CN109810116B - Method for purifying ellagic acid in chestnut shell extracting solution - Google Patents
Method for purifying ellagic acid in chestnut shell extracting solution Download PDFInfo
- Publication number
- CN109810116B CN109810116B CN201910140586.4A CN201910140586A CN109810116B CN 109810116 B CN109810116 B CN 109810116B CN 201910140586 A CN201910140586 A CN 201910140586A CN 109810116 B CN109810116 B CN 109810116B
- Authority
- CN
- China
- Prior art keywords
- ellagic acid
- solution
- chestnut shell
- acid
- reaction
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Images
Landscapes
- Cosmetics (AREA)
- Medicines Containing Plant Substances (AREA)
- Heterocyclic Carbon Compounds Containing A Hetero Ring Having Oxygen Or Sulfur (AREA)
Abstract
The ellagic acid is purified by utilizing the complexation of metal salt ions and the ellagic acid. The method comprises the following steps: polyphenols such as ellagic acid extracted by solvent method can form coordination complex with metal salt ion under alkaline condition; separating out the complex; adding substances with stronger chelating ability with metal salt ions, such as EDTA, acid, etc., to decomplex the metal salt-polyphenol complex and release polyphenol substances. The purpose of purifying the ellagic acid is realized through the difference of the chelating capacity of different phenolic substances and metal ions. The method has the advantages of simple and efficient operation, low cost and small pollution burden.
Description
Technical Field
The invention provides a method for purifying ellagic acid in a chestnut shell extracting solution, and belongs to the field of natural compound purification.
Background
The chestnut shell contains multiple polyphenol components such as gallic acid, ellagic acid, shikimic acid, quercetin, protocatechuic acid, oleanolic acid, ursolic acid, etc. The natural plant polyphenol can improve the metabolism condition of a body, reduce the incidence rate of cardiovascular and cerebrovascular diseases, and simultaneously has good effects on the aspects of tumor resistance, virus resistance, aging resistance, oxidation resistance and the like.
The extractive solution obtained by extracting chestnut shell with solvent contains multiple bioactive substances such as polyphenols, flavonoids and saccharides, wherein ellagic acid is the component with the maximum content in polyphenols of chestnut shell extractive solution, and accounts for about 50% of total phenols content. Therefore, the high-purity ellagic acid is obtained by separating and purifying the polyphenols in the chestnut shell extracting solution, and the utilization value of the chestnut shell is favorably improved.
Ellagic acid is a polyphenol dilactone, a dimeric derivative of gallic acid. The intramolecular large pi bond conjugated system and the molecular space configuration of the ortho-position dihydroxyl determine that the ellagic acid phenolic hydroxyl group has strong capability of chelating metal ions (such as longchumei, etc.. complexing agent in the process of preparing tea polyphenol by complexing precipitation method and Fe3+Influence [ J]Application chemistry, 2005,22(12): 1387-. Under alkaline conditions, phenolic hydroxyl groups can react with OH-The ions react to generate corresponding negative ions, so that the polyphenol substances have high complexing ability with metal salt ions in an alkaline medium, thereby generating the metal salt ionsm- (phenol)nThe ligand can utilize the difference of complexation ability of phenols such as ellagic acid and the like in the extracting solution and metal salt ions to achieve the purpose of separating and purifying ellagic acid in the extracting solution of chestnut shells. Ethylenediaminetetraacetic acid (EDTA) is a strong chelating agent for metal ions, and when EDTA is added to a polyphenol-metal salt ion complex precipitate, the metal ions are generated due to the stronger complexing ability of EDTA with the metal ionsm-EDTAnThe complex thereby competing with the polyphenol species to free the complexed metal ion from complexation with the polyphenolWhich in turn complexes with EDTA, releasing polyphenols. In addition, the polyphenol-metal salt ion complex can also be destroyed in an acidic environment due to the large amount of H in the acidic environment+The polyphenol molecules are reformed to open coordination bonds. Therefore, EDTA or acidic environment can be used to release polyphenol substances from polyphenol-metal complex, so as to realize the purification of ellagic acid. In the process of forming the complex, zinc ions and copper ions can be used as complex ions, and hydrochloric acid, acetic acid and Ethylene Diamine Tetraacetic Acid (EDTA) can be used as a decomplexing agent.
Therefore, the invention designs a method for purifying ellagic acid in the chestnut shell extracting solution by forming polyphenol-metal salt ion complexes and then opening the complexes.
Disclosure of Invention
The invention aims to develop a method for simply, conveniently, quickly and efficiently purifying ellagic acid in a chestnut shell extracting solution by utilizing the characteristics that polyphenols are easy to form a complex with metal salt ions and can release the polyphenols in the presence of a decomplexing agent.
The method has the characteristics of no use of toxic and harmful reagents, no dangerous operation such as high temperature and high pressure and the like in the process of purifying the ellagic acid.
The purpose of the invention is realized by the following technical scheme: a method for purifying ellagic acid in a chestnut shell extracting solution mainly utilizes metal salt ions to be complexed with polyphenols in the chestnut shell extracting solution so as to realize the purpose of purifying the ellagic acid, and comprises the following steps:
A. extracting the chestnut shell by using an 80% ethanol water solution solvent method to obtain an alcohol water extracting solution of the chestnut shell. Measuring a certain amount of alcohol-water extracting solution of chestnut shells, and adjusting the pH value by using an alkaline solution; adding a certain amount of metal salt ion solution, wherein the addition amount of the metal salt ion solution ensures that the ellagic acid can be completely complexed, and performing centrifugal separation and complexation reaction to generate precipitate. The complexing reaction time is 30 min. The temperature of the complexation reaction is 30-50 ℃, and preferably 30 ℃; the pH used is 9-12, preferably 9.5. The metal salt ion is zinc ion salt or copper ion salt, preferably zinc ion salt.
B. And adding a certain amount of decomplexing agent into the precipitate, wherein the addition amount ensures that the polyphenol-metal complex is dissociated, releasing polyphenol substances, removing the precipitate generated by the reaction, and evaporating the supernatant to obtain the ellagic acid product.
The decomplexing agent used in the decomplexing reaction may be hydrochloric acid, EDTA or acetic acid, preferably hydrochloric acid. Performing high performance liquid chromatography analysis on the supernatant obtained by complexing ellagic acid and zinc salt in the chestnut shell extract and the solution obtained by adding a decomplexing agent for decomplexing, and obtaining a chromatogram shown in the attached drawing. The chromatographic conditions employed were: the chromatographic column was Agilent Eclipse Plus C18(4.6 mm. times.250 mm, 5 μm), the mobile phase was methanol-0.1% formic acid aqueous solution, gradient elution was performed (0min, 15:85 v/v; 10min, 30:70 v/v; 15min, 45:55 v/v; 18min, 65:35 v/v; 30min, 15:85 v/v; 0.0: 35 v/min), the flow rate was 1.0m L/min, the detection wavelength was 254nm, the sample injection amount was 10 μ L, and the column temperature was room temperature.
The invention achieves the following beneficial results:
1. the purification method of the ellagic acid in the chestnut shells has the advantages that the used reagent is low in price, no toxic or harmful reagent is used, and the burden on the environment is small;
2. the purification method of the invention has simple operation, simple mixing and separation at normal temperature, no high-temperature and high-pressure operation and good safety.
Drawings
FIG. 1 is an ellagic acid structural formula.
FIG. 2 is the ionic structural formula of ellagic acid complex zinc salt.
FIG. 3 is a high performance liquid chromatogram of an extracting solution, a supernatant obtained by complexing ellagic acid with zinc salt in the extracting solution, and a solution obtained by adding hydrochloric acid for decomplexing.
FIG. 4 is a high performance liquid chromatogram of an extract, a supernatant obtained by complexing ellagic acid with a copper salt in the extract, and a solution obtained by adding hydrochloric acid to perform decomplexation.
The specific implementation mode is as follows:
the method for purifying ellagic acid in chestnut shell extract of the present invention is further described below with reference to the accompanying drawings and specific examples, so as to facilitate the understanding of the present invention by those skilled in the art, but the present invention is not limited thereto.
Example 1
A. Measuring 10mL of chestnut shell extract, adjusting pH to 9.5, adding ZnSO with certain mass concentration4Solution, added in an amount to ensure that ellagic acid can be completely complexed (molar ratio 1: 1). After the addition, the complexation reaction time was 30 min. The temperature of the complex reaction is 30 ℃, and precipitates are generated after the centrifugal separation complex reaction;
B. and adding 200 mu L of hydrochloric acid into the precipitate, adding the hydrochloric acid in an amount which ensures that the complex is hydrolyzed, performing ultrasonic decomplexing, performing centrifugal separation on the precipitate generated after the decomplexing reaction, and evaporating the supernatant to obtain the ellagic acid product. The detection shows that the content of the ellagic acid in the extract is increased from 2.59% to 10.01% in the purification process, and the recovery rate of the ellagic acid is 82.83%.
Example 2
A. Measuring 10mL of chestnut shell extract, adjusting pH to 9.5, adding ZnSO with certain mass concentration4Solution, added in an amount to ensure that ellagic acid can be completely complexed (molar ratio 1: 1). After the addition, the complexation reaction time was 30 min. The temperature of the complex reaction is 40 ℃, and precipitates are generated after the centrifugal separation complex reaction;
B. and adding 400 mu L of acetic acid into the precipitate to ensure that the complex is hydrolyzed, performing ultrasonic decomplexing, performing centrifugal separation on the precipitate generated after the decomplexing reaction, and evaporating the supernatant to obtain the ellagic acid product. The detection shows that the content of the ellagic acid in the extract is increased from 2.59% to 9.51% in the purification process, and the recovery rate of the ellagic acid is 81.54%.
Embodiment 3
A. Measuring 10mL of chestnut shell extract, adjusting pH to 9.5, adding ZnSO with certain mass concentration4Solution, added in an amount to ensure that ellagic acid can be completely complexed (molar ratio 1: 1). After the addition, the complexation reaction time was 30 min. The temperature of the complex reaction is 50 ℃, and precipitates are generated after the centrifugal separation complex reaction;
B. and adding EDTA (ethylene diamine tetraacetic acid) with a molar ratio of 1:1 into the precipitate, performing ultrasonic decomplexing, performing centrifugal separation on the precipitate generated after the decomplexing reaction, and evaporating supernatant to obtain an ellagic acid product. The detection shows that the content of the ellagic acid in the extract is increased from 2.59% to 9.58% in the purification process, and the recovery rate of the ellagic acid is 83.73%.
Example 4
A. Measuring 10mL of chestnut shell extract, adjusting pH to 12, adding ZnSO with certain mass concentration4Solution, added in an amount to ensure that ellagic acid can be completely complexed (molar ratio 1: 1). After the addition, the complexation reaction time was 30 min. The temperature of the complex reaction is 50 ℃, and precipitates are generated after the centrifugal separation complex reaction;
B. and adding EDTA (ethylene diamine tetraacetic acid) with a molar ratio of 1:1 into the precipitate, performing ultrasonic decomplexing, performing centrifugal separation on the precipitate generated after the decomplexing reaction, and evaporating supernatant to obtain an ellagic acid product. The detection shows that the content of the ellagic acid in the extract is increased from 2.59% to 8.41% in the purification process, and the recovery rate of the ellagic acid is 75.11%.
Example 5
A. Measuring 10mL of chestnut shell extract, adjusting the pH value to 12, and adding ZnCl with a certain mass concentration2Solution, added in an amount to ensure that ellagic acid can be completely complexed (molar ratio 1: 1). After the addition, the complexation reaction time was 30 min. The temperature of the complex reaction is 30 ℃, and precipitates are generated after the centrifugal separation complex reaction;
B. and (3) adding EDTA (ethylene diamine tetraacetic acid) with a molar ratio of (1: 1) into the precipitate, performing ultrasonic decomplexing, performing centrifugal separation on the precipitate generated after the decomplexing reaction, and evaporating supernatant to obtain an ellagic acid product. The detection shows that the content of the ellagic acid in the extract is increased from 2.59% to 9.56% in the purification process, and the recovery rate of the ellagic acid is 72.98%.
Example 6
A. Measuring 10mL of chestnut shell extract, adjusting the pH value to 9.5, and adding a certain mass concentration of CuSO4Solution, added in an amount to ensure that ellagic acid can be completely complexed (molar ratio 1: 1). After the addition, the complexation reaction time was 30 min. The temperature of the complex reaction is 30 ℃, and precipitates are generated after the centrifugal separation complex reaction;
B. and adding 200 mu L of hydrochloric acid into the precipitate to ensure that the complex is hydrolyzed, centrifugally separating the precipitate generated after the decomplexation reaction, and evaporating the supernatant to dryness to obtain the ellagic acid product. The detection shows that the content of the ellagic acid in the extract is increased from 2.59% to 5.23% in the purification process, and the recovery rate of the ellagic acid is 81.88%.
Example 7
A. Measuring 10mL of chestnut shell extract, adjusting the pH value to 9.5, and adding a certain mass concentration of CuSO4Solution, added in an amount to ensure that ellagic acid can be completely complexed (molar ratio 1: 1). After the addition, the complexation reaction time was 30 min. The temperature of the complex reaction is 30 ℃, and precipitates are generated after the centrifugal separation complex reaction;
B. and adding 200 mu L of acetic acid into the precipitate, performing ultrasonic decomplexing, performing centrifugal separation on the precipitate generated after the decomplexing reaction, and evaporating supernatant to obtain the ellagic acid product. The detection shows that the content of the ellagic acid in the extract is increased from 2.59% to 7.35% in the purification process, and the recovery rate of the ellagic acid is 17.13%.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents, improvements and the like that fall within the spirit and principle of the present invention are intended to be included therein.
Claims (3)
1. A method for purifying ellagic acid in a chestnut shell extracting solution is characterized by comprising the following steps:
A. extracting chestnut shell with ethanol-water solvent to obtain chestnut shell ethanol-water extractive solution, wherein the ethanol-water solution is 80% ethanol water solution;
B. measuring the chestnut shell alcohol-water extract, and adjusting the pH value by using an alkaline solution; adding a metal ion salt solution, wherein the metal ion salt solution is a zinc ion salt solution or a copper ion salt solution, the addition amount ensures that ellagic acid can be completely complexed, the pH of a complexing reaction solution is 9.5, the temperature of the complexing reaction is 30 ℃, a precipitate is generated after the centrifugal separation complexing reaction, and the complexing reaction time is 30 min;
C. and adding a decomplexing agent into the precipitate, wherein the decomplexing agent is hydrochloric acid, EDTA or acetic acid, the addition amount of the decomplexing agent ensures that the polyphenol-metal complex is dissociated, the polyphenol substances are released, the precipitate generated in the reaction is removed, and the supernatant is evaporated to dryness to obtain the ellagic acid product.
2. The method for purifying ellagic acid in chestnut shell extract according to claim 1, wherein: the metal ion salt in the complexation reaction is a zinc ion salt.
3. The method for purifying ellagic acid in chestnut shell extract according to claim 1, wherein: the decomplexing agent in the decomplexing reaction is hydrochloric acid.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910140586.4A CN109810116B (en) | 2019-02-26 | 2019-02-26 | Method for purifying ellagic acid in chestnut shell extracting solution |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910140586.4A CN109810116B (en) | 2019-02-26 | 2019-02-26 | Method for purifying ellagic acid in chestnut shell extracting solution |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN109810116A CN109810116A (en) | 2019-05-28 |
| CN109810116B true CN109810116B (en) | 2021-06-04 |
Family
ID=66607355
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201910140586.4A Active CN109810116B (en) | 2019-02-26 | 2019-02-26 | Method for purifying ellagic acid in chestnut shell extracting solution |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN109810116B (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112891442A (en) * | 2021-03-27 | 2021-06-04 | 广州础研网络科技有限公司 | Method for extracting polyphenol substances from plantain leaf and stem scales |
| CN114605427A (en) * | 2022-03-25 | 2022-06-10 | 大连理工大学盘锦产业技术研究院 | Method for extracting and preparing raspberry ellagic acid |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR1478523A (en) * | 1966-03-11 | 1967-04-28 | Prod Chim Et Celluloses Rey | Ellagic acid purification process |
| CN1429097A (en) * | 2000-05-18 | 2003-07-09 | 欧莱雅 | Use of ellagic acid as anti-pollution cosmetic agent |
| CN102579516A (en) * | 2012-03-07 | 2012-07-18 | 齐齐哈尔大学 | Method for separating purified seabuckthorn flavonoid from large berry seabuckthorn marc |
| CN107759648A (en) * | 2017-11-02 | 2018-03-06 | 北京理工大学 | A kind of method that Hyperoside and isoquercitrin are isolated and purified from Golden flower |
| CN108101924A (en) * | 2018-01-03 | 2018-06-01 | 北京理工大学 | A kind of method that ellagic acid is extracted in the hair shell from Chinese chestnut |
-
2019
- 2019-02-26 CN CN201910140586.4A patent/CN109810116B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR1478523A (en) * | 1966-03-11 | 1967-04-28 | Prod Chim Et Celluloses Rey | Ellagic acid purification process |
| CN1429097A (en) * | 2000-05-18 | 2003-07-09 | 欧莱雅 | Use of ellagic acid as anti-pollution cosmetic agent |
| CN102579516A (en) * | 2012-03-07 | 2012-07-18 | 齐齐哈尔大学 | Method for separating purified seabuckthorn flavonoid from large berry seabuckthorn marc |
| CN107759648A (en) * | 2017-11-02 | 2018-03-06 | 北京理工大学 | A kind of method that Hyperoside and isoquercitrin are isolated and purified from Golden flower |
| CN108101924A (en) * | 2018-01-03 | 2018-06-01 | 北京理工大学 | A kind of method that ellagic acid is extracted in the hair shell from Chinese chestnut |
Also Published As
| Publication number | Publication date |
|---|---|
| CN109810116A (en) | 2019-05-28 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Chriswell et al. | Chromatographic determination of phenols in water | |
| CN109810116B (en) | Method for purifying ellagic acid in chestnut shell extracting solution | |
| Luo et al. | Size characterization of silver nanoparticles after separation from silver ions in environmental water using magnetic reduced graphene oxide | |
| CN108693257A (en) | The method for directly detecting tealeaves glucosides bound state aroma precursor substance | |
| Xu et al. | Ultramicro chitosan-assisted in-syringe dispersive micro-solid-phase extraction for flavonols from healthcare tea by ultra-high performance liquid chromatography | |
| CN101322758B (en) | Method for producing spina date seed extract using complex enzyme | |
| CN103387620A (en) | Polysaccharide, total flavonoid and total alksloid prepared from lotus plumule and preparation method thereof | |
| Sotouneh et al. | Simultaneous preconcentration and determination of trace metals in edible plants and water samples by a novel solvent bar microextraction using a meltblown layer of facemask as the extractant phase holder combined with FAAS | |
| Chen et al. | Speciation of metal–EDTA complexes by flow injection analysis with electrospray ionization mass spectrometry and ion chromatography with inductively coupled plasma mass spectrometry | |
| CN101530607B (en) | Method for extracting gingerol type material from ginger with high efficiency | |
| CN100582102C (en) | Process for preparing methylation catechin by tea | |
| CN107497409B (en) | Preparation method of macroporous resin for purifying total polyphenols in ilicifolius trifoliate | |
| Zhu et al. | Solid‐phase Extraction of β‐Sitosterol from Oldenlandia diffusa Using Molecular Imprinting Polymer | |
| CN104098734A (en) | Preparation method for phenylboronic group modified macroporous resin and application of phenylboronic group modified macroporous resin in separation of rebaudiodside A and stervioside | |
| CN102659861B (en) | Purification method of rhubarb stilbene glucoside | |
| CN102603632A (en) | Method for preparing sinomenine hydrochloride by using non-organic solvent | |
| Hansen et al. | Quantitative HPLC-ICP-MS analysis of antimony redox speciation in complex sample matrices: new insights into the Sb-chemistry causing poor chromatographic recoveries | |
| CN105198734B (en) | Method of preparing gallic acid | |
| Hsieh et al. | Novel vinylene-based covalent organic framework as a promising adsorbent for the rapid extraction of beta-agonists in meat samples | |
| CN106645439B (en) | Detection method of components in rhizoma acori graminei extract | |
| CN105413663A (en) | Bisphenol A adsorption material and preparation method and application thereof | |
| CN105646781A (en) | Preparation method and application of adamantanamine simulated magnetic molecularly-imprinted material | |
| Wang et al. | A novel preconcentration technique using crosslinked chitosan for the determination of mercury by CVAAS | |
| CN104833564A (en) | Sample pretreatment method suitable for detection of basic orange II in bean product | |
| CN105796619A (en) | Application of microspheric silica gel with weak polarity to condensation of Panax notoginsenosides extract |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |