CN114344941A - Application of strong acid oxidation electrolyzed water in improving extraction content of selenium active component - Google Patents

Application of strong acid oxidation electrolyzed water in improving extraction content of selenium active component Download PDF

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CN114344941A
CN114344941A CN202210014068.XA CN202210014068A CN114344941A CN 114344941 A CN114344941 A CN 114344941A CN 202210014068 A CN202210014068 A CN 202210014068A CN 114344941 A CN114344941 A CN 114344941A
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selenium
strongly acidic
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water
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任占冬
王紫倩
朱玉婵
韩娟娟
衡娅萍
王铭
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Wuhan Polytechnic University
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Abstract

The invention belongs to the field of extraction of selenium-rich components, and particularly relates to application of strong acid oxidation electrolyzed water in improving the extraction content of selenium active components. The application is preferably the application in improving the selenium extraction content in plants. The method for extracting the active components of the plants in an auxiliary manner can improve the yield of the selenium-rich components in the subsequent steps, and the pretreatment operation steps are simple. The oxidized electrolyzed water has the characteristics of safety, environmental protection, no toxicity, no harm and the like, and can not cause the problem of environmental pollution.

Description

Application of strong acid oxidation electrolyzed water in improving extraction content of selenium active component
Technical Field
The invention belongs to the field of extraction of selenium-rich components, and particularly relates to application of strongly acidic oxidized electrolyzed water in improving the extraction content of selenium active components.
Background
The plant has rich kinds of active components, and the extract contains rutin, sophonediol, quercetin, organic selenium element and other components, and has the functions of resisting bacteria, diminishing inflammation, clearing away heat and toxic material, promoting metabolism, etc. especially, the organic selenium element has the pharmacological functions of preventing and resisting cancer. The main forms of organic selenium include selenomethionine, selenoprotein, etc. Selenium is a component of glutathione peroxidase, which catalyzes a redox reaction between reduced glutathione and peroxide, so that it can exert a significant antioxidant effect and is an important radical scavenger. Besides glutathione peroxidase, selenase such as glutathione transferase, catalase, thioredoxin reductase and the like and various selenoproteins also have antioxidant effect, can effectively protect cell membranes from being damaged by peroxide, prevent peroxide from accumulating in vivo, reduce DNA damage, prevent mutation and achieve the aim of inhibiting canceration. In addition, the antioxidant action mechanism of the vitamin E is different from that of the vitamin E, but the vitamin E and the vitamin E can complement each other and have a synergistic effect, and the vitamin E together form a defense system for resisting free radical damage of an organism.
At present, the extraction method of active components in plants comprises the common traditional methods such as an alkali extraction and acid precipitation method, an ethanol reflux method, a mixed acid digestion method, a magnetic stirring method and the like. The active ingredients in the plants have better solubility in ethanol, so that the ethanol reflux method has the advantages of lower cost, no environmental pollution, simple and convenient operation, safe product and wide application. In addition, in order to further improve the extraction efficiency, more scholars choose to use ultrasonic assistance, microwave assistance, pressurized solvent method and other methods for auxiliary extraction. However, these methods are based on the introduction of special instruments (ultrasound, microwaves and pressure) to improve the extraction and thus complicate the process.
In summary, no method for extracting selenium-rich active components from plants is environment-friendly and easy to operate, so that a new method for improving the extraction of the selenium-rich active components from the plants without the assistance of special instruments is needed.
Disclosure of Invention
The invention aims to provide a novel method for extracting selenium-rich components in plants by oxidizing electrolyzed water in an auxiliary manner aiming at the defects of the prior art. The acidic electrolyzed oxidizing water has three characteristics: low pH value, high redox potential value and certain effective chlorine content. It can destroy the surface structure of biological cell by oxidation, increase membrane permeability and increase substance dissolving effect. The selenium-rich plants are pretreated by using the oxidized electrolyzed water, so that the extraction rate of the selenium-rich active ingredients in the plants is improved.
In order to achieve the purpose, the invention provides application of strong-acid oxidized electrolyzed water in improving the extraction content of selenium active components.
Furthermore, the application is the application in improving the extraction content of the selenium active component in the plants.
Preferably, the plant includes at least one of gynostemma pentaphyllum, sophora flower bud, cardamine and lotus vein agrestis, and of course, other selenium-rich plants or plants containing selenium can be used.
Preferably, in the application of the strongly acidic electrolyzed oxidizing water in improving the extraction content of the selenium active component, the pH value of the strongly acidic electrolyzed oxidizing water is less than or equal to 2.7. Under the condition of the low pH value, the strongly acidic electrolyzed oxidizing water can destroy the surface structure of biological cells through oxidation, hydrolyze the structure of plant cells, increase the membrane permeability and increase the dissolution effect of substances.
Preferably, in the application of the strongly acidic electrolyzed oxidizing water in improving the extraction content of selenium active components, the content of available chlorine in the strongly acidic electrolyzed oxidizing water is 10-200 mg/L, more preferably 40-175 mg/L, even more preferably 90-150 mg/L, and most preferably 125 mg/L. Under the condition of satisfying the above chlorine content, strongly acidic oxidized electrolyzed water can destroy the structure of peptidoglycan on cell walls by chemical oxidation of compounds such as hypochlorous acid, etc., and also induce peroxidation of lipids and proteins on cell membranes, resulting in impaired membrane integrity, shrinkage, deformation, rupture or occurrence of pores.
Preferably, in the application of the strongly acidic electrolyzed oxidizing water in improving the extraction content of the selenium active component, the oxidation-reduction potential value of the strongly acidic electrolyzed oxidizing water is more than or equal to 1050 mV. Under the condition of meeting the oxidation-reduction potential value, the strongly acidic electrolyzed oxidizing water can destroy the surface structure of biological cells through physical oxidation, increase the membrane permeability and increase the dissolution effect of substances. The oxidation potential value is essentially a physical parameter of the overall oxidation that reflects the type and content of all the oxidative active species in the oxidized electrolyzed water. The high oxidation potential value means the enhancement of the overall oxidation capacity of the oxidation electrolysis water, and the surface layer of the cell is efficiently damaged, so that the oxidation of the cell surface sulfhydryl mixture is caused.
As a preferred scheme, the specific application of the strongly acidic electrolyzed oxidizing water in improving the extraction content of the selenium active component comprises the following steps:
mixing selenium-rich plants with the strongly acidic oxidized electrolyzed water, optionally heating, stirring, filtering, drying, and grinding to obtain selenium-rich plant powder; according to the invention, in view of extraction efficiency, the time for mixing the selenium-rich plants with the strongly acidic oxidized electrolyzed water can be 0.5-8 h, preferably 2-6 h, further preferably 3-5 h, and most preferably 4 h.
Mixing the selenium-rich plant powder with an extraction solvent, heating and refluxing for extraction, taking the first supernatant for centrifugal separation, and taking the second supernatant as a selenium-rich plant selenium extracting solution.
According to the invention, strong acid oxidation electrolysis water is used for assisting treatment, so that hemicellulose of cells can be effectively degraded, and a small amount of lignin is removed, thereby causing the stripping of cluster fibers, and increasing the porosity and the specific surface area of the biomass substrate. In addition, the cell wall deconstruction is promoted to a certain extent, so that the enzymatic hydrolysis is accelerated, the hemicellulose and phenol components in the biomass are removed, and the porosity of the biomass is increased by changing the microscopic morphology and chemical composition of the plant cell wall. Accelerate the dissolution of part of the active substance. The auxiliary treatment of the oxidation electrolysis water and the reflux extraction of the extraction solvent are organically combined, so that the extraction content of the selenium-rich component in the plant can be further improved.
According to the present invention, the term "optionally" means that stirring with or without heating may be carried out. When the temperature of the system meets certain requirements, the system can be stirred without heating.
As a preferred scheme, the feed-liquid ratio of the selenium-rich plants to the strongly acidic oxidized electrolyzed water is 1 g: (10-100) mL. The dosage of the strongly acidic oxidation electrolyzed water is 10-100mL relative to 1g of the selenium-rich plants.
As a preferred scheme, the material-liquid ratio of the selenium-rich plant powder to the extraction solvent is 1 g: (10-50) mL. The dosage of the extraction solvent is 10-50mL relative to 1g of selenium-rich plant powder. The material-liquid ratio of the selenium-rich plant powder to the extraction solvent is preferably 1 g: (30-40) mL, most preferably 1 g: 36 mL.
Preferably, the average grain size of the selenium-rich plants is 40-60 meshes.
Preferably, the mixing temperature is 20-40 ℃ and the mixing time is 10-120 min. The heating and stirring are also a mixing process, so that the heating temperature is 20-40 ℃ on the premise of heating and stirring.
Preferably, the extraction solvent is at least one selected from the group consisting of ethanol, water, n-butanol, methanol and ethyl acetate. In a further preferred embodiment, the extraction solvent is ethanol, such as ethanol with a volume fraction of 50% to 90%, and most preferably ethanol with a volume fraction of 80%.
As a preferred scheme, the temperature for heating reflux extraction is 60-80 ℃, and the time is 90-150 min.
Preferably, the method for preparing strongly acidic oxidized electrolyzed water comprises the following steps:
in an ion exchange membrane electrolytic cell, a homogeneous ion exchange membrane is adopted to divide the electrolytic cell into a cathode area and an anode area; the anode adopts an oxide composite electrode, and the cathode adopts a titanium plate electrode; and respectively adding sodium chloride aqueous solution as electrolyte in a cathode area and an anode area, and performing constant current electrolysis to obtain strong acid oxidation electrolyzed water in the anode area and alkaline reduction electrolyzed water in the cathode area.
Further preferably, in the method for producing strongly acidic electrolyzed oxidizing water, the concentration of the aqueous solution of sodium chloride is 1 to 3 g/L.
In a further preferred embodiment, in the method for producing strongly acidic electrolyzed oxidizing water, the constant current density of the constant current electrolysis is 20 to 70mA/cm2And the constant-current electrolysis time is 10-90 min.
In a further preferred embodiment, in the method for preparing strongly acidic electrolyzed oxidizing water, the distance between the cathode plate and the anode plate is 1-3 cm.
In one particular embodiment, the effective area of the electrode may be 3.5cm according to the present invention2
The technical scheme of the invention has the following beneficial effects:
(1) the method for extracting the active components of the plants in an auxiliary manner can improve the yield of the selenium-rich components in the subsequent steps, and the pretreatment operation steps are simple.
(2) The oxidized electrolyzed water has the characteristics of safety, environmental protection, no toxicity, no harm and the like, and can not cause the problem of environmental pollution.
Additional features and advantages of the invention will be set forth in the detailed description which follows.
Detailed Description
Preferred embodiments of the present invention will be described in more detail below. While the following describes preferred embodiments of the present invention, it should be understood that the present invention may be embodied in various forms and should not be limited by the embodiments set forth herein. Rather, these embodiments are provided so that this disclosure will be thorough and complete, and will fully convey the scope of the invention to those skilled in the art.
In the following examples and comparative examples, the antioxidant effect of the extract and the selenium content of the extract were measured by spectrophotometry and fluorospectrophotometry, wherein the formulas for the clearance of 1, 1-diphenyl-2-trinitrophenylhydrazine (DPPH) free radical and the selenium content were respectively:
Figure BDA0003459149130000051
wherein: a. theiAbsorbance of the sample; a. thexEthanol replaces the absorbance of DPPH solution; a. the0Blank control (pure water substitute sample)
Figure BDA0003459149130000052
In the following examples and comparative examples, homogeneous anion exchange membranes and homogeneous cation exchange membranes used in ion membrane electrolyzers were purchased from Hangzhou environmental protection technologies, Inc. under the model number HoCEM Grion 0011T; the anode adopts a titanium-based oxide composite electrode, and the preparation method of the composite electrode is shown in example 1 of the invention patent with the patent number of ZL 201410452379.X, namely the preparation method of a platinum-iridium oxide alloy electrode, wherein the molar ratio of platinum to iridium is 1: 1.
Example 1
In the ion membrane electrolytic cell, a homogeneous cation exchange membrane is adopted to divide the ion membrane electrolytic cell into a cathode region and an anode region according to the volume ratio of 1:1, the distance between a cathode plate and an anode plate is 2cm, and the effective area of an electrode is 3.5cm2. Taking a NaCl solution of 2g/L as an electrolyte, and adding 400mL of sodium chloride solution into an anode region and a cathode region respectively. And respectively connecting an anode electrode and a cathode electrode on a potentiostat to perform constant current electrolysis, wherein the whole electrolysis reaction is dynamically performed. In the electrolytic process, the constant current density is 60mA/cm2Electrolyzing for 30min to obtain oxidized electrolyzed water in the anode area. Through detection, the pH value of the electrolyzed oxidizing water is 2.20, the oxidation-reduction potential value is 1100mV, and the effective chlorine concentration is 40.00 mg/L. 10.0g of crushed and ground selenium-rich gynostemma pentaphyllum is put into 100mL of oxidation electrolytic water and soaked and stirred for 3.2h at the temperature of 35 ℃. Then filtering and putting into a drying oven, keeping the temperature at 60 ℃ until drying, and then grinding into powder in a mortar (the average particle size after grinding is 40-60 meshes). Weighing 2.0g of the pretreated selenium-rich gynostemma pentaphyllum sample, adding 72mL of 80% ethanol solution according to the solid-to-liquid ratio of 1:36, and extracting by adopting an ethanol reflux method. The extraction temperature is 70 deg.C, and the extraction time is 120 min. After cooling under reflux, the supernatant was centrifuged. Centrifuging, collecting supernatant, determining its antioxidant effect by DPPH free radical scavenging method of 94.23%, determining selenium content in herba Gynostemmatis by fluorescence spectrophotometry of 0.21 μ g/g, and the extraction effect is obviously better than that of comparative example 1.
Example 2
In an ionic membrane electrolytic cell, a homogeneous cation exchange membrane is adopted according to the volume ratio of 1:1The ionic membrane electrolytic cell is divided into a cathode region and an anode region, the distance between a cathode plate and an anode plate is 2cm, and the effective area of the electrode is 3.5cm2. Taking a NaCl solution of 2g/L as an electrolyte, and adding 400mL of sodium chloride solution into an anode region and a cathode region respectively. And respectively connecting an anode electrode and a cathode electrode on a potentiostat to perform constant current electrolysis, wherein the whole electrolysis reaction is dynamically performed. In the electrolytic process, the constant current density is 60mA/cm2Electrolyzing for 30min to obtain oxidized electrolyzed water in the anode area. Through detection, the pH value of the electrolyzed oxidizing water is 2.20, the oxidation-reduction potential value is 1100mV, and the effective chlorine concentration is 40.00 mg/L. 10.0g of crushed and ground common gynostemma pentaphylla is put into 100mL of acidic oxidation electrolysis water and soaked and stirred for 3.2h at the temperature of 35 ℃. Then filtering and putting into a drying oven, drying at constant temperature of 60 ℃, and then grinding into powder in a mortar (the average particle size after grinding is 40-60 meshes). Weighing 2.0g of the pretreated common gynostemma pentaphylla sample, and putting the sample into 72mL of 80% ethanol solution according to the solid-to-liquid ratio of 1: 36. Extracting with ethanol under reflux. The extraction temperature is 70 deg.C, and the extraction time is 120 min. After cooling under reflux, the supernatant was centrifuged. Centrifuging, collecting supernatant, determining antioxidant effect by DPPH free radical scavenging method to be 93.05%, determining selenium content in common Gynostemma pentaphyllum to be 0.06 μ g/g by fluorescence spectrophotometry, and the extraction effect is obviously superior to that of comparative example 2.
The only difference from example 1 is that ordinary gynostemma pentaphylla was used.
Example 3
In the ion membrane electrolytic cell, a homogeneous cation exchange membrane is adopted to divide the ion membrane electrolytic cell into a cathode region and an anode region according to the volume ratio of 1:1, the distance between a cathode plate and an anode plate is 2cm, and the effective area of an electrode is 3.5cm2. Taking a NaCl solution of 2g/L as an electrolyte, and adding 400mL of sodium chloride solution into an anode region and a cathode region respectively. And respectively connecting an anode electrode and a cathode electrode on a potentiostat to perform constant current electrolysis, wherein the whole electrolysis reaction is dynamically performed. In the electrolytic process, the constant current density is 60mA/cm2Electrolyzing for 60min to obtain oxidized electrolyzed water in the anode area. Through detection, the pH value of the oxidation electrolyzed water is 2.20, the oxidation-reduction potential value is 1100mV, andthe concentration of the available chlorine is 90.00 mg/L. 10.0g of crushed and ground selenium-rich gynostemma pentaphyllum is put into 100mL of oxidation electrolytic water and soaked and stirred for 4.0h at the temperature of 35 ℃. Then filtering and putting into a drying oven, keeping the temperature at 60 ℃ until drying, and then grinding into powder in a mortar (the average particle size after grinding is 40-60 meshes). Weighing 2.0g of the pretreated selenium-rich gynostemma pentaphyllum sample, adding 72mL of 80% ethanol solution according to the solid-to-liquid ratio of 1:36, and extracting by adopting an ethanol reflux method. The extraction temperature is 70 deg.C, and the extraction time is 120 min. After cooling under reflux, the supernatant was centrifuged. Centrifuging, collecting supernatant, determining antioxidant effect by DPPH free radical scavenging method to be 95.25%, and determining selenium content in herba Gynostemmatis to be 0.28 μ g/g by fluorescence spectrophotometry.
Example 4
In the ion membrane electrolytic cell, a homogeneous cation exchange membrane is adopted to divide the ion membrane electrolytic cell into a cathode region and an anode region according to the volume ratio of 1:1, the distance between a cathode plate and an anode plate is 2cm, and the effective area of an electrode is 3.5cm2. Taking a NaCl solution of 2g/L as an electrolyte, and adding 400mL of sodium chloride solution into an anode region and a cathode region respectively. And respectively connecting an anode electrode and a cathode electrode on a potentiostat to perform constant current electrolysis, wherein the whole electrolysis reaction is dynamically performed. In the electrolytic process, the constant current density is 60mA/cm2Electrolyzing for 90min to obtain oxidized electrolyzed water in the anode area. Through detection, the pH value of the electrolyzed oxidizing water is 2.20, the oxidation-reduction potential value is 1150mV, and the effective chlorine concentration is 125.00 mg/L. 10.0g of crushed and ground selenium-rich gynostemma pentaphyllum is put into 100mL of oxidation electrolytic water and soaked and stirred for 4.0h at the temperature of 35 ℃. Then filtering and putting into a drying oven, keeping the temperature at 60 ℃ until drying, and then grinding into powder in a mortar (the average particle size after grinding is 40-60 meshes). Weighing 2.0g of the pretreated selenium-rich gynostemma pentaphyllum sample, putting the selenium-rich gynostemma pentaphyllum sample into 70mL of 80% ethanol solution according to the solid-to-liquid ratio of 1:36, and extracting by adopting an ethanol reflux method. The extraction temperature is 70 deg.C, and the extraction time is 120 min. After cooling under reflux, the supernatant was centrifuged. Centrifuging, collecting supernatant, scavenging DPPH free radical to determine its antioxidant effect of 95.62%, and determining selenium content in herba Gynostemmatis of 0.31 μ g/g by fluorescence spectrophotometry.
Comparative example 1
10.0g of selenium-rich gynostemma pentaphyllum which is cut and ground is put into 100mL of deionized water and stirred for 3.2h at the temperature of 35 ℃. Then filtering and putting into a drying oven, drying at constant temperature of 60 ℃, and then grinding into powder in a mortar (the average particle size after grinding is 40-60 meshes). Weighing 2.0g of the pretreated selenium-rich gynostemma pentaphylla sample, and putting the selenium-rich gynostemma pentaphylla sample into 72mL of 80% ethanol solution according to the solid-to-liquid ratio of 1: 36. Extracting with ethanol under reflux. The extraction temperature is 70 deg.C, and the extraction time is 120 min. And (3) after refluxing, taking the supernatant, cooling and centrifuging, measuring the antioxidant effect of the supernatant to be 85.10% by a DPPH free radical scavenging method, and measuring the content of selenium in the selenium-rich gynostemma pentaphylla to be extracted to be 0.13 mug/g by a fluorescence spectrophotometry method.
Comparative example 2
10.0g of chopped and ground common gynostemma pentaphylla is put into 100mL of deionized water and stirred for 3.2h at 35 ℃. Then filtering and putting into a drying oven, drying at constant temperature of 60 ℃, and then grinding into powder in a mortar (the average particle size after grinding is 40-60 meshes). Weighing 2.0g of the pretreated gynostemma pentaphylla sample, and putting the gynostemma pentaphylla sample into 72mL of 80% ethanol solution according to the solid-to-liquid ratio of 1: 36. Extracting with ethanol under reflux. The extraction temperature is 70 deg.C, and the extraction time is 120 min. And (3) after refluxing, taking the supernatant, cooling and centrifuging, measuring the antioxidant effect of the supernatant to be 81.05% by a DPPH free radical scavenging method, and measuring the content of selenium in the gynostemma pentaphylla to be extracted to be 0.02 mug/g by a fluorescence spectrophotometry method.
Having described embodiments of the present invention, the foregoing description is intended to be exemplary, not exhaustive, and not limited to the embodiments disclosed. Many modifications and variations will be apparent to those of ordinary skill in the art without departing from the scope and spirit of the described embodiments.

Claims (10)

1. The application of strong acidic electrolyzed oxidizing water in improving the extraction content of selenium active components.
2. The use of strongly acidic oxidized electrolyzed water as claimed in claim 1 for increasing the extraction content of selenium-active components in plants.
3. The use of the strongly acidic oxidized electrolyzed water as claimed in claim 2 for increasing the extraction content of selenium active components, wherein the plant comprises at least one of gynostemma pentaphyllum, sophora flower bud, camelina sativa, and lotus japonicus.
4. The use of strongly acidic oxidized electrolyzed water according to claim 1 for increasing the extraction content of selenium-active components,
the pH value of the strongly acidic electrolyzed oxidizing water is less than or equal to 2.7;
the content of available chlorine in the strongly acidic electrolyzed oxidizing water is 10-200 mg/L, preferably 40-175 mg/L, and more preferably 90-150 mg/L;
the oxidation-reduction potential value of the strongly acidic electrolyzed oxidizing water is more than or equal to 1050 mV.
5. The use of strongly acidic oxidized electrolyzed water as claimed in claim 1 for increasing the extraction content of selenium-active components, wherein the use comprises:
mixing selenium-rich plants with the strongly acidic oxidized electrolyzed water, optionally heating, stirring, filtering, drying, and grinding to obtain selenium-rich plant powder;
mixing the selenium-rich plant powder with an extraction solvent, heating and refluxing for extraction, taking the first supernatant for centrifugal separation, and taking the second supernatant as a plant selenium extracting solution rich in selenium active components.
6. The use of strongly acidic oxidized electrolyzed water according to claim 5 for increasing the extraction content of selenium-active components,
the feed-liquid ratio of the selenium-rich plants to the strongly acidic oxidized electrolyzed water is 1 g: (10-100) mL;
the material-liquid ratio of the selenium-rich plant powder to the extraction solvent is 1 g: (10-50) mL, preferably 1 g: (30-40) mL.
7. The use of strongly acidic oxidized electrolyzed water according to claim 5 for increasing the extraction content of selenium-active components,
the average grain size of the selenium-rich plants is 40-60 meshes;
the mixing temperature is 20-40 ℃, and the mixing time is 10-120 min;
the extraction solvent is at least one selected from ethanol, water, n-butanol, methanol and ethyl acetate;
the temperature of heating reflux extraction is 60-80 ℃, and the time is 90-150 min.
8. The use of strongly acidic electrolyzed oxidizing water as claimed in claim 1 for increasing the extraction content of selenium active components, wherein the preparation method of the strongly acidic electrolyzed oxidizing water comprises:
in an ion exchange membrane electrolytic cell, a homogeneous ion exchange membrane is adopted to divide the electrolytic cell into a cathode area and an anode area; the anode adopts an oxide composite electrode, and the cathode adopts a titanium plate electrode; and respectively adding sodium chloride aqueous solution as electrolyte in a cathode area and an anode area, and performing constant current electrolysis to obtain strong acid oxidation electrolyzed water in the anode area and alkaline reduction electrolyzed water in the cathode area.
9. The use of the strongly acidic electrolyzed oxidizing water as claimed in claim 7 for increasing the extraction content of selenium active components, wherein the concentration of the aqueous sodium chloride solution is 1-3 g/L.
10. The use of strongly acidic oxidized electrolyzed water according to claim 7 for increasing the extraction content of selenium-active components,
the constant current density of the constant current electrolysis is 20-70 mA/cm2The constant-current electrolysis time is 10-90 min;
the distance between the cathode plate and the anode plate is 1-3 cm.
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Application publication date: 20220415