CN110668982B - Preparation method of high-purity alliin - Google Patents
Preparation method of high-purity alliin Download PDFInfo
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- CN110668982B CN110668982B CN201911109776.6A CN201911109776A CN110668982B CN 110668982 B CN110668982 B CN 110668982B CN 201911109776 A CN201911109776 A CN 201911109776A CN 110668982 B CN110668982 B CN 110668982B
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- C07—ORGANIC CHEMISTRY
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- C07C315/00—Preparation of sulfones; Preparation of sulfoxides
- C07C315/06—Separation; Purification; Stabilisation; Use of additives
Abstract
The invention relates to a production process of a garlic extract, in particular to a preparation method of alliin. The method comprises the following steps: (1) constructing a vesicle system; (2) preparing high-purity alliin concentrated solution by micelle reinforced ultrafiltration technology. (3) Crystallizing and drying; the recovery rate and purity of the prepared alliin are higher than 88% and 99%; compared with the common surfactant, the gemini surfactant used in the invention has very low Critical Micelle Concentration (CMC) and 1-2 orders of magnitude lower dosage. Meanwhile, by compounding with sodium deoxycholate, the CMC is further reduced, and the synergistic extraction effect is achieved.
Description
Technical Field
The invention relates to a production process of a garlic extract, in particular to a preparation method of alliin.
Background
Alliin, ginkgo leaf extract and ginsenoside are named as three main plant medicines which are most important in the 21 st century and have the market prospect. At present, alliin is obtained mainly by three methods of extraction, chemical synthesis and tissue culture from natural products. The method for extracting the natural product is more suitable for industrial production and the product can better meet the market demand.
China is the biggest garlic producing country and export country in the world and has abundant resources. But the international market gap between the industry of China mainly carrying out rough processing (such as pickling, grinding, slicing and drying) and the garlic product with high added value is very large. Aiming at the current situation, the patent further develops a high-purity alliin production technology on the basis of an ultrasonic-assisted double-aqueous-phase alliin extraction patent (CN 104059002A), and has profound significance for filling the blank of domestic garlic high-added-value products.
The micelle-enhanced ultrafiltration (MEUF) technology is a typical method for applying a molecular self-assembly system to chemical separation. This technology is being developed from the initial use for treating heavy metals in wastewater to the removal of substances such as aromatic organic substances. The basic principle is that molecular self-assembly aggregates such as micelles and vesicles are constructed, when the diameter of the aggregates is larger than the aperture of a filter membrane, the aggregates can be intercepted by the ultrafiltration membrane, and a solution can pass through the ultrafiltration membrane, so that separation is completed.
Disclosure of Invention
According to the prior art background and the current situation of preparing alliin at the present stage, the invention develops a preparation method of high-purity alliin, namely a method for preparing high-purity alliin by using a micelle reinforced ultrafiltration technology, and the obtained alliin product has high recovery rate and high purity.
A preparation method of high-purity alliin comprises the following steps:
(1) constructing a vesicle system;
(2) preparing high-purity alliin concentrated solution by micelle reinforced ultrafiltration technology.
(3) Crystallizing and drying.
The process of the step (1) is as follows: fixed cationic surfactant-Gemini imidazolyl ionic liquid [ C14-6-C14im]Br2(14-6-14 for short, the structural formula is shown as formula 1) with the concentration of 0.07-0.12 mmol/L, and mixing with anionic surfactant-sodium deoxycholate aqueous solution (SDC for short) according to the molar ratio of 1: 4, stirring the solution, fully contacting the solution through ultrasonic treatment, and standing to form the unilamellar spherical vesicle aggregate with positive charges.
Formula 1.
The process of the step (2) is as follows:
s1 adding an alliin crude extract with the same volume to the vesicle aggregate solution, adjusting the pH of the system to about 11.0 by using a 4-5% sodium hydroxide solution, and fully oscillating to form an alliin-vesicle aggregation system;
s2 ultra-filtering the mixed solution by using a PVDF hollow fiber ultra-filtration membrane with the aperture of 0.2 micron under the pressure of 0.17-0.5 MPa to obtain the high-purity alliin concentrated solution.
The preparation method of the alliin crude extract in the step (2) comprises the following steps:
j1 adding Beriten-Robinson buffer solution with pH of 2.0-4.0 into inorganic salt to dissolve, adding organic solvent ethanol, n-propanol or isopropanol, mixing, standing, and separating phase to obtain aqueous two-phase system;
j2 adding Bulbus Allii powder into aqueous two-phase system, extracting at constant temperature for 20-40min under oscillation, centrifuging, standing, and separating phases to obtain lower phase coarse extractive solution rich in alliin.
The process of the step (3) is as follows: adjusting the pH of the concentrated solution obtained in the step (2) to be near the isoelectric point (4.86) of alliin by using hydrochloric acid with the mass concentration of 4-5%; adding ethanol until the ethanol concentration is 50-70%, cooling to 25-30 deg.C at a speed of 2-10 deg.C per hour, washing with 70% ethanol, evaporating under reduced pressure, crystallizing, and drying to obtain high purity alliin product.
The Gemini type amphiphilic ionic liquid used in the invention not only has the advantages of common ionic liquid such as low vapor pressure, good thermal stability and wide electrochemical window, but also is beneficial to improving the surface charge property of the traditional amphiphilic molecular aggregate, and meanwhile, the ionic liquid exists in a W aggregate form and is not easy to run off. Compared with the traditional surfactant, the gemini amphiphilic molecule has the advantages of low CMC value, better surface activity and more action sites, and is beneficial to the extraction process. Gemini type amphiphilic ionic liquid [ C14-6-C14im ] constructed by the invention]Br2(14-6-14 for short) and anionic surfactant-sodium deoxycholate (SDC for short), the formed monolayer vesicle system has the advantages of high selectivity, high extraction efficiency, less solvent consumption, no toxicity, easy recovery of alliin monomer products and the like, and can realize complete separation of inorganic salt components and alliin products in a double aqueous phase extraction system, and the product purity is high after crystallization.
The invention has the beneficial effects that:
1. high product recovery rate and purity
The recovery rate and the purity of the alliin prepared by the method are respectively 88.2 percent and 99.5 percent.
2. Low critical micelle concentration, low solvent consumption, and solvent saving
Compared with the common surfactant, the Critical Micelle Concentration (CMC) of the gemini surfactant is very low, and the dosage of the surfactant is 1 to 2 orders of magnitude lower. Meanwhile, by compounding with sodium deoxycholate, the CMC is further reduced, and the synergistic extraction effect is achieved.
3. The preparation process is simple
Under the alkaline condition, alliin molecules with negative charges are combined with a vesicle aggregate system with positive charges through the action of electrostatic attraction, and the separation of the alliin-vesicle system from polysaccharide and small molecular salt is realized through a micelle reinforced ultrafiltration technology, wherein the retention rate of the system to the alliin-vesicle system is 92%. Adjusting the pH of the concentrated solution to cause alliin to have an isoelectric point close to the isoelectric point, and adding ethanol for crystallization to obtain a high-purity product. The Gemini amphiphilic ionic liquid vesicle system is utilized to realize the high-efficiency separation of alliin monomers, and the application of the Gemini amphiphilic ionic liquid vesicle system in the field of extraction and separation is expanded.
Detailed Description
Example 1
Preparing coarse alliin extract:
(1) dissolving inorganic salt in Beriten-Robinson buffer solution with pH of 2.0-4.0, adding organic solvent ethanol, n-propanol or isopropanol, mixing, standing, and separating phase to obtain aqueous two-phase system;
(2) adding 20 g of Bulbus Allii powder into 1000 g of aqueous two-phase system, extracting for 30 min, centrifuging at 3000 r/min for 10min, standing, and separating phases to obtain lower phase coarse extractive solution rich in alliin. The extraction rate of the obtained alliin is 19mg/g, namely 19mg of alliin can be extracted from each gram of garlic powder.
Example 2
A preparation method of high-purity alliin comprises the following steps:
(1) construction of vesicle system: fixing the concentration of cationic surfactant-Gemini imidazolyl ionic liquid [ C14-6-C14im ] Br2 (14-6-14 for short, the structural formula is shown as formula 1) to be 0.07 mmol/L, and mixing the fixed cationic surfactant-Gemini imidazolyl ionic liquid with an anionic surfactant-sodium deoxycholate aqueous solution according to the molar ratio of 1: 4, stirring the solution and fully contacting the solution by ultrasonic treatment, and standing for 24 hours to form the unilamellar spherical vesicle aggregates with positive charges.
(2) Extraction and ultrafiltration combined experiment: taking a certain volume of vesicle aggregate solution, adding the alliin crude extract with the same volume, and adjusting the pH of the system to about 11.0 by using a 5% sodium hydroxide solution. The alliin molecules with negative charges and the vesicle aggregates with positive charges on the surface form an alliin-vesicle polymerization system due to the electrostatic effect. After full oscillation contact, filtering the mixed solution by adopting a PVDF hollow fiber ultrafiltration membrane with the aperture of 0.2 micron under the pressure of 0.5MPa, and analyzing the solution obtained after ultrafiltration to obtain the system with the retention rate of the alliin-vesicle aggregate of 95 percent, thereby realizing the separation of alliin, polysaccharide and micromolecular salt.
(3) And (3) crystallizing and drying: the pH of the obtained concentrated solution is adjusted to about 4.86 of isoelectric point of alliin with 4-5% hydrochloric acid. Adding ethanol into the system until the ethanol concentration is 60%, cooling to 25 deg.C at 2 deg.C per hour, washing with 70% ethanol for 3 times, drying in vacuum drying oven at 55 deg.C under reduced pressure, and evaporating for crystallization to obtain high purity alliin product. The recovery rate and purity of the obtained alliin are 86.5% and 99.7%, respectively.
Example 3
A preparation method of high-purity alliin comprises the following steps:
(1) construction of vesicle system: fixed cationic surfactant-Gemini imidazolyl ionic liquid [ C14-6-C14im ]]Br2(14-6-14 for short, the structural formula is shown as formula 1) with the concentration of 0.12 mmol/L, and the anionic surfactant-sodium deoxycholate aqueous solution is mixed with the anionic surfactant-sodium deoxycholate aqueous solution according to the molar ratio of 1: 4, stirring the solution and fully contacting the solution by ultrasonic treatment, and standing for 24 hours to form the unilamellar spherical vesicle aggregates with positive charges.
(2) Extraction and ultrafiltration combined experiment: taking a certain volume of vesicle aggregate solution, adding the alliin crude extract with the same volume, and adjusting the pH of the system to about 11.0 by using a 5% sodium hydroxide solution. The alliin molecules with negative charges and the vesicle aggregates with positive charges on the surface form an alliin-vesicle polymerization system due to the electrostatic effect. After full oscillation contact, filtering the mixed solution by adopting a PVDF hollow fiber ultrafiltration membrane with the aperture of 0.2 micron under the pressure of 0.17MPa, and analyzing the solution obtained after ultrafiltration to obtain the system with the retention rate of 97 percent on the alliin-vesicle system, thereby realizing the separation of alliin, polysaccharide and micromolecular salt. (3) And (3) crystallizing and drying: the pH of the obtained concentrated solution is adjusted to about 4.86 of isoelectric point of alliin with 4-5% hydrochloric acid. Adding ethanol into the system until the ethanol concentration is 60%, cooling to 30 deg.C at 2 deg.C per hour, washing with 70% ethanol for 4 times, drying in vacuum drying oven at 55 deg.C under reduced pressure, and evaporating for crystallization to obtain high purity alliin product. The recovery rate and purity of the obtained alliin are respectively 88.2% and 99.5%.
Embodiment 4 a method for preparing high-purity alliin, comprising the steps of:
(1) construction of vesicle system: fixed cationic surfactant-Gemini imidazolyl ionic liquid [ C14-6-C14im ]]Br2(14-6-14 for short, the structural formula is shown as formula 1) with the concentration of 0.08 mmol/L, and the anionic surfactant-sodium deoxycholate aqueous solution is mixed according to the mol ratio of 1: 4, stirring the solution and fully contacting the solution by ultrasonic treatment, and standing for 24 hours to form the unilamellar spherical vesicle aggregates with positive charges.
(2) Extraction and ultrafiltration combined experiment: taking a certain volume of vesicle aggregate solution, adding the alliin crude extract with the same volume, and adjusting the pH of the system to about 11.0 by using a 5% sodium hydroxide solution. The alliin molecules with negative charges and the vesicle aggregates with positive charges on the surface form an alliin-vesicle polymerization system due to the electrostatic effect. After full oscillation contact, filtering the mixed solution by adopting a PVDF hollow fiber ultrafiltration membrane with the aperture of 0.2 micron under the pressure of 0.26MPa, and analyzing the solution obtained after ultrafiltration to obtain the system with the retention rate of 96 percent on the alliin-vesicle system, thereby realizing the separation of alliin, polysaccharide and micromolecular salt. (3) And (3) crystallizing and drying: the pH of the obtained concentrated solution is adjusted to about 4.86 of isoelectric point of alliin with 4-5% hydrochloric acid. Adding ethanol into the system until the ethanol concentration is 60%, cooling to 30 deg.C at 2 deg.C per hour, washing with 70% ethanol for 4 times, drying in vacuum drying oven at 55 deg.C under reduced pressure, and evaporating for crystallization to obtain high purity alliin product. The recovery rate and purity of the obtained alliin are 87.9% and 99.6%, respectively.
Claims (2)
1. A preparation method of high-purity alliin is characterized by comprising the following steps:
(1) constructing a vesicle system;
(2) adding the alliin crude extract into the vesicle system in the step (1), and preparing a high-purity alliin concentrated solution by adopting a micelle-enhanced ultrafiltration technology;
(3) crystallizing and drying the high-purity alliin concentrated solution obtained in the step (2) to obtain high-purity alliin;
the process of the step (1) is as follows: fixed cationic surfactant-Gemini imidazolyl ionic liquid [ C14-6-C14im]Br2The concentration is 0.07-0.12 mmol/L, and the anionic surfactant-sodium deoxycholate aqueous solution is mixed according to the molar ratio of 1: 4, stirring the solution, fully contacting the solution through ultrasonic treatment, and standing to form a monolayer spherical vesicle aggregate with positive charges;
the process of the step (2) is as follows:
s1 adding an alliin crude extract with the same volume to the vesicle aggregate solution, adjusting the pH of the system to about 11.0 by using a 4-5% sodium hydroxide solution, and fully oscillating to form an alliin-vesicle aggregation system;
s2 ultra-filtering the S1 mixed solution by adopting a PVDF hollow fiber ultra-filtration membrane with the aperture of 0.2 micron under the pressure of 0.17-0.5 MPa to obtain high-purity alliin concentrated solution;
the process of the step (3) is as follows: adjusting the pH of the concentrated solution obtained in the step (2) to be near the isoelectric point of alliin by hydrochloric acid with the mass concentration of 4-5%; adding ethanol until the ethanol concentration is 50-70%, cooling to 25-30 deg.C at a speed of 2-10 deg.C per hour, washing with 70% ethanol, evaporating under reduced pressure, crystallizing, and drying to obtain high purity alliin product.
2. The method according to claim 1, wherein the crude alliin extract obtained in step (2) is prepared by:
j1 adding Beriten-Robinson buffer solution with pH of 2.0-4.0 into inorganic salt to dissolve, adding organic solvent ethanol, n-propanol or isopropanol, mixing, standing, and separating phase to obtain aqueous two-phase system;
j2 adding Bulbus Allii powder into aqueous two-phase system, extracting at constant temperature for 20-40min under oscillation, centrifuging, standing, and separating phases to obtain lower phase coarse extractive solution rich in alliin.
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103598544A (en) * | 2013-11-19 | 2014-02-26 | 徐州绿之野生物食品有限公司 | Extraction process for carrying out comprehensive utilization on garlic as raw material |
| CN105399650A (en) * | 2015-12-16 | 2016-03-16 | 齐鲁工业大学 | Method for extracting alliin through reverse micelles system |
| CN104059002B (en) * | 2014-06-27 | 2016-08-17 | 齐鲁工业大学 | A kind of ultrasonic wave added aqueous two-phase extracts the method for alliin |
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| US8002988B2 (en) * | 2007-04-26 | 2011-08-23 | The Trustees Of Columbia University In The City Of New York | Removal of contaminants from water using sugar based surfactant enhanced ultrafiltration |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103598544A (en) * | 2013-11-19 | 2014-02-26 | 徐州绿之野生物食品有限公司 | Extraction process for carrying out comprehensive utilization on garlic as raw material |
| CN104059002B (en) * | 2014-06-27 | 2016-08-17 | 齐鲁工业大学 | A kind of ultrasonic wave added aqueous two-phase extracts the method for alliin |
| CN105399650A (en) * | 2015-12-16 | 2016-03-16 | 齐鲁工业大学 | Method for extracting alliin through reverse micelles system |
Non-Patent Citations (2)
| Title |
|---|
| Gold Extraction through Vesicles Self-Assembled by Cationic Gemini Surfactant and Sodium Deoxycholate;Shubin Wang 等;《Ind.Eng.Chem.Res.》;20160707;第55卷;第8207-8214页 * |
| 蒜氨酸的分离纯化研究进展;姜秀敏 等;《江苏调味副产品》;20150328(第1期);第6-9页 * |
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