CN111252744A - Preparation method and application of nano-selenium - Google Patents
Preparation method and application of nano-selenium Download PDFInfo
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B19/00—Selenium; Tellurium; Compounds thereof
- C01B19/02—Elemental selenium or tellurium
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K8/00—Cosmetics or similar toiletry preparations
- A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
- A61K8/19—Cosmetics or similar toiletry preparations characterised by the composition containing inorganic ingredients
- A61K8/23—Sulfur; Selenium; Tellurium; Compounds thereof
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
- A61Q19/00—Preparations for care of the skin
- A61Q19/08—Anti-ageing preparations
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/01—Particle morphology depicted by an image
- C01P2004/03—Particle morphology depicted by an image obtained by SEM
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- General Health & Medical Sciences (AREA)
- Public Health (AREA)
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- Acyclic And Carbocyclic Compounds In Medicinal Compositions (AREA)
Abstract
The invention discloses a preparation method and application of nano-selenium, belonging to the technical field of nano-selenium, the method comprises the steps of mixing a polyvinyl alcohol solution and a sodium selenite solution, dripping an ascorbic acid solution into the mixed solution, and carrying out ultrasonic reaction to obtain the nano-selenium; the preparation conditions of the invention are normal pressure, the reaction temperature is lower, the reaction time is short, the whole preparation process is safe and stable, the control is convenient, the implementation is easy, the cost of raw materials is low, the invention is non-toxic and harmless, the obtained product has uniform particle size, smaller particles, good crystallinity and good water solubility and biocompatibility, and the experiment verifies the oxidation resistance of the nano-selenium, thereby providing a good foundation for the research and application of the oxidation resistance of the nano-selenium.
Description
Technical Field
The invention relates to the technical field of nano-selenium, in particular to a preparation method and application of nano-selenium.
Background
Selenium is in group VIA and is a metalloid element, and early studies on selenium were mainly based on its properties and uses. For example, the gray selenium thin layer is widely applied to photocells, rectifiers, copy technologies and the like because of excellent photoelectric characteristics and unidirectional conductivity; selenium is also widely used in the manufacture of railway and navigation signal lights as well as in the paint and ceramic industries because of its good red light transmittance. Selenium is also a necessary trace element for human bodies, various diseases can be caused by selenium deficiency, and the proper amount of selenium supplement can effectively prevent and treat various diseases. And single crystal selenium is an important element semiconductor and has two different existing forms of amorphous form and crystalline form. The amorphous nano-selenium has good biological activity and plays an extremely important role in the important life activities such as oxidation resistance, immunity regulation, harmful heavy metal antagonism and the like. The crystal form selenium has lower melting point, high photoconductivity and high chemical activity, and has wide market application in photocell, mechanical inductor, rectifier, photosensitive element and copying technology. The Chinese patent 97107038.5 discloses a method for preparing active red elemental selenium, which is the first creation at home and abroad through the identification of national authorities and the review of medical experts. Then, there are many patents disclosing the preparation of nano-selenium, which generally uses selenium compound as raw material in the presence of protective agent, and adopts a certain reducing agent to react, so as to reduce the compound into elemental selenium, wherein the nano-selenium has various shapes, such as sphere, filament, rod, and dendritic. Chinese patent specification CN1789113A discloses a method for preparing nano-selenium by reducing selenious acid or selenite with ascorbic acid and hydrocarbon amine hydrochloride in the presence of polyvinylpyrrolidone, polyvinyl alcohol and chitosan protective agent by using ultrasound. The chinese patent application CN1669913A discloses a hydrothermal reaction for preparing elemental selenium nanotube by reducing sodium selenite with glucose. Meanwhile, Chinese patent application specification CN1519195A also discloses a hydrothermal method, which is to use elemental selenium powder to generate a nano selenium tube in a mixed solution of water, alcohol, ammonia water and hydrazine. In summary of the preparation methods, we can find that most of the preparation processes have complex whole systems, complicated preparation processes, various conditions which are difficult to control, and more energy consumption, and the prepared nano selenium has large size and no water solubility and biocompatibility. Therefore, in order to better develop the application of nano-selenium in various aspects, it is important to find a safe, convenient, efficient and energy-saving method capable of generating water-soluble and biocompatible nano-selenium.
Meanwhile, oxidative stress often causes an increase in the free radical content in the body, thereby having a detrimental effect on proteins, lipids and deoxyribonucleic acid. In addition, it also has effects on various pathophysiological processes such as neurodegenerative diseases, cancer, cardiovascular diseases, inflammatory diseases and aging. The antioxidant can reduce oxidative stress, and is beneficial to health. Therefore, in recent years, antioxidant products have become a new favorite for health care and cosmetic enterprises.
Disclosure of Invention
The invention aims to provide a preparation method of nano-selenium and application thereof, so as to solve the problems in the prior art.
In order to achieve the purpose, the invention provides the following scheme:
the invention provides a preparation method of nano-selenium, which comprises the steps of mixing a polyvinyl alcohol solution and a sodium selenite solution, dropwise adding an ascorbic acid solution into the mixed solution, and carrying out ultrasonic reaction to obtain the nano-selenium.
Further, the mass concentration of the polyvinyl alcohol solution is 0.5%.
Further, the concentration of the sodium selenite solution is 0.1 mol/L.
Further, the concentration of the ascorbic acid solution is 0.1 mol/L.
Further, the mass ratio of the polyvinyl alcohol solution to the sodium selenite solution to the ascorbic acid solution is 1:1: 3.
Further, the mixing and dropping process is performed under magnetic stirring.
Further, the reaction is carried out for 2 hours under the conditions of constant temperature heating at 40 ℃ and magnetic stirring.
The invention also provides the nano-selenium prepared by the preparation method of the nano-selenium.
The invention also provides application of the nano-selenium in antioxidant activity and preparation of natural antioxidants.
The invention discloses the following technical effects:
the preparation conditions of the invention are normal pressure, the reaction temperature is lower, the reaction time is short, the whole preparation process is safe and stable, the control is convenient, the implementation is easy, the cost of raw materials is low, the invention is non-toxic and harmless, the obtained product has uniform particle size, smaller particles, good crystallinity and good water solubility and biocompatibility, the selenium is prepared to the nano level, and the obtained nano selenium has high bioactivity and bioavailability. Compared with the traditional selenium product, the nano selenium is lower in toxicity, a new thought and a new development are provided for developing selenium supplement products, the oxidation resistance of the nano selenium is verified through experiments, and a good foundation can be provided for the research and application of the oxidation resistance of the nano selenium.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings needed in the embodiments will be briefly described below, and it is obvious that the drawings in the following description are only some embodiments of the present invention, and it is obvious for those skilled in the art to obtain other drawings without creative efforts.
FIG. 1 is SEM image A of nano-selenium prepared in example 1;
FIG. 2 is SEM image B of nano-selenium prepared in example 1;
FIG. 3 is a graph of DPPH radical clearance rate for example 2;
FIG. 4 is a graph of hydroxyl radical clearance for example 2;
FIG. 5 is a plot of superoxide anion radical clearance rate for example 2;
FIG. 6 is a graph showing the reducing power in example 2.
Detailed Description
Reference will now be made in detail to various exemplary embodiments of the invention, the detailed description should not be construed as limiting the invention but as a more detailed description of certain aspects, features and embodiments of the invention.
It is to be understood that the terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention. Further, for numerical ranges in this disclosure, it is understood that each intervening value, between the upper and lower limit of that range, is also specifically disclosed. Every smaller range between any stated value or intervening value in a stated range and any other stated or intervening value in a stated range is encompassed within the invention. The upper and lower limits of these smaller ranges may independently be included or excluded in the range. Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. Although only preferred methods and materials are described herein, any methods and materials similar or equivalent to those described herein can be used in the practice or testing of the present invention. All documents mentioned in this specification are incorporated by reference herein for the purpose of disclosing and describing the methods and/or materials associated with the documents. In case of conflict with any incorporated document, the present specification will control.
It will be apparent to those skilled in the art that various modifications and variations can be made in the specific embodiments of the present disclosure without departing from the scope or spirit of the disclosure. Other embodiments will be apparent to those skilled in the art from consideration of the specification. The specification and examples are exemplary only.
As used herein, the terms "comprising," "including," "having," "containing," and the like are open-ended terms that mean including, but not limited to.
In the examples of the present invention, the reagents used are all analytical grade, and the source of the reagents used and the source of the apparatus used can be selected by those skilled in the art based on experience or limited experiments.
Example 1 preparation and characterization of Nano-selenium
1. Preparation of nano-selenium
1.1 preparation of the solution
1.1.10.1M sodium selenite solution
1.729g of sodium selenite is precisely weighed, deionized water is used as a solvent, the sodium selenite is dissolved in a beaker by using a proper amount of deionized water and then transferred to a 100mL volumetric flask, and the deionized water is supplemented to a constant volume to a scale mark.
1.1.20.1M ascorbic acid solution
Precisely weighing 0.440g of ascorbic acid, taking deionized water as a solvent, dissolving the ascorbic acid in a beaker by using a proper amount of deionized water, transferring the dissolved ascorbic acid into a 25mL volumetric flask, and supplementing the deionized water to a constant volume to be marked with a scale mark.
1.1.30.5% polyvinyl alcohol solution
0.500g of polyvinyl alcohol is precisely weighed, deionized water is used as a solvent, the solvent is dissolved in a beaker by using a proper amount of deionized water and then transferred to a 100mL volumetric flask, and the deionized water is supplemented to a constant volume to be a scale mark.
1.2 preparation of Nano selenium
Under magnetic stirring, mixing a polyvinyl alcohol solution with the concentration of 0.5 wt% and a sodium selenite solution with the concentration of 0.1M, and dropwise adding an ascorbic acid solution with the concentration of 0.1M into the mixed solution; polyvinyl alcohol solution: sodium selenite solution: the mass ratio of the ascorbic acid solution is 1:1: 3; and (3) placing the reaction mixed solution under a constant-temperature heating magnetic stirring pot at 40 ℃, performing probe type ultrasonic reinforcement auxiliary preparation, wherein the fixed frequency of probe type ultrasonic is 25KHz, the power is 1000W, and reacting for 2h to obtain the nano-selenium.
The probe type ultrasonic method has the advantages of short preparation time, uniform nano particle size and good dispersibility.
2. Characterization of
The obtained nano selenium product is observed under a MERLIN scanning electron microscope to obtain the particle size and the appearance of the product. The nano-selenium obtained by the reaction is in a uniform spherical shape with the diameter of about 105nm under a scanning electron microscope as shown in figures 1 and 2. The polyvinyl alcohol has better dissolving capacity in aqueous solution, and the formed microenvironment has good suspending, emulsifying and stabilizing effects because long-chain molecules are spirally wound with each other. The generated elemental selenium is adsorbed and wrapped by the polyvinyl alcohol, so that the mutual polymerization and agglomeration of the initially formed selenium particles are effectively prevented, and the effects of slowing down and controlling the growth of the selenium particles can be achieved. The nano-selenium obtained by the reaction is red.
Example 2 Nano selenium Oxidation resistance test
2.1 DPPH radical scavenging experiment
2.1.1 preparation of the solution
(1) Accurately weighing 0.0025g of 1, 1-diphenyl-2-trinitrophenylhydrazine (DPPH), dissolving with a small amount of 70% ethanol, transferring into a 50ml brown volumetric flask, fixing the volume with 70% ethanol to obtain 0.05mg/mLDPPH test solution, placing in a refrigerator for storage, and preparing for use on site;
(2) taking the nano selenium solution, and preparing the nano selenium solution into solutions with the concentrations of 0.5, 1.0, 1.5, 2.0 and 2.5 mg/mL.
2.1.2 determination of clearance
5.00mL of each sample solution was precisely aspirated, 5.00mL of a DPPH solution (0.05mg/mL) was added thereto, the mixture was sufficiently shaken, and the mixture was allowed to stand in the dark for 30 min. Determination of the absorbance A of the test solution at 517nmi. After 5.00mL of the sample solution and 5.00mL of the solvent were sufficiently mixed, the absorbance A at 517nm was measuredj. Absorbance A at 517nm after thoroughly mixing 5.00mL of DPPH solution with 5.00mL of solventc。
And (5) sorting and substituting the obtained A value into a formula (2-2) to calculate the DPPH free radical clearance.
In the formula AiThe absorbance of the mixed solution of the sample solution and the DPPH solution; a. thejThe absorbance of the mixed solution of the sample solution and the solvent of 70 percent ethanol; a. thecThe absorbance of the mixture of DPPH solution and 70% ethanol solvent is shown.
The results are shown in FIG. 3, and it can be seen from FIG. 3 that: (1) the clearance rate increases with increasing concentration. (2) The DPPH free radical scavenging capacity of the nano-selenium is 0.662mg/mL by SPSS analysis, and the DPPH scavenging IC50 of the nano-selenium is 0.662 mg/mL.
2.2 hydroxyl radical scavenging experiments
2.2.1 preparation of the solution
(1)6mmol/L FeSO4Solution: accurately weighing FeSO4·7H20.0840g of O powder, using deionized water as a solvent, adding a small amount of deionized water for dissolutionTransferring to a 50ml brown volumetric flask, fixing the volume to a scale with deionized water, and storing in dark place for use;
(2)6mmol/L salicylic acid-ethanol solution: accurately weighing 0.0420g of salicylic acid powder, taking absolute ethyl alcohol as a solvent, adding a small amount of absolute ethyl alcohol for dissolving, transferring into a 50mL volumetric flask, and fixing the volume to a scale by using the absolute ethyl alcohol to obtain the salicylic acid powder;
(3)6mmol/LH2O2solution: precisely absorb 30% H2O2Putting 4.60mL of the solution in a 25mL volumetric flask, and fixing the volume to a scale with deionized water to obtain the product;
(4) nano selenium solution, prepared into solution with concentration of 0.00, 0.25, 0.5, 0.75 and 1.00 mg/mL.
2.2.2 determination of clearance
Accurately absorb 6mmol/L Fe2+2.00mL of the solution and 2.00mL of a 6mmol/L salicylic acid-ethanol solution were placed in a test tube. Respectively adding 2mL of sample solution into the test tubes, fully shaking, and standing for 10 min. 6mmol/L H was added2O2The reaction was started with 2.00mL of the solution and immediately placed in a 37 ℃ water bath for 30 min. And (6) cooling. Measuring absorbance value Ai at 510 nm; replacement of H with deionized water2O2The solution is not changed, and the absorbance value is measured to be Ai0. Replacing sample liquid with deionized water, operating, and measuring absorbance value A0。
And (4) sorting the obtained numerical values and substituting the numerical values into a calculation formula of the clearance rate, such as a formula (2-3).
In the formula AiIs the absorbance value of the sample solution; a. thei0Blank control absorbance value of the sample solution; a. the0Is a blank solution absorbance value.
The results are shown in FIG. 4, and FIG. 4 shows that: the removing capability of the nano-selenium is strong and is enhanced along with the increase of the concentration. The IC50 of nano-selenium to hydroxyl radical was 0.468mg/mL analyzed by SPSS.
2.3 superoxide anion radical scavenging experiments
2.3.1 preparation of the solution
(1) pH 8.2 Tris-HCl buffer solution: 1.2114g of 2-amino-2- (hydroxymethyl) -1, 3-propanediol (Tris) is precisely weighed, and the volume is adjusted to 100mL by deionized water, so as to obtain a Tris solution (0.1 mol/L). Putting 50mL of the Tris solution into a 100mL volumetric flask, adding 22.9mL of 0.1mol/L hydrochloric acid solution, fully and uniformly mixing, and then fixing the volume to a scale with deionized water to obtain the Tris-base aqueous solution;
(2)3mmol/L pyrogallol solution: accurately weighing 0.0191g of pyrogallol, adding a small amount of 10mmol/L HCL solution for dissolving, transferring to a 50mL brown volumetric flask, and fixing the volume to the scale by using 10mmol/L HCL to obtain the pyrogallol;
(3) nano selenium solution, prepared into solution with concentration of 0.050, 0.075, 0.100, 0.125 and 0.150 mg/mL.
2.3.2 determination of clearance
Taking a test tube, adding 4.50mL of Tris-HCL buffer solution (pH 8.2) and 4.20mL of sample solutions with different concentrations, and uniformly mixing. The mixture was transferred to a 25 ℃ water bath for 20 min. After water bath, 0.30mL of pyrogallol solution with concentration of 3mmol/L preheated to 25 ℃ is added, and the mixture is quickly and fully shaken. Quickly poured into a cuvette, and the absorbance of the cuvette was measured at 325nm against a 0.1mol/L HCl solution. The measurement is carried out every 30s for 5min continuously. The sample was replaced with deionized water and the rest of the procedure was unchanged as a control.
2.3.3 calculating the slope of wavelength and time by plotting the wavelength as ordinate and the time as abscissa, the experimental group is KbThe control group is K0。
The obtained value is substituted into the calculation formula of the superoxide radical clearance rate, and the calculation formula is shown as (2-4):
the results are shown in FIG. 5, and the analysis in FIG. 5 shows that: the inhibition rate of the nano selenium on superoxide anion increases along with the increase of concentration, and the increase trend is large and gentle at the concentration of 0.100-0.125 mg/mL. The IC50 of the nano-selenium to the superoxide anion was 0.101mg/mL as analyzed by SPSS software.
2.4 reduction force test
2.4.1 preparation of the solution
(1) pH6.6 phosphoric acid buffer solution: 3.121g of sodium dihydrogen phosphate is precisely weighed, dissolved by deionized water and transferred to a 100mL volumetric flask, and the deionized water is used for constant volume; 7.164g of disodium hydrogen phosphate is precisely weighed, dissolved by deionized water and transferred to a 100mL volumetric flask, and the volume is determined by the deionized water; putting 62.5mL of sodium dihydrogen phosphate and 37.5mL of disodium hydrogen phosphate into a 100mL volumetric flask, and adjusting the pH value to obtain the product;
(2) 1% potassium ferricyanide solution: accurately weighing 1.00g of potassium ferricyanide, dissolving the potassium ferricyanide with deionized water, transferring the potassium ferricyanide into a 100mL volumetric flask, and fixing the volume with the deionized water to obtain the potassium ferricyanide solution;
(3) preparation of 10% trichloroacetic acid solution: accurately weighing 10.00g of trichloroacetic acid, dissolving with deionized water, transferring into a 100mL volumetric flask, and diluting with deionized water to a constant volume to obtain the trichloroacetic acid solution;
(4) 0.1% ferric chloride solution: accurately weighing 0.10g of ferric trichloride, dissolving with deionized water, transferring into a 100mL volumetric flask, and diluting with deionized water to a constant volume to obtain the ferric trichloride solution;
(5) nano selenium solution, prepared into solution with concentration of 0.050, 0.075, 0.100, 0.125 and 0.150 mg/mL.
2.4.2 reduction force measurement
2.5mL of the sample solution, 2.5mL of pH6.6 phosphate buffer solution and 2.5mL of 1% potassium ferricyanide solution were placed in a test tube and mixed well. Water bath at 50 deg.c for 20 min. And (5) rapidly cooling. Then 2.5mL of 10% trichloroacetic acid is added and shaken up, and centrifuged at 3000r/min for 10 min. And adding 4mL of deionized water and 1mL of 0.1% ferric trichloride into 5mL of supernatant, uniformly mixing, and reacting for 10 min. The absorbance was measured at a wavelength of 700 nm.
The reducing power is related to the absorbance value. The larger the absorbance, the stronger the reducing power, and thus the comparison.
As a result, as shown in FIG. 6, the antioxidant (reducing agent) scavenges radicals by giving electrons by reducing action of itself, and the stronger the reducing ability is, the stronger the oxidation resistance is. As can be seen from fig. 6: the reduction force of the nano selenium is obvious under the concentration, and both the nano selenium and the nano selenium increase along with the increase of the concentration, so that the nano selenium has stronger reduction capability.
The nano selenium provided by the embodiment of the invention is applied to antioxidant activity and preparation of natural antioxidants. In the natural antioxidant, the nano-selenium can be directly prepared into the natural antioxidant, or can be mixed with auxiliary materials acceptable in application to prepare the natural antioxidant, and then the natural antioxidant is packaged according to a conventional method. The dosage of the nano-selenium in the invention can be properly changed according to different use scenes, use modes or preparations of the natural antioxidant, but on the premise of ensuring that the natural antioxidant achieves effective antioxidant concentration in the use scenes.
The above-described embodiments are merely illustrative of the preferred embodiments of the present invention, and do not limit the scope of the present invention, and various modifications and improvements of the technical solutions of the present invention can be made by those skilled in the art without departing from the spirit of the present invention, and the technical solutions of the present invention are within the scope of the present invention defined by the claims.
Claims (9)
1. A preparation method of nano-selenium is characterized in that a polyvinyl alcohol solution and a sodium selenite solution are mixed, an ascorbic acid solution is dripped into the mixed solution, and the nano-selenium is obtained through ultrasonic reaction.
2. The method of claim 1, wherein the polyvinyl alcohol solution has a mass concentration of 0.5%.
3. The method of claim 1, wherein the concentration of the sodium selenite solution is 0.1 mol/L.
4. The method of claim 1, wherein the ascorbic acid solution has a concentration of 0.1 mol/L.
5. The method for preparing nano selenium according to claim 1, wherein the mass ratio of the polyvinyl alcohol solution, the sodium selenite solution and the ascorbic acid solution is 1:1: 3.
6. The method of claim 1, wherein the mixing and dropping process is performed under magnetic stirring.
7. The method for preparing nano-selenium according to claim 1, wherein the reaction is carried out for 2 hours under the conditions of constant temperature heating and magnetic stirring at 40 ℃.
8. A nano-selenium prepared by the method for preparing nano-selenium according to any one of claims 1 to 7.
9. Use of the nano-selenium of claim 8 in antioxidant activity and in the preparation of natural antioxidants.
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