenoside becomes a popular field for researching anticancer natural medicines. Later, the secondary metabolic derivatives of the transformed ginsenosides have stronger biological activity (Liurong: the research progress of preparing rare ginsenosides by the biotransformation technology). The secondary metabolic derivative is named as "rare ginsenoside", and the ginsenoside directly extracted from Araliaceae Panax plant is named as "prototype ginsenoside", wherein the higher content ginsenoside is named as common ginsenoside, including ginsenoside Rg1、Re、Rb1、Rc、Rb2、Rb3Rd, etc. At present, more than 60 rare ginsenosides, including Rk, have been discovered2、Rg3、Rh2、Rg5、Rh1、Rh3、Rk1And various rare ginsenosides with different anticancer activities. Research shows that the rare ginsenoside has stronger antitumor activity, and also has pharmacological activities of reducing blood pressure, improving immunity, resisting inflammation and the like. Compared with common ginsenoside, the rare ginsenoside has better pharmacological activity.
In 2000, ginsenoside Rg has been approved in China3Ginsenoside Rh developed in our country in 2006 as a prescription drug2The medicines are approved to be on the market, but the industrialization of the rare ginsenoside is still in the initial stage, and at present, no enterprise which can specially produce the high-purity rare ginsenoside monomer exists in China, and no enterprise which has the industrial production capacity of the rare ginsenoside exists. In the future, enterprises with the capacity of industrial production of rare ginsenoside must have the right of market speaking.
Since rare ginsenosides are secondary metabolites of ginsenosides, and the contents of them in panax plants are very low, and the artificial synthesis is difficult, so far, these rare ginsenosides can only be obtained by means of conversion of common ginsenosides, etc.
The conversion method of ginsenoside mainly comprises a chemical method, a microbiological method and an enzymatic method.
The chemical method comprises the following steps: ginsenoside-linked glycosyl groups can be cleaved when exposed to acids or bases. Under milder conditions, the glycosidic bond of ginsenoside is broken in sequence to obtain corresponding secondary ginsenoside, but if the conditions of hydrolysis reaction are too severe, for example, when strong acid such as sulfuric acid or hydrochloric acid is used as a reaction reagent, the sugar chain part of ginsenoside is completely hydrolyzed, and the glycosidic bond is completely broken to obtain the sapogenin and even the structure of aglycone is changed. Gu Yingying et al dissolve ginsenoside Rd in formic acid solution with pH of 2.0, heat in water bath at 60 deg.C for 5h, separate and identify ginsenoside Rd acid hydrolyzate by liquid chromatography-quadrupole-time-of-flight mass spectrometry, and infer chemical conversion mode of ginsenoside Rd by the identification of hydrolyzate. The total saponins of caulis et folium Panacis Quinquefolii are subjected to alkaline hydrolysis with sodium hydroxide, and are subjected to ethyl acetate extraction, silica gel column chromatography and recrystallization to obtain ginsenoside Rh with high purity1And Rh2
The microbiological method comprises the following steps: microbial conversion of ginsenosides refers to the process of converting a substrate into a target product through a special metabolic pathway by using microorganisms under appropriate conditions. In recent years, the improvement of the pharmacological activity of ginsenoside by microbial transformation is more and more concernedAnd (6) note. The microbial conversion method has the advantages of simple operation, mild conditions, high conversion efficiency of the ginsenoside, no need of purifying crude enzyme, no secondary pollution and the like. The glycosyl side chain of the ginsenoside is degraded by a microbiological method, so that various rare ginsenoside monomers can be obtained. Since 1987, the microbial transformation of 89 ginsenoside monomers of natural origin has been studied. The content of rare ginsenoside in radix Panacis Quinquefolii total saponin is remarkably increased by fermenting Cailai Xiaoyu etc. with medicinal fungi, the total content of rare ginsenoside is increased by 20-150%, and various ginsenoside F1C-K and Rg2The content of rare ginsenoside is also obviously increased. Screening a strain of mold from Ming Yong shan et al, hydrolyzing ginsenoside Re to generate Rg1Separating and purifying with preparative column to obtain ginsenoside Rg with purity of 81.98%1The yield was 71.83%. Screening out TH-20 strain from soil such as coral, and simultaneously converting diol type ginsenoside and triol type ginsenoside to respectively obtain Rb1Re and Rg1Conversion to Rd, Rg2And PPT. The strain CZ2 separated from orange juice can convert ginsenoside Rb1Generating F2And Gyp-XVII. Zelina et al, which uses radix Panacis Quinquefolii extract as substrate to carry out microbial transformation of ginsenoside, and analyzing ginsenoside Re and its fermentation product by High Performance Liquid Chromatography (HPLC). The result shows that the high-efficiency strain S329 can convert ginsenoside Re into ginsenoside Rh1The conversion was 27.65%. Cui Lei et al utilize endophyte JG09 to convert ginsenoside Rb1、Rb2、Rc、Rd、Rg1Respectively converted into corresponding rare ginsenoside F2C-K and Rh1Ginsenoside F2And the maximum conversion of C-K can reach 94.53 percent and 66.34 percent respectively.
An enzymatic conversion method: the enzyme method has the advantages of strong specificity, mild reaction conditions, high conversion efficiency, no pollution and the like, and is considered as the most effective tool in the structural modification and metabolic research of ginsenoside. The glycosidase is used for carrying out structural modification on the sugar chain to improve the biological activity of the compound so as to meet the development of the pharmaceutical industry, and is also the focus of the current ginsenoside research. Shin et al foundThe glucoside hydrolase in the cellulolytic bacterium can hydrolyze D-glucose and L-arabinose outside the C-20 position of ginsenoside, and thus ginsenoside Rc containing L-arabinose can be converted into C-K by the enzyme. The tongqing uses a kind of snailase to convert panaxadiol group ginsenoside to prepare rare ginsenoside C-K, and the ginsenoside C-K with purity higher than 98% is obtained by silica gel column chromatography separation. Converting protopanaxatriol saponin with glycosidase to obtain rare ginsenoside F1And Rh1. Ginsenoside is used as a substrate and is subjected to enzymatic structure modification, so that the method is an effective way for preparing rare ginsenoside. Is prepared from ginsenoside Rb2、Rb3And Rc is used as a substrate, and C-3 site and C-20 site are modified to obtain rare ginsenoside Rg3、Rh2、F2And PPD, and the like. The rare ginsenoside can be prepared in large scale, and the pharmacological activity of the ginsenoside is clear.
Chinese patent CN107468732A discloses a preparation method for increasing trace ginsenoside in a traditional Chinese medicine ginseng leaf extract, which comprises the following steps: the method comprises the steps of rubbing or crushing traditional Chinese medicine ginseng leaves by hands, mixing the crushed ginseng leaves with diatomite at a ratio of 5:3, placing the crushed ginseng leaves and diatomite in an extraction kettle, placing the extraction kettle in a rapid solvent extraction instrument, taking an ethanol water solution as an extraction solution, enabling the volume ratio of a mixture of the ginseng leaves and the diatomite to be 30% -80%, enabling the volume of the extraction solution to be 60% -100% of the volume of the extraction kettle, enabling the extraction temperature to be 110-200 ℃, extracting for 1-4 times, enabling the extraction time to be 1-20 minutes each time, combining the extraction solutions, shaking up, standing for 10-24 hours, taking supernate, concentrating and drying to obtain the ginseng leaf extract in a dry extract state. In the method, solvents such as diatomite, ethanol water and the like are used, so that great troubles are brought to subsequent purification and impurity removal.
The chemical method in the three ginsenoside conversion methods has the defects of difficult control of reaction conditions, complex product, environmental pollution and the like; the microbial transformation method has the defects of poor selectivity, difficult acquisition of microorganisms, incapability of applying some microorganisms to the food industry and the like; the enzyme method has the advantages of strong specificity, mild reaction conditions, high conversion efficiency, no pollution and the like, but the enzyme is very sensitive to temperature, often leads to inactivation, has higher requirements on the reaction conditions, and is difficult to realize industrial production.
Because of the difficulties in preparing rare ginsenosides, there is no ginseng product with high content of rare ginsenosides available for mass production so far.
Therefore, there is a need in the art for a simple, easy to implement, low in pollution, low in organic solvent usage, low in residue, and purely natural ginseng product preparation method that can increase the content of rare ginsenoside and improve the bioactivity of ginseng products.
Disclosure of Invention
There are many methods for processing ginseng in the prior art, and accordingly, different ginseng products can be obtained.
A method comprises collecting Ginseng radix in autumn, cleaning, and sun drying or oven drying to obtain Ginseng radix divided into garden Ginseng radix and wild Ginseng radix; another method comprises collecting Ginseng radix in autumn, cleaning, steaming, and drying to obtain Ginseng radix Rubri. These two methods are the most traditional methods for processing ginseng. As a modern processing method of ginseng, a lactobacillus fermentation method, a high-temperature steaming method and the like appear, and products such as lactobacillus fermented ginseng or 'black ginseng' and the like can be obtained correspondingly. Another kind of ginseng products is various ginseng extracts obtained by extracting fresh ginseng or the ginseng products with water, ethanol or ethanol water, recovering the solvent from the extract under reduced pressure, and drying under vacuum. The other ginseng product is ginsenoside extract obtained by extracting the ginseng product with water, filtering, adsorbing the extract with macroporous adsorption resin, eluting with ethanol, recovering solvent from the eluate under reduced pressure, and vacuum drying.
CN108079033A extracting ginsenoside with 65-80% ethanol under reflux, filtering, removing residue, and recovering solvent from the extractive solution under reduced pressure to obtain total ginsenoside; CN106727806A extracting folium Notoginseng with solvent after coarse crushing, filtering, discarding residue, recovering solvent from the extractive solution under reduced pressure to obtain folium Notoginseng total saponin, wherein the solvent is selected from water and 70% ethanol. Weighing radix Panacis Quinquefolii coarse powder in CN102772462A, adding 70% ethanol solution 6 times the amount of radix Panacis Quinquefolii coarse powder each time, heating and reflux extracting for 3 times, filtering, discarding residue, and recovering solvent from the extractive solution under reduced pressure to obtain radix Panacis Quinquefolii total saponin.
Decocting with water or extracting under reflux with organic solvent, which is the most common method for extracting and separating effective components from Chinese medicinal materials or natural medicinal materials including ginseng to obtain Chinese medicinal material or natural medicinal extract. The specific operation process is that water decoction extraction (or organic solvent reflux extraction) is carried out, filtration is carried out, medicine dregs are discarded, extracting solution is decompressed and solvent is recovered, and then vacuum drying is carried out to obtain extract. In order to obtain the best extraction conditions, factors such as an extraction solvent (water or an organic solvent), an extraction mode (soaking, heating reflux, percolation, ultrasound, supercritical), extraction times and the like are generally considered, so that the chemical components in the medicinal materials are completely extracted in the simplest and most economical mode. That is, in the research of chemical components of traditional Chinese medicine and the pharmaceutical engineering of traditional Chinese medicine, decocting the medicinal materials with water (or reflux extraction by organic solvent), centrifuging, discarding the extract, and taking the residue (dregs) after decoction (or reflux extraction by organic solvent) as a new medicinal substance (product) is a infringement of the conventional affairs, while finding that more chemical components which should enter the extract are retained in the residue (dregs) is not a thing imaginable by the conventional thinking.
The researchers of the invention have engaged in the research works such as the extraction of ginsenoside, the preparation of ginsenoside standard substance and effective part, the content measurement and the bioactivity, etc. for a long time. In the research process of using ginseng as raw material and water as solvent, reflux extracting ginsenoside in the ginseng and screening the optimal extraction process parameters, the influence of the decoction time on the transfer rate of the ginsenoside is repeatedly researched. During the initial extraction process, the content of the common ginsenoside in the water liquid (extract) is gradually increased along with the increase of the decoction time, and the content of the common ginsenoside in the dregs is gradually reduced, so that the result conforming to the general rule of extraction of chemical components of traditional Chinese medicines is obtained. However, in the following research process, it is unexpectedly found that, as the heating reflux extraction time is further prolonged, the content of the common ginsenoside in the water solution (extract) does not increase or decrease, and as the decoction time is further prolonged, the content of the common ginsenoside in the water solution (extract) continuously decreases, and after the water solution (extract) is heated for a certain time, especially 48 hours, the common ginsenoside is basically not contained in the water solution (extract); meanwhile, the rare ginsenoside begins to appear in the water solution and the decoction dregs and gradually rises along with the increase of the extraction time. It was then surprisingly found that after heating for a certain period of time, in particular 48 hours, the rare ginsenoside content in the aqueous liquid began to decrease and finally disappeared, while the rare ginsenoside content in the residue continued to increase and finally reached a maximum, and then the decoction time continued to be extended, the content did not substantially increase and did not decrease, with small fluctuations around the maximum. Based on the above important findings, through a great deal of elaborate researches, the invention finds a method for preparing a new ginseng product which contains more rare ginsenosides and basically does not contain common ginsenosides by taking ginseng as a raw material. Of course, this method can be used to obtain new ginseng products (dregs) containing different proportions of common ginsenosides and rare ginsenosides. The new ginseng product can be used for producing food, health food or medicinal product with health or therapeutic effect.
The ginseng product is preferably herb residue.
The rare ginsenoside comprises 20(S) -Rg2、20(S)-Rh1、20(R)-Rh1、Rg6、F4、Rk3、Rh4、20(S)-Rg3、20(R)-Rg3、Rk1、Rg5、20(S)-Rh2、20(R)-Rh2、Rk2、Rh3The common ginsenoside comprises Rg1、Re、Rb1、Rc、Rb2、Rb3And Rd. The product contains one or more of 15 kinds of rare ginsenoside, specifically 20(S) -Rg2、20(S)-Rh1、20(R)-Rh1、Rg6、F4、Rk3、Rh4、20(S)-Rg3、20(R)-Rg3、Rk1、Rg5、20(S)-Rh2、20(R)-Rh2、Rk2、Rh3The product is substantially free of common ginsenoside including Rg1、Re、Rb1、Rc、Rb2、Rb3、Rd。
Preferably the total amount of rare ginsenosides is not less than 5%, 7%, 8%, 9%, 10%, 11% or 12%, and the total content of common ginsenosides is not more than 3%, 2%, 1%, 0.8%, 0.7%, 0.5%, 0.4%, 0.2% or 0.1%;
preferred rare ginsenosides are Rg3The content is not less than 3%, more preferably not less than 4% or 6%, most preferably not less than 6%.
Preferred rare ginsenosides are Rk1And Rg5The sum of the amounts is not less than 1%, more preferably not less than 2%, 3%, 4%, or 5%.
Preferred rare ginsenosides are Rk6And F4The sum of the contents is not less than 0.5%, more preferably not less than 0.6% or 0.7%.
Preferably the total content of common ginsenosides is not higher than 1%, more preferably not higher than 0.8% or 0.6%, most preferably not higher than 0.4% and 0.3%.
Preferred common ginsenoside Rc contents are not higher than 3%, 2%, 1%, 0.8%, 0.7%, 0.5%, 0.4%, 0.2% or 0.1%.
Preferred common ginsenoside Rg1、Re、Rb1、Rb2、Rb3Rd, more preferably not more than 0.4% or 0.3%, most preferably not more than 0.2%, 0.1% or 0.05%.
Rg described in the present invention3、Rh1Or Rh2Including 20R configuration and/or 20S configuration, the ratio of 20R configuration to 20S configuration is 1:100 to 100:1, preferably 1:10 to 10:1, and more preferably 1: 1.
Rg described in the present invention3Comprises 20(S) -Rg3And/or 20(R) -Rg3;Rh2Comprising 20(S) -Rh2And/or 20(R) -Rh2
The application also relates to a preparation method for preparing the high-content rare ginsenoside product, which comprises any one of the following steps:
a: pulverizing Ginseng radix, adding appropriate amount of water, heating and refluxing under normal pressure for more than 48 hr, preferably 60 hr, 72 hr, 84 hr, 96 hr 108 hr or more than 120 hr, filtering, and drying the residue to obtain the desired product;
b: pulverizing Ginseng radix, adding appropriate amount of water, decocting at high temperature and high pressure for 4 hr or more, preferably 6 hr or more, 8 hr or more, 10 hr or more, 12 hr or more, 14 hr or more, 16 hr or more, 18 hr or more, 20 hr or more, 22 hr or more, 24 hr or more, 28 hr or more, 30 hr or more, 32 hr or more, 34 hr or more, 36 hr or more, 38 hr or more, 40 hr or more, 42 hr or more, 44 hr or more, 48 hr or more, or 50 hr or more, filtering, and drying the residue to obtain the desired product.
The high temperature is 100 deg.C or higher, preferably not lower than 110 deg.C, 115 deg.C, 120 deg.C, 125 deg.C, 130 deg.C, 135 deg.C, 140 deg.C, 145 deg.C or 150 deg.C.
In preparation method A, the liquid-to-feed ratio may be (30-5):1, preferably (25-8):1, more preferably (20-9):1 or (15-10):1, preferably 10: 1.
In preparation method B, the liquid-to-feed ratio may be (30-5):1, preferably (25-6):1, more preferably (20-7):1 or (10-8):1, preferably 7.5: 1.
In the preparation method A, preferably, the ginseng is first soaked in water; more preferably, the ginseng is soaked for more than 6 hours, more than 8 hours, more than 10 hours, more than 12 hours or more than 24 hours, and then heated and refluxed; meanwhile, the hot filtration is carried out after the decoction is finished, and the hot filtration is carried out immediately after the decoction is finished (close to 100 ℃).
In the preparation method B, preferably, the water is heated and then fed, preferably, the water is heated to more than 60 ℃ and then fed, and more preferably, the water is heated to more than 90 ℃ and then fed; most preferred is to heat the water to 100 ℃ before adding it. Meanwhile, the hot filtration is carried out after the decoction is finished, and the hot filtration is carried out immediately after the decoction is finished (close to 100 ℃).
20(S) -Rg in the medicine dregs2The content range of (A) is 0.2% -0.35%; 20(S) -Rh1The content range is 0-0.45%, preferably 0.2% -0.45%; 20(R) -Rh1The content range is 0-0.25%, preferably 0.05% -0.25%; rg (Rg)6The content range is 0-0.15%, preferably 0.1% -0.15%; f4The content range is 0-0.8%, preferably 0.1% -0.7%; rk3The content range is 0-0.2%, preferably 0.02% -0.2%; rh4The content range is 0-0.1%, preferably 0.05% -0.35%; 20(S) -Rg3The content range is 0.2% -4.0%, preferably 0.4% -3.8%; 20(R) -Rg3The content range is 0.2% -3.0%, preferably 0.3% -2.8%; rk1The content range is 0.1% -2.0%, preferably 0.2% -2.0%; rg (Rg)5The content range is 0.2% -3.0%, preferably 0.3% -2.8%; 20(S) -Rh2The content range is 0-0.07%; 20(R) -Rh2The content range is 0-0.05%; rk2The content range is 0-0.04%; rh3The content range is 0-0.06%.
Optionally further preparing the residue into powder, decoction pieces, syrup, oral liquid, suspension, emulsion, tablet, capsule, delayed release agent, quick release agent, controlled release agent, injection, injectable powder, patch, suppository, or drop.
Optionally further extracting the residue with organic solvent or aqueous organic solvent to obtain extract with high content of rare ginsenoside.
The preferred extract contains one or more of 15 rare ginsenosides, specifically 20(S) -Rg2、20(S)-Rh1、20(R)-Rh1、Rg6、F4、Rk3、Rh4、20(S)-Rg3、20(R)-Rg3、Rk1、Rg5、20(S)-Rh2、20(R)-Rh2、Rk2、Rh3The total content of rare ginsenosides is more than 15%, 20%, 25%, 30%, 35%, 40%, 50%, 60%, 70%, 80% or 90%. Preferably, the extract contains Rg3(20S +20R) content of not less than 15%, not less than 18%, not less than 20% or not less than 22%;and/or Rg5The content of (A) is not less than 5%, 6%, 8%, or 9%; and/or Rk1The content of (A) is not less than 5% or 6%; and/or F4The content of (A) is not less than 1%; rg (Rg)6And F4The sum of the contents of (A) and (B) is not less than 1.5% or 2%.
More preferably, the extract is substantially free of common ginsenosides, including Rg1、Re、Rb1、Rc、Rb2、Rb3And Rd. The content of common ginsenoside is not higher than 10%, preferably not higher than 8%, 6%, 5%, 4%, 3%, 2% or 1%. More preferably, less than 0.8%, 0.6%, 0.5% or 0.1%.
20(S) -Rg in the extract2The content range of (A) is 0.2% -1.5%; 20(S) -Rh1The content range is 0.5% -1.6%; 20(R) -Rh1The content range is 0.5% -0.8%; rg (Rg)6The content range is 0.3% -0.8%; f4The content range is 1% -2.5%; rk3The content range is 0.5% -1.2%; rh4The content range is 0.5% -1.6%; 20(S) -Rg3The content range is 5% -13%; 20(R) -Rg3The content range is 5% -12%; rk1The content range is 5% -10%; rg (Rg)5The content range is 6% -12%; 20(S) -Rh2The content range is 0.1% -0.3%; 20(R) -Rh2The content range is 0.1% -0.3%; rk2The content range is 0.05% -0.2%; rh3The content range is 0.1% -0.4%.
The organic solvent may be methanol, ethanol, ethyl acetate, chloroform, n-butanol, acetone or isopropanol.
The present application also provides a composition comprising rare ginsenosides, preferably the composition has synergistic anti-tumor activity.
The rare ginsenoside comprises Rg3And Rg5The composition of (1) to (20): (1-20), preferably (2-20): (2-20); (4-6) and (1-3); or (7-11.5) to (3.5-5).
The rare ginsenoside comprises F4And Rh2The composition of (1) to (100): (1-100), preferably (A)1-10): (10-100), (10-100): (1-10), (1-10): (10-1), (1-100): (1-10); most preferred is 10:1, 1:1 or 1: 10.
The rare ginsenoside contains Rh4And Rh2The composition of (1) to (100): (1-100), preferably (1-90): (1-90), (10-100): (1-10), (1-10): (10-1), (1-20): (1-20).
The rare ginsenoside in the composition optionally further comprises S-Rg2、S-Rh1、R-Rh1、Rg6、F4、Rk3、Rh4、S-Rg3、R-Rg3、Rk1、Rg5、S-Rh2、R-Rh2、Rk2、Rh3One or more rare ginsenosides in (1).
Preferably, the composition also comprises 20(S) -Rg2、20(S)-Rh1、20(R)-Rh1、Rg6、F4、Rk3、Rh4、20(S)-Rg3、20(R)-Rg3、Rk1、Rg5、20(S)-Rh2、20(R)-Rh2、Rk2And/or Rh3
Preferably, the composition also comprises 20(S) -Rg2、20(S)-Rh1、20(R)-Rh1、Rg6、F4、Rk3、Rh4、20(S)-Rg3、20(R)-Rg3、Rk1、Rg5、20(S)-Rh2、20(R)-Rh2、Rk2、Rh3
Preferably, the composition is substantially free of common ginsenosides, including Rg1、Re、Rb1、Rc、Rb2、Rb3And Rd. The content of common ginsenoside is less than 10%, preferably less than 8%, 6%, 5%, 4%, 3%, 2% or 1%. More preferably, less than 0.8%, 0.6%, 0.5% or 0.1%.
The application also provides a ginseng product containing any one of the compositions, preferably a product prepared by taking natural ginseng or common ginsenoside as raw materials, preferably herb residue or extract.
Preferably, the properties and parameters of the product are characterized as any one of the above.
The ginseng comprises one or more of dried or fresh ginseng root, ginseng rootlets and ginseng reed head.
The application also provides the application of the product or the composition in treating and/or preventing tumors, wherein the tumors can be lung cancer, colon cancer and glioma.
The application of any one of the products or the composition in the preparation of medicines, health-care foods or foods, in particular to the application in the foods, the health-care foods or the medicines which are known in the prior art and have the functions of reducing blood sugar, resisting fatigue and viruses, and treating diabetes, cardiovascular diseases, central nervous system diseases, biological metabolism, reproductive function, immune function, renal function and other diseases; which may contain pharmaceutically or food acceptable carriers or additives.
Any of the products or compositions described above of the present application, which may contain a pharmaceutically acceptable carrier.
Optionally, the product or composition is administered orally, by injection or transdermally.
Optionally, the product or composition is in the form of powder, decoction pieces, syrup, oral liquid, suspension, emulsion, tablet, capsule, sustained release preparation, quick release preparation, controlled release preparation, injection, injectable powder, patch, suppository, or drop.
Drawings
FIG. 1: reacting Leptoradix Ginseng residue at 100 deg.C and Rg in water3The content is changed;
FIG. 2: reacting Leptoradix Ginseng residue at 100 deg.C and Rg in water3And Rh2A change in total amount;
FIG. 3: reacting ginseng rootlets dregs and Rk in water at 100 DEG C1And Rg5A change in total amount;
FIG. 4: reacting Leptoradix Ginseng residue at 100 deg.C and Rg in water6And F4A change in total amount;
FIG. 5: reacting ginseng rootlets dregs at 100 ℃ to neutralize the total amount change of 15 rare ginsenosides in water;
FIG. 6: reacting ginseng rootlets dregs and 7 common ginsenosides in water at 100 ℃;
FIGS. 7A and 7B show the total amount of 15 rare ginsenosides in the residue at 115 deg.C and 120 deg.C, respectively;
fig. 8A and 8B are respectively: the total amount of 15 rare ginsenosides in the residue at 125 deg.C and 130 deg.C is changed;
fig. 9A and 9B are respectively: the total amount of 15 rare ginsenosides in the residue at 135 deg.C and 140 deg.C is changed;
FIG. 10 is a diagram: the total amount of 15 rare ginsenosides in the residue is changed at 145 ℃;
FIG. 11: 20(S) Rg in medicine dregs at 115 DEG C3+20(R)Rg3And Rg5+Rk1The content is changed;
FIG. 12: 20(S) Rg in the medicine dregs at 120 DEG C3+20(R)Rg3And Rg5+Rk1The content is changed;
FIG. 13: 20(S) Rg in medicine dregs at 125 DEG C3+20(R)Rg3And Rg5+Rk1The content is changed;
FIG. 14: 20(S) Rg in dregs of a decoction at 130 DEG C3+20(R)Rg3And Rg5+Rk1The content is changed;
FIG. 15: 20(S) Rg in dregs of a decoction at 135 DEG C3+20(R)Rg3And Rg5+Rk1The content is changed;
FIG. 16: 20(S) Rg in dregs of a decoction at 140 DEG C3+20(R)Rg3And Rg5+Rk1The content is changed;
FIG. 17: 20(S) Rg in medicine dregs at 145 DEG C3+20(R)Rg3And Rg5+Rk1The content was varied.
Detailed Description
The present invention will be further described with reference to the following examples.
Determining the content of common ginsenoside by high performance liquid chromatography:
1. ginsenoside Rg1、Re、Rb2、Rb3Determination of the content of Rd
1.1 chromatographic conditions
Octadecylsilane chemically bonded silica gel as filler (column length 250mm, inner diameter 4.6mm, particle size 5 μm), acetonitrile as mobile phase A, water as mobile phase B, gradient elution according to the following table, column temperature 25 deg.C,
the flow rate is 1ml/min, the detection wavelength is 203nm, and the sample injection amount is 20 mu L.
Time (minutes) Mobile phase A (%) Mobile phase B (%)
0~35 19.5 80.5
35~35.1 19.5→20 80.5→80
35.1~55 20 80
55~55.1 20→29 80→71
55.1~84 29→36 27→64
84~90 36 64
1.2 preparation of control solutions:
collecting ginsenoside Rg1Ginsenoside Re and ginsenoside Rb2Ginsenoside Rb3And a proper amount of ginsenoside Rd reference substance, precisely weighing, and adding methanol to obtain a mixed standard solution with the following concentration.
Ginsenoside Rg1The concentration is 0.201mg/ml
The ginsenoside Re concentration is 0.205mg/ml
Ginsenoside Rb2The concentration is 0.174mg/ml
Ginsenoside Rb3The concentration is 0.111mg/ml
The concentration of ginsenoside Rd is 0.201mg/ml
1.3 preparation of test solution:
1.3.1, herb residue
Taking 2.0g of sample (dried ginseng residue), precisely weighing, adding methanol, refluxing and extracting twice, wherein the amount of the methanol is 250ml, each time lasts for 2 hours, filtering, recovering the methanol from the filtrate under reduced pressure, and metering the volume of the residue to 100ml with the methanol.
1.3.2, water solution
Taking 25ml of water solution, adding methanol to a volume of 50ml volumetric flask.
2. Ginsenoside Rb1Measurement of Rc content
2.1 chromatographic conditions:
a chromatographic column: XAmide column (column length 250mm, inner diameter 4.6mm, particle size 5 μm) was subjected to gradient elution with acetonitrile as mobile phase A and water as mobile phase B according to the following table. The column temperature was 25 ℃, the flow rate was 1ml/min, the detection wavelength was 203nm, and the sample volume was 20. mu.L.
Time (minutes) Mobile phase A (%) Mobile phase B (%)
0~30 90→84 10→16
30~65 84 16
2.2 preparation of control solutions:
collecting ginsenoside Rb1And a proper amount of ginsenoside Rc reference substance is precisely weighed and added with methanol to prepare a mixed standard solution with the following concentration. Ginsenoside Rb1The concentration is 0.121mg/ml
Ginsenoside Rc concentration is 0.156mg/ml
2.3 preparation of test solution:
2.3.1, herb residue
Taking 2.0g of sample (dried ginseng residue), precisely weighing, extracting with methanol under reflux twice each for 2 hr, wherein the amount of methanol is 250ml, filtering, discarding residue, recovering methanol from filtrate under reduced pressure, and diluting residue with methanol to 100 ml.
2.3.2, water solution
Taking 25ml of water solution, adding methanol to a volume of 50ml volumetric flask.
High performance liquid chromatography for determining content of rare ginsenoside
1. Chromatographic conditions are as follows:
octadecylsilane chemically bonded silica (ODS) was used as a filler (column length 250mm, inner diameter 4.6mm, particle size 5 μm), acetonitrile was used as a mobile phase A, water was used as a mobile phase B, and gradient elution was performed according to the following table, with a column temperature of 25 ℃, a flow rate of 0.8ml/min, a detection wavelength of 203nm, and a sample introduction amount of 20 μ L.
Time (minutes) Mobile phase A (%) Mobile phase B (%)
0~10 29 71
10~25 29→40 71→60
25~50 40→60 60→40
50~60 60→73 40→27
60~75 73 27
2. Preparation of control solutions:
collecting ginsenoside 20(S) -Rg2Ginsenoside 20(S) -Rh1And (20) ginsenoside R-Rh1Ginsenoside Rg6Ginsenoside F4Ginsenoside Rk3Ginsenoside Rh, ginsenoside Rh4Ginsenoside 20(S))-Rg3Ginsenoside 20(R) -Rg3Ginsenoside Rk1Ginsenoside Rg5Ginsenoside 20(S) -Rh2Ginsenoside 20(R) -Rh2Ginsenoside Rk2Ginsenoside Rh, ginsenoside Rh3The appropriate amount of reference substance is precisely weighed and added with methanol to prepare mixed standard solution with the following concentration.
Ginsenoside 20(S) -Rg2The concentration is 0.2268mg/ml
Ginsenoside 20(S) -Rh1The concentration is 0.1792mg/ml
Ginsenoside 20(R) -Rh1The concentration is 0.1692mg/ml
Ginsenoside Rg6The concentration is 0.1632mg/ml
The ginsenoside F4 concentration is 0.1240mg/ml
Ginsenoside Rk3The concentration is 0.1248mg/ml
Ginsenoside Rh4The concentration is 0.1256mg/ml
Ginsenoside 20(S) -Rg3The concentration is 0.1296mg/ml
Ginsenoside 20(R) -Rg3The concentration is 0.0596mg/ml
Ginsenoside Rk1The concentration is 0.1580mg/ml
Ginsenoside Rg5The concentration is 0.1560mg/ml
Ginsenoside 20(S) -Rh2The concentration is 0.1388mg/ml
Ginsenoside 20(R) -Rh2The concentration is 0.1324mg/ml
Ginsenoside Rk2The concentration is 0.1324mg/ml
Ginsenoside Rh3The concentration is 0.0688mg/ml
3. Preparation of a test solution:
3.1, herb residue
Taking 3.0g of dried ginseng dregs, precisely weighing, carrying out methanol reflux extraction twice for 2 hours each time, wherein the amount of methanol is 250ml, filtering, discarding the dregs, recovering methanol from the filtrate under reduced pressure, and metering the volume of the residue to a volumetric flask of 250ml by using methanol.
3.2, water solution
Taking 25ml of water solution, adding methanol to a volume of 50ml volumetric flask.
Example 1: decocting Ginseng radix at 100 deg.C under normal pressure-distributing ginsenoside in water solution and residue
Weighing 1500g of ginseng rootlets as raw materials, crushing, adding 10 times of water for soaking overnight, heating and refluxing at 100 ℃ (normal pressure), and sampling and filtering respectively to obtain a water solution (liquid) and dregs, wherein the water solution (liquid) and dregs are dried to obtain dry dregs after 0 hour (before the soaking overnight begins to heat and reflux), 60min after the beginning of heating, A (90min, just begins to boil), 1 hour, 2 hours, 3 hours, 4 hours, 6 hours, 8 hours, 10 hours, 12 hours, 14 hours, 16 hours, 18 hours, 24 hours, 36 hours, 48 hours, 60 hours, 72 hours, 84 hours, 96 hours, 108 hours, 120 hours, 132 hours, 144 hours, 156 hours, 168 hours, 180 hours, 192 hours, 204 hours, 216 hours, 228 hours, 240 hours and 252 hours. And analyzing the contents of the rare ginsenoside and the common ginsenoside in the water solution and the medicine residue by using 15 rare ginsenosides and 7 common ginsenosides as standard substances through an HPLC method. 600g ginseng rootlets are heated and refluxed for 84 hours to obtain 201g of dry medicine dregs, and 5750ml of centrifugal water is obtained.
I. The content of ginsenoside in water varies
TABLE 1100 deg.C under normal pressure reflux for 252 hr, the content of ginsenoside changes (mg/ml, after 96 hr, 0)
Figure BDA0002708350310000111
Table 2100 deg.C normal pressure reflux ginseng rootlets 252 hours common ginsenoside content in herb residue (%, after 132 hours reflux all 0)
Figure BDA0002708350310000112
Figure BDA0002708350310000121
From the above table, it can be seen that, after ginseng is soaked in 10 times of water for 12 hours, the ginseng begins to be heated and decocted, and is heated to be within 4.5 hours (boiling begins for 3.0 hours), the content of the common ginsenoside in the water solution keeps rising, the content of the common ginsenoside in the water solution reaches the maximum (4.399mg/ml) after boiling for 3 hours, then the content of the common ginsenoside in the water solution begins to fall, only one common ginsenoside is detected in 84 hours, the content is only 0.05%, and no common ginsenoside is detected in 96 hours. Correspondingly, the content of the common ginsenoside in the medicine residue is gradually reduced, only 2 common ginsenosides are detected in 120 hours, only 1 common ginsenosides is detected in 132 hours, the content of the common ginsenosides can be basically ignored, and the content of the common ginsenosides in 144 hours is detected to be 0.
Table 3100 deg.C, reflux extracting ginseng rootlets under normal pressure for 252 hours, content (mg/ml) of 15 rare ginsenosides in water solution
Figure BDA0002708350310000122
Figure BDA0002708350310000131
Table 4100 deg.C content (%)% of 15 rare ginsenosides in the residue after refluxing Leptoradix Ginseng under normal pressure for 252 hr
Figure BDA0002708350310000132
Figure BDA0002708350310000141
Figure BDA0002708350310000151
Rare ginsenoside can not be detected in the water liquid and the dregs of a decoction of the ginseng rootlets after being soaked for one night, which indicates that the ginseng rootlets originally do not contain rare ginsenoside.
When the water solution is heated to boiling, rare ginsenoside begins to appear in the water solution, and the content of rare ginsenoside in the water solution gradually increases with the increase of the heating time until the highest content is reached at 36h (2.897 mg/ml). Then the content of rare ginsenoside in water solution begins to gradually decrease to 0.127mg/ml after 252h, and decreases to less than 5% of the peak.
Correspondingly, rare ginsenoside begins to appear in the medicine residue when the medicine residue is heated to be boiled, the content of the rare ginsenoside gradually increases to 12.431% when the medicine residue is heated to be boiled for 84h, and then the content of the rare ginsenoside shows a small fluctuation trend around the value.
Rare ginsenoside Rg3(20(S)Rg3+20(R)Rg3) And Rh2(20(S)Rh2+20(R)Rh2) Before refluxing for 36 hours, the content of the water solution is increased and gradually decreased after 36 hours, and after 120 hours, the content is negligibly low.
Rg in herb residues3And Rh2The content of (A) gradually rises, and the content can reach more than 5 percent; rg (Rg)3And Rh2The total content of the two components can reach more than 5 percent, and particularly after 84 hours, the sum of the two components can reach 6.3 percent at most.
In addition, Rk in rare ginsenoside1And Rg5The total amount can reach more than 4 percent. Rg in rare ginsenoside6And F4The content sum is not less than 0.5 percent and can reach more than 0.6 percent or 0.7 percent.
In order to maximally enrich the rare ginsenoside in the medicine residues, reduce the loss of the rare ginsenoside in water liquid and shorten the preparation time, the ginseng fibrous root decoction takes ginseng rootlets as raw materials and carries out a high-temperature high-pressure decoction experiment.
Example 2: high-temperature high-pressure decoction of Leptoradix Ginseng, distribution of ginsenoside in water solution and residue
Taking Leptoradix Ginseng as raw material, weighing 1000 g Leptoradix Ginseng, pulverizing, adding 7.5 times of water, decocting at high temperature and high pressure, sampling at a certain time interval from 0 hr (the temperature in the kettle reaches the set temperature), filtering to obtain residue and water solution, and oven drying the residue to obtain dry residue. Analyzing the contents of rare ginsenoside and common ginsenoside in water solution and residue by HPLC.
The temperature is respectively designed to be 115 ℃, 120 ℃, 125 ℃, 130 ℃, 135 ℃, 140 ℃ and 145 ℃, the liquid-material ratio is designed to be 5:1, 7:1 and 10:1, and orthogonal tests are carried out to screen the optimal preparation process.
Compared with the high-temperature high-pressure decoction and the normal-pressure reflux at 100 ℃, the change rule of common ginsenoside and rare ginsenoside in the water liquid and the decoction dregs is basically consistent, and the content of the rare ginsenoside in the prepared decoction dregs is basically the same, but the high-temperature high-pressure decoction has the advantage of greatly shortening the preparation time compared with the normal-pressure reflux.
Experiments show that Rg in medicine dregs under the conditions of high temperature and high pressure3The content of Rg in the medicine residue is more than 5%, especially when the temperature is 125-140 deg.C, the liquid-material ratio is (6-9):13The content of (A) can reach more than 6%. After a period of decoction, the contents of the common ginsenoside in the dregs and the water are both 0.
The following data were collated and analyzed for experimental data at 115 ℃, 120 ℃, 125 ℃, 130 ℃, 135 ℃, 140 ℃ and 145 ℃ (all liquid-to-material ratios were 7.5: 1).
Table 5: the contents of 7 common ginsenosides in ginseng rootlet dregs decocted at the high temperature and the high pressure of 115%
2h 4h 6h 8h 12h 16h 20h 24h 28h 32h 36h 40h 44h 48h 52h
Rg1 0.061 0.042 0.028 0.015 0.003 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000
Re 0.273 0.181 0.112 0.058 0.017 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000
Rb1 1.168 0.972 0.915 0.738 0.470 0.170 0.085 0.049 0.000 0.000 0.000 0.000 0.000 0.000 0.000
Rc 0.955 0.802 0.734 0.588 0.346 0.147 0.065 0.027 0.000 0.000 0.000 0.000 0.000 0.000 0.000
Rb2 0.618 0.511 0.477 0.397 0.290 0.097 0.051 0.031 0.010 0.004 0.000 0.000 0.000 0.000 0.000
Rb3 0.093 0.076 0.070 0.057 0.043 0.014 0.007 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000
Rd 0.547 0.498 0.492 0.448 0.402 0.212 0.174 0.161 0.105 0.068 0.036 0.027 0.000 0.000 0.000
Total amount (%) 3.715 3.082 2.828 2.301 1.571 0.640 0.382 0.268 0.115 0.072 0.036 0.027 0.000 0.000 0.000
Table 6: decocting Leptoradix Ginseng at 115 deg.C under high temperature and high pressure to obtain 7 common ginsenoside contents (mg/ml, 4 hr, 8 hr and 48 hr for three time points)
4h 8h 48h
Rg1 0.138 0.048 0.000
Re 0.508 0.175 0.000
Rb1 1.543 1.031 0.000
Rc 1.276 0.807 0.000
Rb2 0.829 0.540 0.000
Rb3 0.122 0.084 0.000
Rd 0.694 0.530 0.000
Total amount (mg/ml) 5.110 3.215 0.000
Table 7115 ℃ high temperature high pressure decoction of 15 rare ginsenosides in Leptoradix Ginseng residue (%)
2h 4h 6h 8h 12h 16h 20h 24h 28h 32h 36h 40h 44h 48h 52h
S-Rg2 0.183 0.233 0.282 0.307 0.338 0.281 0.298 0.314 0.320 0.324 0.298 0.357 0.219 0.235 0.169
S-Rh1 0.405 0.407 0.432 0.421 0.404 0.279 0.280 0.304 0.321 0.345 0.342 0.445 0.316 0.360 0.288
R-Rh1 0.025 0.034 0.038 0.048 0.068 0.063 0.081 0.096 0.112 0.131 0.140 0.203 0.184 0.225 0.199
Rg6 0.029 0.047 0.063 0.074 0.091 0.074 0.089 0.105 0.123 0.138 0.132 0.166 0.124 0.136 0.118
F4 0.063 0.099 0.134 0.157 0.204 0.175 0.213 0.262 0.324 0.373 0.393 0.561 0.417 0.514 0.428
Rk3 0.016 0.022 0.029 0.034 0.042 0.040 0.050 0.062 0.079 0.095 0.105 0.159 0.149 0.179 0.158
Rh4 0.025 0.033 0.044 0.050 0.067 0.063 0.079 0.096 0.127 0.155 0.172 0.268 0.235 0.308 0.279
S-Rg3 0.196 0.328 0.482 0.637 1.041 0.990 1.335 1.724 2.077 2.408 2.550 3.560 2.781 3.348 2.730
R-Rg3 0.116 0.186 0.300 0.452 0.926 0.605 0.946 1.426 1.057 1.460 1.711 2.324 2.419 2.713 1.695
Rk1 0.096 0.162 0.238 0.315 0.523 0.470 0.639 0.864 1.081 1.254 1.345 1.912 1.487 1.839 1.535
Rg5 0.141 0.231 0.337 0.444 0.734 0.658 0.899 1.233 1.551 1.805 1.953 2.784 2.167 2.712 2.296
S-Rh2 0.020 0.021 0.022 0.024 0.026 0.025 0.031 0.037 0.045 0.052 0.058 0.076 0.051 0.071 0.068
R-Rh2 0.012 0.014 0.013 0.015 0.019 0.020 0.025 0.028 0.028 0.033 0.031 0.048 0.030 0.032 0.025
Rk2 0.000 0.000 0.000 0.000 0.002 0.001 0.003 0.006 0.009 0.010 0.013 0.029 0.029 0.038 0.024
Rh3 0.000 0.000 0.004 0.005 0.007 0.008 0.011 0.015 0.022 0.026 0.029 0.048 0.027 0.048 0.052
Rg3Total amount of 0.313 0.513 0.783 1.089 1.967 1.595 2.281 3.150 3.134 3.867 4.260 5.884 5.200 6.061 4.425
Rh2Total amount of 0.032 0.034 0.036 0.038 0.046 0.045 0.056 0.065 0.073 0.085 0.090 0.124 0.081 0.103 0.093
Rg3+Rh2 0.345 0.548 0.818 1.127 2.012 1.640 2.337 3.216 3.207 3.952 4.350 6.008 5.280 6.163 4.518
Rk1+Rg5 0.237 0.393 0.575 0.759 1.257 1.128 1.538 2.097 2.632 3.059 3.298 4.696 3.654 4.551 3.831
Rg6+F4 0.092 0.146 0.197 0.231 0.295 0.249 0.302 0.367 0.447 0.511 0.525 0.727 0.541 0.650 0.546
Total amount (%) 1.327 1.817 2.418 2.983 4.492 3.752 4.979 6.572 7.276 8.609 9.272 12.940 10.635 12.758 10.064
Table 8: decocting Leptoradix Ginseng at 115 deg.C under high temperature and high pressure to obtain 15 kinds of rare ginsenoside contents (mg/ml, 4 hr, 8 hr and 48 hr for three time points)
Figure BDA0002708350310000171
Figure BDA0002708350310000181
Table 9: 15 rare ginsenoside contents in ginseng rootlets dregs decocted at high temperature and high pressure of 125 (%)
1h 6h 8h 12h 16h 20h 24h 28h 32h 36h 40h 44h 48h
S-Rg2 0.209 0.288 0.284 0.359 0.292 0.245 0.155 0.135 0.079 0.065 0.061 0.045 0.033
S-Rh1 0.302 0.270 0.272 0.404 0.370 0.383 0.323 0.282 0.199 0.178 0.182 0.160 0.129
R-Rh1 0.029 0.072 0.082 0.151 0.180 0.222 0.211 0.231 0.186 0.191 0.204 0.194 0.158
Rg6 0.042 0.086 0.097 0.167 0.157 0.157 0.128 0.113 0.087 0.078 0.082 0.060 0.050
F4 0.086 0.188 0.224 0.454 0.494 0.583 0.541 0.539 0.409 0.398 0.401 0.352 0.269
Rk3 0.024 0.047 0.058 0.125 0.157 0.211 0.227 0.264 0.232 0.265 0.320 0.327 0.298
Rh4 0.034 0.068 0.086 0.194 0.255 0.358 0.398 0.474 0.438 0.513 0.633 0.661 0.608
S-Rg3 0.318 1.090 1.350 2.690 2.801 3.260 2.963 3.080 2.423 2.467 2.681 2.486 2.065
R-Rg3 0.214 0.653 1.097 2.212 2.275 2.890 2.296 2.833 2.180 2.172 3.145 2.938 2.594
Rk1 0.160 0.545 0.689 1.495 1.615 1.966 1.898 2.091 1.745 1.875 2.164 2.147 1.894
Rg5 0.216 0.740 0.938 2.082 2.276 2.812 2.752 3.089 2.658 2.913 3.380 3.446 3.039
S-Rh2 0.018 0.029 0.036 0.064 0.072 0.088 0.088 0.097 0.084 0.094 0.114 0.119 0.111
R-Rh2 0.017 0.022 0.030 0.048 0.052 0.069 0.060 0.066 0.052 0.054 0.070 0.068 0.062
Rk2 0.000 0.000 0.000 0.018 0.028 0.029 0.027 0.033 0.030 0.037 0.043 0.051 0.051
Rh3 0.000 0.007 0.010 0.036 0.047 0.064 0.065 0.080 0.078 0.093 0.120 0.135 0.136
Rg3Total amount of 0.532 1.743 2.447 4.902 5.076 6.150 5.259 5.913 4.603 4.639 5.826 5.424 4.659
Rh2Total amount of 0.035 0.051 0.066 0.112 0.124 0.157 0.148 0.163 0.136 0.148 0.184 0.187 0.173
Rg3+Rh2 0.567 1.794 2.513 5.014 5.200 6.307 5.407 6.076 4.739 4.787 6.010 5.611 4.832
Rk1+Rg5 0.376 1.285 1.627 3.577 3.891 4.778 4.650 5.180 4.403 4.788 5.544 5.593 4.933
Rg6+F4 0.128 0.274 0.321 0.621 0.651 0.740 0.669 0.652 0.496 0.476 0.483 0.412 0.319
Total amount (%) 1.669 4.106 5.252 10.500 11.070 13.335 12.131 13.406 10.879 11.393 13.599 13.189 11.497
Table 10125 deg.c high-temperature high-pressure decoction of 7 kinds of common ginsenoside content (%)
Figure BDA0002708350310000182
Figure BDA0002708350310000191
Table 11: 15 rare ginsenoside contents in ginseng rootlets dregs decocted at high temperature and high pressure of 130%
20min 40min 1h 1.5h 2h 2.5h 10h 12h 14h 16h 20h
S-Rg2 0.162 0.212 0.243 0.267 0.273 0.290 0.183 0.250 0.197 0.173 0.097
S-Rh1 0.284 0.311 0.293 0.306 0.284 0.288 0.238 0.352 0.335 0.326 0.249
R-Rh1 0.028 0.026 0.035 0.047 0.054 0.061 0.107 0.191 0.198 0.227 0.201
Rg6 0.032 0.046 0.056 0.065 0.070 0.082 0.100 0.168 0.164 0.147 0.113
F4 0.058 0.089 0.109 0.130 0.139 0.161 0.291 0.524 0.564 0.599 0.529
Rk3 0.023 0.023 0.028 0.032 0.035 0.046 0.094 0.177 0.213 0.249 0.269
Rh4 0.032 0.034 0.042 0.049 0.053 0.068 0.146 0.292 0.359 0.430 0.490
S-Rg3 0.244 0.384 0.491 0.636 0.715 0.880 1.714 2.879 3.028 3.189 2.807
R-Rg3 0.172 0.247 0.438 0.592 0.671 0.687 2.186 2.684 2.812 3.193 2.832
Rk1 0.116 0.182 0.233 0.302 0.339 0.424 0.922 1.698 1.876 2.075 2.017
Rg5 0.166 0.248 0.307 0.411 0.453 0.575 1.304 2.416 2.699 2.999 3.002
S-Rh2 0.019 0.016 0.017 0.020 0.021 0.024 0.041 0.071 0.079 0.089 0.091
R-Rh2 0.005 0.016 0.020 0.021 0.021 0.022 0.041 0.060 0.063 0.069 0.063
Rk2 0.000 0.000 0.000 0.000 0.000 0.000 0.006 0.018 0.024 0.031 0.036
Rh3 0.000 0.000 0.003 0.003 0.004 0.006 0.022 0.042 0.052 0.064 0.076
Rg3Total amount of 0.416 0.631 0.929 1.228 1.386 1.567 3.900 5.563 5.840 6.382 5.639
Rh2Total amount of 0.024 0.032 0.037 0.041 0.042 0.046 0.082 0.131 0.142 0.158 0.154
Rg3+Rh2 0.440 0.663 0.966 1.269 1.428 1.613 3.982 5.694 5.982 6.540 5.793
Rk1+Rg5 0.282 0.430 0.540 0.713 0.792 0.999 2.226 4.114 4.575 5.074 5.019
Rg6+F4 0.090 0.135 0.165 0.195 0.209 0.243 0.391 0.692 0.728 0.746 0.642
Total amount (%) 1.341 1.834 2.315 2.881 3.132 3.614 7.395 11.822 12.663 13.860 12.872
The table 12130 ℃ high-temperature high-pressure reaction of 7 common ginsenoside contents in ginseng rootlets dregs (%)
20min 40min 1h 1.5h 2h 2.5h 10h 12h 14h 16h 20h
Rg1 0.043 0.033 0.021 0.013 0.006 0.004 0.000 0.000 0.000 0.000 0.000
Re 0.166 0.127 0.080 0.050 0.027 0.016 0.000 0.000 0.000 0.000 0.000
Rb1 0.687 0.646 0.465 0.440 0.273 0.212 0.000 0.000 0.000 0.000 0.000
Rc 0.593 0.555 0.419 0.366 0.269 0.202 0.000 0.000 0.000 0.000 0.000
Rb2 0.374 0.333 0.237 0.216 0.160 0.118 0.000 0.000 0.000 0.000 0.000
Rb3 0.052 0.043 0.029 0.025 0.019 0.014 0.000 0.000 0.000 0.000 0.000
Rd 0.381 0.369 0.304 0.294 0.236 0.223 0.014 0.000 0.000 0.000 0.000
Total amount (%) 2.296 2.106 1.555 1.404 0.990 0.789 0.014 0.000 0.000 0.000 0.000
As can be seen from tables 5 to 8, the change rule of the common ginsenoside is similar to that of the common ginsenoside decocted at 100 ℃ and normal pressure when the common ginsenoside is decocted at high temperature and high pressure. With the time, the content of the common ginsenoside in the water and the decoction dregs is gradually reduced, and the common ginsenoside can not be detected in the decoction dregs (44 hours) and the water liquid (48 hours). The rare ginsenoside changes in the way that the content of the rare ginsenoside in the water solution and the herb residue gradually increases from the beginning to the end. But the content of rare ginsenoside in the water solution begins to gradually decrease after the rare ginsenoside in the water solution increases to a certain degree, and the content of ginsenoside decreases to 0.703 percent after 48 hours; the content of rare ginsenoside in the medicine residue is continuously increased along with the prolonging of the decoction time, and reaches 12.94% after 40 hours, and then a rule of small fluctuation around the value is presented.
The same trends were observed at 120 deg.C, 125 deg.C, 130 deg.C, 135 deg.C, 140 deg.C and 145 deg.C thereafter, except that the time was continuously shortened as the temperature was increased.
For example, as can be seen from tables 9-12, the contents of rare ginsenosides in the residue gradually increase to a certain level and then remain unchanged, while the contents of common ginsenosides in the residue gradually decrease to 0.
When the temperature is designed to be 150 ℃, the change rule of various ginsenosides is not changed, but the total amount of rare ginsenosides generated in the decoction dregs is obviously reduced, so the decoction temperature is not suitable to exceed 150 ℃.
As can be seen from FIGS. 7A to 10, the total amount of rare ginsenosides in the residue reaches a maximum value of 13% or more at 125 deg.C and 130 deg.C, and the optimal decoction time is 20 hours or more and 16 hours or so, respectively.
As can be seen from FIGS. 11 to 17, for rare ginsenoside Rg3The optimum temperature is 125 ℃ and 130 ℃, and the content of the slag can reach 6.15 percent and 6.38 percent; the optimal decoction time is 20 hr or more and 16 hr or so.
For rare ginsenoside Rk1And Rg5The optimum temperature is 125 deg.C and 145 deg.C, the content can respectively reach 5.59% and 5.6%, and the optimum decocting time is 40 hr or more and 5 hr or more.
Example 3: reducing Rg in water3Experimental condition screening of content
Under the conditions of decocting at 120 deg.C, 130 deg.C, 135 deg.C and liquid-material ratio of 7.5:1 for 3, 4, 5, and hours, comparing the centrifugation immediately after the decoction and the next day centrifugation, adding Rg in water at normal temperature and heating to higher temperature (60-100 deg.C), adding Rg in water3Influence of the content.
The experimental result shows that the Rg in the hot water is immediately centrifuged3The content is lower than that of the next day of centrifugation, and Rg in the decoction dregs3The content was increased with a difference of 0.3%. Heating to a higher temperature (60-100 deg.C) for feeding, and adding Rg in the residue at a temperature higher than normal temperature3The content is higher, and the difference value reaches about 0.1 percent.
Example 4: preparing extract from medicinal residue
Collecting Leptoradix Ginseng, decocting at 115-145 deg.C with water temperature of 7.5:1 at 90 deg.C for 4-48 hr (corresponding to different decoction temperatures), centrifuging while hot, and removing centrifugal water to obtain residue. Drying the residue, extracting with ethanol under reflux, recovering ethanol from the extractive solution under reduced pressure, and drying to obtain the desired extract. The HPLC method detects that the main components comprise 15 rare ginsenosides: 20(S) -Rg2、20(S)-Rh1、20(R)-Rh1、Rg6、F4、Rk3、Rh4、20(S)-Rg3、20(R)-Rg3、Rk1、Rg5、20(S)-Rh2、20(R)-Rh2、Rk2、Rh3The total content of the ginseng extract reaches over 36 percent, and the ginseng extract basically does not contain common ginsenoside Rg1、Re、Rb1、Rc、Rb2、Rb3、Rd。
The yield of the medicine residue is that the weight of the medicine residue/the weight of the American ginseng leaves is multiplied by 100 percent
The extract yield is the weight of the extract/the weight of the medicine residue multiplied by 100 percent
Table 13: decocting Leptoradix Ginseng to obtain residue and extract
Figure BDA0002708350310000211
Table 14: content (%) of rare ginsenoside in the extract:
145℃ 140 135℃ 130℃ 125 120℃ 115℃
S-Rg2 0.238 0.600 0.853 0.361 0.747 1.193 0.894
S-Rh1 0.619 1.068 1.201 0.869 1.248 1.577 1.370
R-Rh1 0.576 0.637 0.587 0.741 0.736 0.727 0.665
Rg6 0.356 0.592 0.716 0.464 0.535 0.679 0.605
F4 1.541 1.889 1.752 1.662 1.771 1.816 1.767
Rk3 0.950 0.877 0.565 0.897 0.674 0.577 0.606
Rh4 1.424 1.167 0.826 1.471 1.092 0.906 1.070
S-Rg3 6.742 9.100 8.689 9.883 11.198 12.406 12.032
R-Rg3 7.955 8.567 7.402 9.882 9.739 10.167 9.220
Rk1 6.098 6.487 5.583 6.730 6.419 6.489 6.488
Rg5 8.786 8.985 7.600 9.772 9.103 9.201 9.573
S-Rh2 0.228 0.214 0.215 0.247 0.197 0.172 0.165
R-Rh2 0.210 0.186 0.133 0.154 0.132 0.121 0.075
Rk2 0.116 0.096 0.104 0.120 0.105 0.084 0.072
Rh3 0.232 0.149 0.177 0.245 0.183 0.151 0.133
Rg3total amount of 14.697 17.667 16.100 19.765 20.938 22.572 21.252
Rh2Total amount of 0.437 0.400 0.348 0.401 0.329 0.292 0.240
Rg3+Rh2 15.134 18.067 16.447 20.166 21.267 22.865 21.492
Rk1+Rg5 14.884 15.472 13.138 16.502 15.522 15.690 16.060
Rg6+F4 1.897 2.482 2.462 2.126 2.306 2.495 2.372
Total amount (%) 36.070 40.614 36.413 43.499 43.881 46.265 44.734
It can be seen that the total content of rare ginsenosides in the extract obtained by high temperature and high pressure decoction is between 30% and 50%, which is surprising. And at the temperature of 115-130 ℃, the total content of rare ginsenoside can reach more than 40%, and the total content of Rg3 can reach more than 14%, even more than 20%; the total content of Rk1 and Rg5 reaches more than 13 percent, even more than 15 percent. The extract with higher purity, the content of which reaches more than 50 percent and even more than 90 percent, is obtained by treating the extract with an organic solvent or by column chromatography.
Example 5: comparison of fresh Ginseng radix and dried Ginseng radix under normal pressure reflux and high temperature and high pressure
Heating dried Ginseng radix at 120 deg.C, 125 deg.C, 130 deg.C, and 135 deg.C for 5-16 hr with liquid-material ratio of 7.5:1, centrifuging, and oven drying to obtain residue. At this time, the content of rare ginsenoside in water solution is very low, and Rg enriched in herb residue3Is 16 times of that in water, F4、Rk3、Rh4The content is also higher, and is more than 10 times of that in water liquid.
The trend of the obtained experimental results is the same as that of the above experiments by using fresh ginseng with 70% of water content as a raw material and decocting at high temperature and high pressure under the same experimental conditions. The content of common ginsenoside in water solution and residue is gradually reduced, and the content of rare ginsenoside in residue is gradually increased.
Only because of the fresh ginseng, the obtained medicine dregs have much lower content of rare ginsenoside than the dried ginseng.
Example 6: inhibiting effect of different proportions of rare ginsenoside components on cancer cells
100 mu L of A549 human lung cancer cell suspension is inoculated in a 96-well plate, and the inoculation density is 8000 cells/well. The 96-well cell culture plate was placed in a cell incubator (culture conditions 37 ℃ C., 5% CO)2) And culturing for 24 h. The rare ginsenoside components with different proportions are prepared into high-concentration stock solutions by DMSO. Under the condition that the cells are in logarithmic growth, preparing a proper concentration gradient sample by using the stock solution, and co-culturing 24 groups of samples to be detected with different concentrations and the cells for 24 hours. When the cell activity is detected, cell supernatant of each group of the 96-well plate is discarded, a culture medium containing 10% of CCK-8 detection reagent is prepared, 100 mu L of the culture medium is added into each reaction hole, and the culture plate is placed in an incubator to be incubated for about 1 h. Absorbance at 450nm was measured with a microplate reader. Sample pair A549 tumor cell IC50The values are shown in the following table.
100 μ L of DLD1 human colon cancer cell suspension was seeded in 96-well plates at 8000 cells/well. The 96-well cell culture plate was placed in a cell incubator (culture conditions 37 ℃ C., 5% CO)2) And culturing for 24 h. The rare ginsenoside components with different proportions are prepared into high-concentration stock solutions by DMSO. Under the condition that the cells are in logarithmic growth, preparing a proper concentration gradient sample by using the stock solution, and co-culturing 24 groups of samples to be detected with different concentrations and the cells for 24 hours. When the cell activity is detected, cell supernatant of each group of the 96-well plate is discarded, a culture medium containing 10% of CCK-8 detection reagent is prepared, 100 mu L of the culture medium is added into each reaction hole, and the culture plate is placed in an incubator to be incubated for about 1 h. Absorbance at 450nm was measured with a microplate reader. Sample pair DLD1 tumor cell IC50The values are shown in the following table.
U251 human glioma cell suspension was seeded at 100 μ L in 96-well plates at 8000 cells/well. The 96-well cell culture plate was placed in a cell incubator (culture conditions 37 ℃ C., 5% CO)2) And culturing for 24 h. The rare ginsenoside components with different proportions are prepared into high-concentration stock solutions by DMSO. Under the condition that the cells are in logarithmic growth, preparing a proper concentration gradient sample by using the stock solution, and co-culturing 24 groups of samples to be detected with different concentrations and the cells for 24 hours. When the cell activity is detected, cell supernatant of each group of the 96-well plate is discarded, a culture medium containing 10% of CCK-8 detection reagent is prepared, 100 mu L of the culture medium is added into each reaction hole, and the culture plate is placed in an incubator to be incubated for about 1 h. Using enzyme labelsThe absorbance at 450nm was measured. 24 groups of samples for U251 tumor cells IC50The values are shown in the following table.
TABLE 15 inhibition of cancer cells by different proportions of rare ginsenoside components
Figure BDA0002708350310000221
Figure BDA0002708350310000231
Through screening tests, a combination with better cancer cell inhibition activity in different rare ginsenoside combinations is screened out, and the combination shows synergistic antitumor activity on three kinds of cancer cells.
The applicant finds that the extract is also applicable to other active parts of ginseng and plants containing other ginsenosides, such as American ginseng, pseudo-ginseng and the like, and researches on ginseng leaves, pseudo-ginseng leaves, American ginseng and American ginseng leaves respectively through a large number of experiments, so that the same results are obtained, and a better extraction method is obtained, and the specific steps are as follows:
a method for preparing a product with high content of rare ginsenoside comprises any one of the following steps:
a: pulverizing folium Ginseng, adding appropriate amount of water, heating and refluxing under normal pressure for 36 hr or more, preferably 40 hr, 60 hr, 72 hr, 84 hr, 96 hr 108 hr or 120 hr or more, filtering, and drying the residue to obtain the desired product;
b: pulverizing folium Ginseng, adding appropriate amount of water, decocting at high temperature and under high pressure for 1 hr or more, 2 hr or more, 3 hr or more, 4 hr or more, 5 hr or more, preferably 6 hr or more, 8 hr or more, 10 hr or more, 12 hr or more, 14 hr or more, 16 hr or more, 18 hr or more, 20 hr or more, 22 hr or more, 24 hr or more, 28 hr or more, 30 hr or more, 32 hr or more, 34 hr or more, 36 hr or more, 38 hr or more, 40 hr or more, 42 hr or more, 44 hr or more, 48 hr or more, or 50 hr or more, filtering, and drying the residue to obtain the desired product.
A product for preparing high-content rare ginsenoside is prepared by any one of the following methods:
a: pulverizing Notoginseng radix, adding appropriate amount of water, heating and refluxing under normal pressure for more than 48 hr, preferably 60 hr, 72 hr, 84 hr, 96 hr 108 hr or more than 120 hr, filtering, and drying the residue to obtain the desired product;
b: pulverizing Notoginseng radix, adding appropriate amount of water, decocting at high temperature and high pressure for more than 4 hr, preferably more than 6 hr, more than 8 hr, more than 10 hr, more than 12 hr, more than 14 hr, more than 16 hr, more than 18 hr, more than 20 hr, more than 22 hr, more than 24 hr, more than 28 hr, more than 30 hr, more than 32 hr, more than 34 hr, more than 36 hr, more than 38 hr, more than 40 hr, more than 42 hr, more than 44 hr, more than 48 hr or more than 50 hr, filtering, and drying the residue to obtain the desired product.
A method for preparing a product with high content of rare ginsenoside comprises any one of the following steps:
a: drying and pulverizing folium Notoginseng, adding appropriate amount of water, heating and refluxing under normal pressure for more than 48 hr, preferably 60 hr, 72 hr, 84 hr, 96 hr 108 hr or more than 120 hr, filtering, and drying the residue to obtain the desired product;
b: drying and pulverizing folium Notoginseng, adding appropriate amount of water, decocting at high temperature and high pressure for more than 2 hr, preferably more than 4 hr, preferably more than 6 hr, more than 8 hr, more than 10 hr, more than 12 hr, more than 14 hr, more than 16 hr, more than 18 hr, more than 20 hr, more than 22 hr, more than 24 hr, more than 28 hr, more than 30 hr, more than 32 hr, more than 34 hr, more than 36 hr, more than 38 hr, more than 40 hr, more than 42 hr, more than 44 hr, more than 48 hr or more than 50 hr, filtering, and drying the residue to obtain the desired product.
A product for preparing high-content rare ginsenoside is prepared by any one of the following methods:
a: pulverizing radix Panacis Quinquefolii, adding appropriate amount of water, heating and refluxing under normal pressure for more than 48 hr, preferably 60 hr, 72 hr, 84 hr, 96 hr or 108 hr, filtering, and drying the residue to obtain the desired product;
b: drying and pulverizing radix Panacis Quinquefolii, adding appropriate amount of water, decocting at high temperature and high pressure for more than 4 hr, preferably more than 6 hr, more than 8 hr, more than 10 hr, more than 12 hr, more than 14 hr, more than 16 hr, more than 18 hr, more than 20 hr, more than 22 hr, more than 24 hr, more than 28 hr, more than 30 hr, more than 32 hr, more than 34 hr, more than 36 hr, more than 38 hr, more than 40 hr, more than 42 hr, more than 44 hr, more than 48 hr or more than 50 hr, filtering, and drying the residue to obtain the desired product.
A method for preparing a product with high content of rare ginsenoside comprises any one of the following steps:
a: drying and pulverizing folium Panacis Quinquefolii, adding appropriate amount of water, and heating and refluxing under normal pressure for more than 48 hr, preferably 60 hr, 72 hr, 84 hr, 96 hr or more than 108 hr; more preferably 90 hours; filtering, and drying the residues to obtain the required product;
b: drying and pulverizing folium Panacis Quinquefolii, adding appropriate amount of water, decocting at high temperature and high pressure for 2 hr or more than 4 hr, preferably 6 hr or more, 8 hr or more, 10 hr or more, 12 hr or more, 14 hr or more, 16 hr or more, 18 hr or more, 20 hr or more, 22 hr or more, 24 hr or more, 28 hr or more, 30 hr or more, 32 hr or more, 34 hr or more, 36 hr or more, 38 hr or more, 40 hr or more, 42 hr or more, 44 hr or more, 48 hr or more, or 50 hr or more, filtering, and drying the residue to obtain the desired product.
Because the experimental data is too huge, the applicant carries out divisional application on different parts and different plants, and the detailed data is shown in patent application on the same day.
The foregoing description is a general description of the invention. Although specific terms are employed herein, they are used in a generic and descriptive sense only and not for purposes of limitation, as form changes and equivalents may be employed. Various changes or modifications may be effected therein by one skilled in the art and equivalents may be made thereto without departing from the scope of the invention as defined in the claims appended hereto.

Claims (10)

1. A product prepared from Ginseng radix contains high content of rare ginsenoside, and does not contain common ginsenoside; wherein the rare ginsenoside comprises: 20(S) -Rg2、20(S)-Rh1、20(R)-Rh1、Rg6、F4、Rk3、Rh4、20(S)-Rg3、20(R)-Rg3、Rk1、Rg5、20(S)-Rh2、20(R)-Rh2、Rk2、Rh3And the common ginsenoside comprises: rg (Rg)1、Re、Rb1、Rc、Rb2、Rb3、Rd。
2. The product of claim 1, wherein the total content of rare ginsenosides is not less than 5%, and the total content of common ginsenosides is less than 1%.
3. A method for preparing a high-content rare ginsenoside product is characterized in that the preparation method comprises the following steps:
a: pulverizing Ginseng radix, adding appropriate amount of water, heating and refluxing under normal pressure for more than 48 hr, preferably 60 hr, 72 hr, 84 hr, 96 hr, 108 hr or more than 120 hr, filtering, and drying the residue to obtain desired product;
b: pulverizing Ginseng radix, adding appropriate amount of water, decocting at high temperature and high pressure for more than 4 hr, preferably more than 6 hr, more than 8 hr, more than 10 hr, more than 12 hr, more than 14 hr, more than 16 hr, more than 18 hr, more than 20 hr, more than 22 hr, more than 24 hr, more than 28 hr, more than 30 hr, more than 32 hr, more than 34 hr, more than 36 hr, more than 38 hr, more than 40 hr, more than 42 hr, more than 44 hr, more than 48 hr or more than 50 hr, filtering, and drying the residue to obtain desired product; the high temperature and high pressure is 100 deg.C or more, preferably not less than 110 deg.C, 115 deg.C, 120 deg.C, 125 deg.C, 130 deg.C, 135 deg.C, 140 deg.C, 145 deg.C or 150 deg.C.
4. The process according to claim 3, wherein:
in preparation method A, the liquid-to-material ratio can be (30-5):1, preferably (25-8):1, more preferably (20-9):1 or (15-10):1, preferably 10: 1;
in preparation method B, the liquid-to-feed ratio may be (30-5):1, preferably (25-6):1, more preferably (20-7):1 or (10-8):1, preferably 7.5: 1.
5. The process according to claim 3 or 4, wherein: optionally further extracting the residue with organic solvent or aqueous organic solvent to obtain extract with high content of rare ginsenoside.
6. The production method according to any one of claims 3 to 5, characterized in that:
the extract or residue contains one or more of 15 rare ginsenosides, specifically 20(S) -Rg2、20(S)-Rh1、20(R)-Rh1、Rg6、F4、Rk3、Rh4、20(S)-Rg3、20(R)-Rg3、Rk1、Rg5、20(S)-Rh2、20(R)-Rh2、Rk2、Rh3Substantially free of common ginsenoside including Rg1、Re、Rb1、Rc、Rb2、Rb3、Rd;
The total content of rare ginsenoside in the residue is not less than 5%, 7%, 8%, 9%, 10%, 11% or 12%, and the total content of common ginsenoside is not more than 3%, 2%, 1%, 0.8%, 0.7%, 0.5%, 0.4%, 0.2% or 0.1%;
the total content of rare ginsenoside in the extract is more than 20%, 25%, 30%, 35% or 40%, and the total content of common ginsenoside is less than 10%, preferably less than 8%, 6%, 5%, 4%, 3%, 2% or 1%.
7. A composition comprising a rare ginsenoside, comprising a composition of any one of:
Rg3and Rg5The composition of (1) to (20): (1-20); comprising F4And Rh2The composition of (1) to (100): (1-100), preferably (1-10): (10-100), (10-100): (1-10), (1-10): (10-1), (1-100): (1-10); most preferred is 10:1, 1:1 or 1: 10. Containing Rh4And Rh2The composition of (1) to (100): (1-100), preferably (1-90): (1-90), (10-100): (1-10), (1-10): (10-1), (1-20): (1-20).
Optionally further comprises 20(S) -Rg2、20(S)-Rh1、20(R)-Rh1、Rg6、F4、Rk3、Rh4、20(S)-Rg3、20(R)-Rg3、Rk1、Rg5、20(S)-Rh2、20(R)-Rh2、Rk2、Rh3One or more rare ginsenosides in (1).
Preferably, the composition is substantially free of common ginsenosides, including Rg1、Re、Rb1、Rc、Rb2、Rb3And Rd. The total content of common ginsenoside is less than 10%, preferably less than 8%, 6%, 5%, 4%, 3%, 2% or 1%. More preferably, less than 0.8%, 0.6%, 0.5% or 0.1%.
8. A ginseng product comprising the composition of claim 7.
9. The ginseng product of claim 8, wherein the ginseng product is a residue or extract prepared from ginseng.
10. Use of a product or composition according to any one of claims 1, 2, 7, 8, 9 for the preparation of an anti-tumour product.
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