CN112375106B - Purification and refining method of citrus flavonoid - Google Patents
Purification and refining method of citrus flavonoid Download PDFInfo
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- CN112375106B CN112375106B CN202011389244.5A CN202011389244A CN112375106B CN 112375106 B CN112375106 B CN 112375106B CN 202011389244 A CN202011389244 A CN 202011389244A CN 112375106 B CN112375106 B CN 112375106B
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- C—CHEMISTRY; METALLURGY
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D311/00—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only hetero atom, condensed with other rings
- C07D311/02—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only hetero atom, condensed with other rings ortho- or peri-condensed with carbocyclic rings or ring systems
- C07D311/04—Benzo[b]pyrans, not hydrogenated in the carbocyclic ring
- C07D311/22—Benzo[b]pyrans, not hydrogenated in the carbocyclic ring with oxygen or sulfur atoms directly attached in position 4
- C07D311/26—Benzo[b]pyrans, not hydrogenated in the carbocyclic ring with oxygen or sulfur atoms directly attached in position 4 with aromatic rings attached in position 2 or 3
- C07D311/40—Separation, e.g. from natural material; Purification
Abstract
The invention belongs to the technical field of deep processing of agricultural products, and particularly relates to a method for purifying and refining citrus flavonoid. The method comprises the following steps: washing pericarp of citrus, drying to constant weight, pulverizing, and sieving; preparing a buffer solution of sodium hydroxide and borax; adding the obtained powder into the mixed solution, and extracting for a certain time under the ultrasonic condition at the temperature of 40-50 ℃; filtering with 150 mesh filter cloth to remove residue to obtain citrus flavone liquid; evaporating and concentrating the obtained flavone liquid to obtain a mixture with a certain concentration; and purifying the obtained mixture by adopting macroporous resin to obtain the citrus flavonoid, wherein the purity of the citrus flavonoid prepared by the steps reaches 96.2-98.5%.
Description
Technical Field
The invention belongs to the technical field of deep processing of agricultural products. More particularly relates to a purification and refining method of citrus flavonoid.
Background
Citrus fruits are traditional Chinese medicinal materials in China all the time, and the content of flavonoid substances in the citrus fruits is rich. The flavone is mainly present in the outer skin of citrus fruits. Researches show that the flavonoid compound has multiple biological effects, such as anti-inflammatory and antibacterial effects, antioxidation effects, blood sugar reduction, blood fat reduction, anticancer effects, anti-tumor effects, immunity enhancement effects and the like, is safe and nontoxic, and is widely applied to the aspects of medicine, food processing and the like. Recently, reports about citrus flavones are increasing at home and abroad, the citrus flavones draw attention to people due to the specific physiological activity, a large number of various health care products and foods prepared by taking natural flavone substances as dietary supplements are available on the market at present, and the citrus flavones as food additives have wide development prospects.
The extraction method of citrus flavone mainly comprises organic solvent extraction, supercritical extraction, ultrasonic-assisted extraction, acid-base water extraction, purification membrane separation technology, column chromatography, etc. The Liyao and the like take citrus peel residues as raw materials, and research and optimization are performed on the extraction process of flavonoid substances in the citrus peel residues. The results show that the citrus peel residues are dried and then crushed into powder, petroleum ether is used for pretreatment, 70% ethanol is used for extraction for 4 hours, concentration and drying are carried out, and the extraction rate of flavone can reach more than 80%.
Although the method can obtain the citrus flavonoid with certain purity, the purity of the citrus flavonoid cannot meet the requirement of actual production, and how to improve the purity of the citrus flavonoid is still a technical problem to be solved urgently.
Disclosure of Invention
The invention aims to solve the technical problem of overcoming the defect and the defect of low purity of the existing citrus flavone purification, and provides a method for purifying and refining the citrus flavone.
The above purpose of the invention is realized by the following technical scheme:
a purification and refining method of citrus flavonoid comprises the following steps:
(1) Washing citrus peel, drying to constant weight, pulverizing, and sieving;
(2) Preparing a buffer solution of sodium hydroxide and sodium carbonate,
(3) Adding the powder obtained in the step (1) into the mixed solution, and extracting for a certain time at 40-50 ℃ under the ultrasonic condition; filtering with 150-mesh filter cloth to remove residues, and adjusting the pH value to 4-6 with acetic acid to obtain a crude product;
(4) Evaporating and concentrating the crude product obtained in the step (3) to obtain a mixture with a certain concentration;
(5) And (4) purifying the mixture obtained in the step (4) by adopting macroporous resin to obtain the citrus flavonoid.
Preferably, in the step (1), the sieving is 100-150 mesh sieving.
Preferably, in step (1), the citrus peel is mandarin orange peel or shaddock peel.
Preferably, in the step (1), the drying temperature is 60 to 90 ℃.
Preferably, in the step (2), the molar ratio of the sodium hydroxide to the sodium carbonate is 1.
Preferably, in step (2), the pH of the buffer solution =10.
Preferably, in the step (3), the ratio of the mixed solution to the powder is 10 to 15ml,
preferably, in step (5), the macroporous resin is HDP100.
Preferably, in step (5), the separation and purification conditions are: adjusting the pH value of the mixture to 4-6; the sample feeding flow rate is 1-3 BV/h; the eluent is NaOH aqueous solution with the concentration of 0.05-0.1 mol/L; the desorption flow rate is 1 to 3BV/h; collecting eluent after 6-8 h, and carrying out vacuum freeze drying to obtain the citrus flavonoid.
Preferably, the vacuum freezing conditions are as follows: freeze drying at-40-60 deg.c for 14-18 hr.
The invention has the following beneficial effects:
the method adopts the buffer solution of sodium hydroxide and sodium carbonate as the alkaline extracting solution, can fully extract the citrus flavone in the citrus peel, then adopts acetic acid to separate out the citrus flavone, and then adopts macroporous resin to be HDP100 for purification and purification to obtain the high-purity citrus flavone, wherein the purity reaches 96.2-98.5 percent.
Detailed Description
The present invention is further illustrated by the following specific examples, which are not intended to limit the invention in any way. Reagents, methods and apparatus used in the present invention are conventional in the art unless otherwise indicated.
Unless otherwise indicated, reagents and materials used in the following examples are commercially available.
Example 1
A purification and refining method of citrus flavonoid comprises the following steps:
(1) Washing and drying citrus peel to constant weight, crushing and sieving by a 130-mesh sieve; the citrus peel is mandarin orange peel; the drying temperature is 70 ℃;
(2) Preparing 100mL of a buffer solution of sodium hydroxide and sodium carbonate, wherein the molar ratio of the sodium hydroxide to the sodium carbonate is 1; the pH of the buffer solution =10;
(3) Adding the powder obtained in the step (1) into the mixed solution, and extracting for 45min at 45 ℃ under the ultrasonic condition of 400W; the proportion of the mixed solution to the powder is 12mL; filtering with 150-mesh filter cloth to remove residues, and adjusting pH to 5 with acetic acid to obtain a crude product;
(4) Evaporating and concentrating the crude product obtained in the step (3) to obtain a mixture with a certain concentration;
(5) Purifying the mixture obtained in the step (4) by adopting HDP100 macroporous resin to obtain citrus flavone; the separation and purification conditions are as follows: adjusting the pH of said mixture to 5; the sample feeding flow rate is 2BV/h; the eluent is NaOH aqueous solution, and the concentration is 0.07mol/L; the desorption flow rate is 2BV/h; collecting eluent after 7h, and carrying out vacuum freeze drying to obtain the citrus flavonoid; the vacuum freezing conditions are as follows: vacuum freeze-drying at-50 deg.C for 16h.
Example 2
A purification and refining method of citrus flavonoid comprises the following steps:
(1) Washing and drying citrus peel to constant weight, crushing and sieving by a 150-mesh sieve; the citrus peel is mandarin orange peel; the drying temperature is 90 ℃;
(2) Preparing 100mL of a buffer solution of sodium hydroxide and sodium carbonate, wherein the molar ratio of the sodium hydroxide to the sodium carbonate is 1; the pH of the buffer solution =10;
(3) Adding the powder obtained in the step (1) into the mixed solution, and extracting for 60min at 50 ℃ under the ultrasonic condition of 500W; the ratio of the mixed solution to the powder is 15mL; filtering with 150-mesh filter cloth to remove residue, and adjusting pH to 6 with acetic acid to obtain crude product;
(4) Evaporating and concentrating the crude product obtained in the step (3) to obtain a mixture with a certain concentration;
(5) Purifying the mixture obtained in the step (4) by adopting HDP100 macroporous resin to obtain citrus flavonoid; the separation and purification conditions are as follows: adjusting the pH of said mixture to 6; the sample feeding flow rate is 3BV/h; the eluent is NaOH aqueous solution with the concentration of 0.1mol/L; the desorption flow rate is 3BV/h; collecting eluent after 6 hours, and carrying out vacuum freeze drying to obtain the citrus flavonoid; the vacuum freezing conditions are as follows: vacuum freeze-drying at-60 deg.C for 14h.
Example 3
A purification and refining method of citrus flavonoid comprises the following steps:
(1) Washing and drying citrus peel to constant weight, crushing and sieving by a 100-mesh sieve; the citrus peel is shaddock peel; the drying temperature is 60 ℃;
(2) Preparing 100mL of a buffer solution of sodium hydroxide and sodium carbonate, wherein the molar ratio of the sodium hydroxide to the sodium carbonate is 1; the pH of the buffer solution =10;
(3) Adding the powder obtained in the step (1) into the mixed solution, and extracting for 30min at 40 ℃ under the ultrasonic condition of 400W; the proportion of the mixed solution to the powder is 10mL; filtering with 150-mesh filter cloth to remove residues, and adjusting pH to 4 with acetic acid to obtain a crude product;
(4) Evaporating and concentrating the crude product obtained in the step (3) to obtain a mixture with a certain concentration;
(5) Purifying the mixture obtained in the step (4) by adopting HDP100 macroporous resin to obtain citrus flavone; the separation and purification conditions are as follows: adjusting the pH of said mixture to 4; the sample feeding flow rate is 1BV/h; the eluent is NaOH aqueous solution with the concentration of 0.05mol/L; the desorption flow rate is 1BV/h; collecting eluent after 8h, and carrying out vacuum freeze drying to obtain the citrus flavonoid; the vacuum freezing conditions are as follows: vacuum freeze-drying at-40 deg.C for 18h.
Comparative example 1
A purification and refining method of citrus flavonoid comprises the following steps:
(1) Washing and drying citrus peel to constant weight, crushing and sieving by a 130-mesh sieve; the citrus peel is mandarin orange peel; the drying temperature is 70 ℃;
(2) Preparing 100mL of a buffer solution of sodium hydroxide and sodium carbonate, wherein the molar ratio of the sodium hydroxide to the sodium carbonate is 1; the pH of the buffer solution =10;
(3) Adding the powder obtained in the step (1) into the mixed solution, and extracting for 45min at 45 ℃ under the ultrasonic condition of 400W; the proportion of the mixed solution to the powder is 12mL; filtering with 150-mesh filter cloth to remove residues, and adjusting pH to 5 with hydrochloric acid to obtain a crude product;
(4) Evaporating and concentrating the crude product obtained in the step (3) to obtain a mixture with a certain concentration;
(5) Purifying the mixture obtained in the step (4) by adopting HDP100 macroporous resin to obtain citrus flavonoid; the separation and purification conditions are as follows: adjusting the pH of said mixture to 5; the sample feeding flow rate is 2BV/h; the eluent is NaOH aqueous solution with the concentration of 0.07mol/L; the desorption flow rate is 2BV/h; collecting eluent after 7h, and carrying out vacuum freeze drying to obtain the citrus flavonoid; the vacuum freezing conditions are as follows: vacuum freeze-drying at-50 deg.C for 16h.
Comparative example 2
A purification and refining method of citrus flavonoid comprises the following steps:
(1) Washing and drying citrus peel to constant weight, crushing and sieving by a 130-mesh sieve; the citrus peel is mandarin orange peel; the drying temperature is 70 ℃;
(2) Preparing 100mL of sodium hydroxide solution; the pH of the sodium hydroxide solution =10;
(3) Adding the powder obtained in the step (1) into the mixed solution, and extracting for 45min at 45 ℃ under the ultrasonic condition of 400W; the proportion of the mixed solution to the powder is 12mL; filtering with 150-mesh filter cloth to remove residues, and adjusting pH to 5 with acetic acid to obtain a crude product;
(4) Evaporating and concentrating the crude product obtained in the step (3) to obtain a mixture with a certain concentration;
(5) Purifying the mixture obtained in the step (4) by adopting HDP100 macroporous resin to obtain citrus flavone; the separation and purification conditions are as follows: adjusting the pH of said mixture to 5; the sample feeding flow rate is 2BV/h; the eluent is NaOH aqueous solution, and the concentration is 0.07mol/L; the desorption flow rate is 2BV/h; collecting eluent after 7h, and carrying out vacuum freeze drying to obtain the citrus flavonoid; the vacuum freezing conditions are as follows: vacuum freeze-drying at-50 deg.C for 16h.
The purity of the citrus flavone was checked by HPLC on the products obtained in examples 1-3 and comparative examples 1-2, and the specific steps were as follows:
taking citrus flavonoid as raw material, mixing the citrus flavonoid with 1:3: adding ultrapure water and methanol at a ratio of 5 for dissolving, uniformly mixing, centrifuging for 15min at 4000rmp/min, taking the supernatant, drying the methanol, extracting for 3 times by using ethyl acetate with the volume 5 times that of the methanol, drying the extract, adding 150 mu L of acetonitrile into the extract, centrifuging for 20 min at 12000rmp/min, taking the supernatant, and detecting the purity of the citrus flavone by HPLC. Specific results are shown in table 1:
| example 1 | Example 2 | Example 3 | Comparative example 1 | Comparative example 2 | |
| Purity (%) | 98.5 | 96.2 | 97.4 | 92.5 | 90.3 |
By comparing the examples 1-3 with the comparative examples 1-2, it can be seen that the orange flavone in the citrus peel can be fully extracted by using the buffer solution of sodium hydroxide and sodium carbonate as the alkaline extracting solution, then the orange flavone is separated out by using acetic acid, and then the high-purity orange flavone is obtained by purifying and purifying the orange flavone by using macroporous resin as HDP100, wherein the purity is up to 96.2-98.5%
The above embodiments are preferred embodiments of the present invention, but the present invention is not limited to the above embodiments, and any other changes, modifications, substitutions, combinations, and simplifications which do not depart from the spirit and principle of the present invention should be construed as equivalents thereof, and all such modifications are intended to be included in the scope of the present invention.
Claims (2)
1. A purification and refining method of citrus flavonoid is characterized in that: the method comprises the following steps:
(1) Washing and drying citrus peel to constant weight, crushing, and sieving by a sieve of 100 to 150 meshes; the drying temperature is 60 to 90 ℃;
(2) Preparing a buffer solution of sodium hydroxide and sodium carbonate, the pH of the buffer solution =10;
(3) Adding the powder obtained in the step (1) into a mixed solution, and extracting for a certain time under the ultrasonic condition at 40-50 ℃; filtering with 150-mesh filter cloth to remove residues, and adjusting the pH value to 4-6 with acetic acid to obtain a crude product; the ratio of the mixed solution to the powder is (10) - (15mL);
(4) Evaporating and concentrating the crude product obtained in the step (3) to obtain a mixture with a certain concentration;
(5) Purifying the mixture obtained in the step (4) by adopting macroporous resin to obtain citrus flavone;
in the step (1), the citrus peel is tangerine peel or shaddock peel;
in the step (2), the molar ratio of the sodium hydroxide to the sodium carbonate is 1 to 2 to 3;
in step (5), the purification conditions are: adjusting the pH value of the mixture to be 4-6; the sampling flow rate is 1 to 3BV/h; the eluent is NaOH aqueous solution, and the concentration is 0.05 to 0.1mol/L; the desorption flow rate is 1 to 3BV/h; collecting eluent after 6 to 8 hours, and carrying out vacuum freeze drying to obtain the citrus flavonoid; the vacuum freezing conditions are as follows: vacuum freeze drying at-40 to-60 ℃ for 14 to 18h.
2. The method for purifying and refining citrus flavonoid according to claim 1, wherein the method comprises the following steps: in step (5), the macroporous resin is HDP100.
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