CN113603737B - Method for extracting and separating liquiritin and glycyrrhizic acid - Google Patents
Method for extracting and separating liquiritin and glycyrrhizic acid Download PDFInfo
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- CN113603737B CN113603737B CN202110903344.3A CN202110903344A CN113603737B CN 113603737 B CN113603737 B CN 113603737B CN 202110903344 A CN202110903344 A CN 202110903344A CN 113603737 B CN113603737 B CN 113603737B
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07H—SUGARS; DERIVATIVES THEREOF; NUCLEOSIDES; NUCLEOTIDES; NUCLEIC ACIDS
- C07H15/00—Compounds containing hydrocarbon or substituted hydrocarbon radicals directly attached to hetero atoms of saccharide radicals
- C07H15/26—Acyclic or carbocyclic radicals, substituted by hetero rings
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- C07—ORGANIC CHEMISTRY
- C07H—SUGARS; DERIVATIVES THEREOF; NUCLEOSIDES; NUCLEOTIDES; NUCLEIC ACIDS
- C07H1/00—Processes for the preparation of sugar derivatives
- C07H1/06—Separation; Purification
- C07H1/08—Separation; Purification from natural products
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- C07J63/00—Steroids in which the cyclopenta(a)hydrophenanthrene skeleton has been modified by expansion of only one ring by one or two atoms
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- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/54—Improvements relating to the production of bulk chemicals using solvents, e.g. supercritical solvents or ionic liquids
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Abstract
The invention discloses a method for extracting and separating liquiritin and glycyrrhizic acid, which comprises the following steps: s1, mixing the ionic liquid with licorice powder, and extracting liquiritin and glycyrrhizic acid; s2, after extraction is finished, carrying out solid-liquid separation, taking supernate, adding NaOH solution, heating to 65-80 ℃ to obtain an ionic liquid phase containing liquiritin and a water phase containing glycyrrhizic acid, and separating the water phase from the ionic liquid phase; wherein the ionic liquid is a temperature response type ionic liquid. According to the invention, the temperature-responsive ionic liquid is used as an extracting agent, and the temperature of the system is changed after extraction is finished, so that the liquiritin and the glycyrrhizic acid can be separated.
Description
Technical Field
The invention relates to the field of extraction of liquiritin and glycyrrhizic acid, and particularly relates to a method for extracting and separating liquiritin and glycyrrhizic acid.
Background
The licorice is the dry root or rhizome of the perennial herb and the plant of the leguminous, is a tonifying Chinese herbal medicine, and has the effects of tonifying spleen and qi, clearing away heat and toxic materials, eliminating phlegm and stopping cough, relieving spasm and pain and harmonizing the medicines.
Modern chemical research shows that licorice mainly contains flavonoid glycoside components (liquiritin, isoliquiritin and the like) and glycyrrhizic acid components, wherein the content of the liquiritin and the glycyrrhizic acid is the highest. Liquiritin belongs to flavonoid compounds and has the functions of neuroprotection, oxidation resistance and myocardial fibrosis resistance; glycyrrhizic acid belongs to triterpenoid saponin compounds, and has pharmacological effects of resisting inflammation, resisting virus, protecting liver and the like. The traditional method for extracting liquiritin and glycyrrhizic acid usually adopts organic solvent or water as an extracting agent, or combines ultrasonic extraction and microwave-assisted extraction. These methods consume large amounts of organic solvents, causing serious environmental impact. And the traditional solid-liquid extraction method can not effectively separate the liquiritin and the glycyrrhizic acid. There are related documents reporting new methods for simultaneously extracting and separating glycyrrhizin and glycyrrhizic acid by using an aqueous two-phase system and a three-phase extraction system, and these methods, although effective, also use a large amount of organic solvents. The high-speed counter-current chromatography is used for separating and purifying the liquiritin and the glycyrrhizic acid, has complex equipment and high cost, and limits the application of the liquiritin and the glycyrrhizic acid.
The ionic liquid is a salt composed of anions and cations and in a molten state at or near room temperature. Compared with the traditional organic solvent, the ionic liquid has the characteristics of non-volatility, non-flammability, strong extraction capacity and the like, so the ionic liquid is considered to be a novel green solvent. The research on extracting and separating bioactive substances from natural plant resources by using ionic liquid as an extracting agent is increasing. However, these methods have a great problem. Due to the non-volatility of ionic liquids, the desired product is difficult to separate from the extractant. Therefore, back extraction and column chromatography separation methods using organic solvents are still widely used.
Disclosure of Invention
Based on the technical problems in the prior art, the invention aims to provide a method for extracting and separating liquiritin and glycyrrhizic acid, wherein the liquiritin and glycyrrhizic acid can be separated by using temperature-responsive ionic liquid as an extracting agent and changing the system temperature after extraction is finished, the method is simple, and the used ionic liquid can be recycled and reused, so that the method is green and environment-friendly.
In order to achieve the purpose, the technical scheme of the invention is as follows:
a method for extracting and separating glycyrrhizin and glycyrrhizic acid comprises the following steps:
s1, mixing the ionic liquid with licorice powder, and extracting;
s2, after extraction is finished, carrying out solid-liquid separation, taking supernate, adding NaOH solution, heating to 65-80 ℃ to obtain an ionic liquid phase containing liquiritin and a water phase containing glycyrrhizic acid, and separating the water phase from the ionic liquid phase;
wherein the ionic liquid is a temperature response type ionic liquid.
The temperature response type ionic liquid is a special ionic liquid and has the characteristic of changing state or property by changing the temperature of the external environment. The temperature response type ionic liquid serving as a novel green solvent can replace the traditional volatile organic solvent to be applied to extraction and separation of active ingredients of natural products.
The invention utilizes the characteristic that temperature response type ionic liquid can change according to the temperature generation state or property as an extracting agent to extract the liquorice so as to realize the extraction and separation of liquiritin and glycyrrhizic acid in the liquorice.
In some embodiments, the ionic liquid is tetrabutylphosphonium p-toluenesulfonate.
In some embodiments, in step S1, the ionic liquid concentration is 20 to 80%.
In some embodiments, in step S1, the extraction temperature is 40 to 60 ℃.
In some embodiments, in step S1, the solid-to-liquid ratio is 1 g.
In some embodiments, in step S1, the extraction time is 10 to 60min.
In some embodiments, in step S2, a NaOH solution is added to form a mixed solution, wherein the concentration of the NaOH is 0 to 2%.
In some embodiments, further comprising the steps of:
and S3, adding a tannic acid aqueous solution into the ionic liquid phase, and then carrying out solid-liquid separation to obtain liquiritin and ionic liquid.
In some embodiments, the aqueous tannic acid solution has a concentration of 0.95 to 7.5%.
In some embodiments, the aqueous tannic acid solution has a concentration of 3.33 to 7.5%.
Compared with the prior art, the invention has the following beneficial effects:
the invention creatively takes the temperature response type ionic liquid as an extractant to extract the liquorice, then sodium hydroxide solution is added, and the temperature of the solution system is changed to realize the separation of the water phase and the ionic liquid, thereby realizing the extraction and the separation of the liquiritin and the glycyrrhizic acid.
The method can effectively separate the liquiritin and the glycyrrhizic acid, and the used ionic liquid can be recycled and recycled by a simple method, so that the cost is saved, and the method is green and environment-friendly.
Detailed Description
In the following description, numerous specific details are set forth in order to provide a thorough understanding of the present invention. This invention may, however, be embodied in many different forms than those specifically described herein, and it will be apparent to those skilled in the art that many more modifications are possible without departing from the spirit and scope of the invention.
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. The terminology used in the description of the invention herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention.
The ionic liquid used in the following examples is tetrabutyl phosphonium p-toluenesulfonate sodium which is one of temperature response type ionic liquids, the ionic liquid can be homogeneous with water at low temperature, and the ionic liquid can be separated into two phases with water at elevated temperature. The ionic liquid is prepared by the following method:
mixing tetrabutyl phosphonium bromide and sodium p-toluenesulfonate in water according to a molar ratio of 1:1, magnetically stirring, heating to 70 ℃ for reacting for 24 hours, and evaporating water to dryness to obtain a residual liquid, namely the ionic liquid tetrabutyl phosphonium p-toluenesulfonate.
The method for extracting and separating the liquiritin and the glycyrrhizic acid in the following embodiments comprises the following steps:
s1, mixing the ionic liquid with licorice powder, and extracting;
s2, after extraction is finished, carrying out solid-liquid separation, taking supernate, adding NaOH solution, heating to 65-80 ℃ to obtain an ionic liquid phase containing liquiritin and a water phase containing glycyrrhizic acid, and separating the water phase from the ionic liquid phase.
Examples 1 to 5
The method of the step S1 is adopted to extract the licorice, and in the examples 1 to 5, other extraction conditions are the same, specifically: the solid-liquid ratio is 1 g. After the extraction, the extraction effects of glycyrrhizin and glycyrrhizic acid were measured, as shown in table 1.
TABLE 1 Effect of ionic liquids of different concentrations on the extraction yield of glycyrrhizin and glycyrrhizic acid
| Examples | Concentration of Ionic liquid (%) | Glycyrrhiza glycosides extraction rate (mg/g) | Glycyrrhetinic acid extraction yield (mg/g) |
| 1 | 20 | 5.52 | 15.00 |
| 2 | 40 | 5.71 | 15.30 |
| 3 | 50 | 5.79 | 19.82 |
| 4 | 60 | 6.61 | 25.04 |
| 5 | 80 | 6.22 | 18.79 |
Examples 6 to 10
The method of the step S1 is adopted to extract the glycyrrhiza, and in the embodiments 6 to 10, other extraction conditions are the same, specifically: the concentration of the ionic liquid is 60%, the extraction temperature is 50 ℃, and the extraction time is 30min, wherein the difference is that the solid-liquid ratio is different. After the extraction, the extraction effects of glycyrrhizin and glycyrrhizic acid were respectively tested, as shown in table 2.
TABLE 2 influence of different solid-liquid ratios on the extraction rates of glycyrrhizin and glycyrrhizic acid
| Examples | Solid to liquid ratio (g/ml) | Glycyrrhiza glycosides extraction rate (mg/g) | Glycyrrhetinic acid extraction yield (mg/g) |
| 6 | 1:100 | 7.81 | 25.47 |
| 7 | 1:50 | 11.27 | 25.58 |
| 8 | 1:40 | 8.10 | 20.38 |
| 9 | 1:25 | 7.21 | 16.46 |
| 10 | 1:20 | 7.13 | 14.30 |
Examples 11 to 15
The method of the step S1 is adopted to extract the licorice, and in examples 11 to 15, the other conditions are the same, specifically: the concentration of the ionic liquid is 60%, the solid-liquid ratio is 1g:50mL, and 30min of extraction time, with the difference that the extraction temperature is different. After the extraction, the extraction effects of glycyrrhizin and glycyrrhizic acid were measured, as shown in table 3.
TABLE 3 Effect of different extraction temperatures on the extraction yield of Glycyrrhiza glycosides and Glycyrrhiza acids
| Examples | Temperature (. Degree.C.) | Glycyrrhiza glycosides extraction rate (mg/g) | Glycyrrhetinic acid extraction yield (mg/g) |
| 11 | 40 | 9.41 | 23.33 |
| 12 | 45 | 10.78 | 23.94 |
| 13 | 50 | 11.22 | 24.89 |
| 14 | 55 | 9.65 | 28.29 |
| 15 | 60 | 8.61 | 26.78 |
Examples 16 to 20
The method of the step S1 is adopted to extract the licorice, and in the examples 16 to 20, the other conditions are the same, specifically: the concentration of the ionic liquid is 60%, the solid-to-liquid ratio is 1g:50mL, and an extraction time of 55 ℃ except that the extraction time was varied. After the extraction, the extraction effects of glycyrrhizin and glycyrrhizic acid were measured, as shown in table 4.
TABLE 4 Effect of different extraction times on the extraction of Glycyrrhiza glycosides and glycyrrhizic acids
| Examples | Time (min) | Glycyrrhiza glycosides extraction rate (mg/g) | Glycyrrhetinic acid extraction rate (mg/g) |
| 16 | 10 | 9.65 | 22.41 |
| 17 | 20 | 9.72 | 24.32 |
| 18 | 30 | 9.63 | 28.51 |
| 19 | 40 | 9.13 | 25.75 |
| 20 | 60 | 9.20 | 25.59 |
As can be seen from the above examples 1-20, when tetrabutyl phosphonium is selected to use sodium methanesulfonate as an ionic liquid as an extractant to extract glycyrrhizin and glycyrrhizic acid from licorice, the extraction effect is affected by the concentration of the ionic liquid, the solid-liquid ratio, the extraction temperature and the extraction time, and when the concentration of the ionic liquid is 60%, the solid-liquid ratio is 1g: the extraction effect on the liquiritin and the glycyrrhizic acid is best when the volume is 40mL, the extraction temperature is 55 ℃ and the extraction time is 30 min.
Examples 21 to 24
The method of the step S2 is adopted to separate the liquiritin and the glycyrrhizic acid, and the specific operation is as follows: after extraction, performing solid-liquid separation by centrifugation, taking supernatant, adding NaOH solution, and heating to 70 deg.C to obtain liquiritin-containing ionic liquid phase and glycyrrhizic acid-containing water phase. Examples 21 to 24 differ in the NaOH solution added, as shown in Table 5.
TABLE 5 Effect of different NaOH concentrations on the extraction and separation of glycyrrhizic acid and glycyrrhizin
| Examples | NaOH concentration (%) | Distribution coefficient of liquiritin | Distribution coefficient of glycyrrhizic acid | Coefficient of system selectivity |
| 21 | 0 | 11.17 | 0.09 | 0.96 |
| 22 | 0.5 | 4.22 | 2.36 | 9.95 |
| 23 | 1 | 3.19 | 4.16 | 13.27 |
| 24 | 2 | 2.09 | 3.56 | 7.45 |
Examples 25 to 29
The liquiritin and glycyrrhizic acid were extracted and separated by the method of the above step S2, and in examples 25 to 29, the concentrations of the added NaOH solutions were all 1%, except that the extraction temperatures were different, as shown in table 6.
TABLE 6 influence of different extraction temperatures on the extraction and separation of glycyrrhizin and glycyrrhizic acid
From examples 21 to 29, it is understood that the effect of separating glycyrrhizin from glycyrrhizic acid was the best when the concentration of NaOH solution added was 1% and the extraction time was 70 ℃.
Separating the ionic liquid phase and the water phase, adding tannic acid into the ionic liquid phase, allowing the tannic acid to complex with liquiritin in the ionic liquid phase to form precipitate, separating liquiritin from the ionic liquid, and performing solid-liquid separation to obtain liquiritin and the ionic liquid. The ionic liquid may be diluted 5-fold prior to the addition of tannic acid. The influence of different tannin concentrations on the liquiritin separation effect is examined and is specifically shown in table 7.
TABLE 7 Effect of different tannin concentrations on liquiritin separation Effect
| Tannin concentration (%) | Distribution coefficient of liquiritin |
| 0.95 | 23.18 |
| 3.33 | 67.41 |
| 4.62 | 71.51 |
| 5.71 | 76.74 |
| 6.67 | 87.38 |
| 7.50 | 88.08 |
In summary, the most preferred embodiments of the method of the present invention are:
s1, mixing 60% ionic liquid and licorice powder according to a solid-to-liquid ratio of 1g: mixing 50mL of the components, and extracting at the temperature of 55 ℃ for 30min;
s2, after extraction is finished, carrying out solid-liquid separation, taking supernate, adding 1% NaOH solution, heating to 70 ℃ to obtain an ionic liquid phase containing liquiritin and a water phase containing glycyrrhizic acid, and separating the ionic liquid phase and the water phase.
Adding tannin with concentration of 7.5% into the ionic liquid phase to separate out liquiritin from the ionic liquid phase to obtain liquiritin and ionic liquid. The separated ionic liquid can be circularly used for extracting liquiritin and glycyrrhizic acid.
All possible combinations of the technical features of the above embodiments may not be described for the sake of brevity, but should be considered as within the scope of the present disclosure as long as there is no contradiction between the combinations of the technical features.
The above-mentioned embodiments only express several embodiments of the present invention, and the description thereof is more specific and detailed, but not construed as limiting the scope of the invention. It should be noted that, for a person skilled in the art, several variations and modifications can be made without departing from the inventive concept, which falls within the scope of the present invention. Therefore, the protection scope of the present patent shall be subject to the appended claims.
Claims (8)
1. A method for extracting and separating liquiritin and glycyrrhizic acid is characterized by comprising the following steps:
s1, mixing the ionic liquid with licorice powder, and extracting liquiritin and glycyrrhizic acid;
s2, after extraction is finished, carrying out solid-liquid separation, taking supernate, adding NaOH solution, heating to 65-80 ℃ to obtain an ionic liquid phase containing liquiritin and a water phase containing glycyrrhizic acid, and separating the water phase from the ionic liquid phase;
wherein the ionic liquid is tetrabutyl phosphonium p-toluenesulfonate sodium;
in step S1, the extraction temperature is 40-60 ℃.
2. The method for extracting and separating glycyrrhizin and glycyrrhizic acid according to claim 1, wherein in step S1, the ionic liquid concentration is 20-80%.
3. The method for extracting and separating glycyrrhizic acid from glycyrrhizic acid according to claim 1, wherein in step S1, the solid-to-liquid ratio is 1g.
4. The method for extracting and separating glycyrrhizin and glycyrrhizic acid according to claim 1, wherein in step S1, the extraction time is 10-60 min.
5. The method for extracting and separating glycyrrhizic acid from glycyrrhizin according to claim 1, wherein in step S2, naOH solution is added to form a mixed solution, wherein the concentration of NaOH is 0-2%.
6. The method for extracting and separating glycyrrhizin and glycyrrhizic acid according to any one of claims 1 to 5, further comprising the steps of:
and S3, adding a tannic acid aqueous solution into the ionic liquid phase, and then carrying out solid-liquid separation to obtain liquiritin and ionic liquid.
7. The method for extracting and separating glycyrrhizin and glycyrrhizic acid according to claim 6, wherein the concentration of the aqueous solution of tannic acid is 0.95-7.5%.
8. The method for extracting and separating glycyrrhizin and glycyrrhizic acid according to claim 7, wherein the concentration of the aqueous solution of tannic acid is 3.33-7.5%.
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| CN104861015A (en) * | 2015-01-16 | 2015-08-26 | 李玉山 | Synergistic clean extraction method of effective components in licorice root |
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| 甘草总黄酮研究进展;董庄庄 等;《池州学院学报》;20201231;第437-445页 * |
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