CN112125284A - Preparation method and medical application of amorphous nano-selenium with biological activity - Google Patents
Preparation method and medical application of amorphous nano-selenium with biological activity Download PDFInfo
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- CN112125284A CN112125284A CN202010897943.4A CN202010897943A CN112125284A CN 112125284 A CN112125284 A CN 112125284A CN 202010897943 A CN202010897943 A CN 202010897943A CN 112125284 A CN112125284 A CN 112125284A
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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
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K33/00—Medicinal preparations containing inorganic active ingredients
- A61K33/04—Sulfur, selenium or tellurium; Compounds thereof
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K9/00—Medicinal preparations characterised by special physical form
- A61K9/14—Particulate form, e.g. powders, Processes for size reducing of pure drugs or the resulting products, Pure drug nanoparticles
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- A—HUMAN NECESSITIES
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- A61P35/00—Antineoplastic agents
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y5/00—Nanobiotechnology or nanomedicine, e.g. protein engineering or drug delivery
Abstract
The invention discloses a preparation method of amorphous nano-selenium with bioactivity and medical application thereof, belonging to the technical field of synthesis of amorphous nano-selenium and preparation of anticancer drugs. The technical scheme provided by the invention has the key points that: adding a stabilizer solution into a selenosulfate solution, stirring and mixing uniformly, adding an acid solution to adjust the pH value of a mixed system to 2-6 to decompose the selenosulfate, placing the reaction solution under the protection of nitrogen for 8-24 h, centrifuging and washing to remove supernatant, and drying the precipitate to obtain the amorphous nano selenium with antitumor bioactivity and uniform particle size distribution. The amorphous nano-selenium with bioactivity prepared by the invention has bioactivity for resisting various tumors such as HepG2, MCF-7, HeLa, Kyse30 or A549 and the like, has low toxic and side effects on normal cells, and can be further used for preparing antitumor drugs for inhibiting tumor cell proliferation.
Description
Technical Field
The invention belongs to the technical field of synthesis of amorphous nano-selenium and preparation of anticancer drugs, and particularly relates to a preparation method of amorphous nano-selenium with bioactivity and medical application thereof.
Background
Selenium is a trace element essential to the human body. Plays an important role in the important life activities such as oxidation resistance, immunity regulation, harmful heavy metal antagonism and the like. Selenium supplement for human body exists in various selenoproteins mainly in the form of selenocysteine, and the supplement form of inorganic selenium is always limited. The main existing form of inorganic selenium compound is sodium selenite, which is a selenium compound with strong toxicity and poor biological applicability. Another common form of inorganic selenium compound is sodium selenosulfate, which is very unstable in nature. Unlike inorganic selenium compounds, elemental nano-selenium has the advantages of long half-life, quick absorption, safe use and the like, so the nano-selenium is a replaceable selenium source for preventing and treating selenium deficiency diseases. The nano-selenium solid has three structures: black hexagonal system, red monoclinic system and amorphous state. Under general conditions, the prepared nano-selenium is mainly two crystals, has low melting point, high photoconductivity and the like, and has wide application in photocells, rectifiers, mechanical sensing devices, photosensitive elements and copying technologies.
The reported preparation methods of the elemental nano-selenium are various, and the simple method is a reduction method, namely reducing high-price selenide by using different reducing agents to obtain the elemental selenium. For example, Chinese patent (CN 1184776A) in 1998 discloses the reduction of Na by using protein or polypeptide as raw material2SeO3Or Na2SeO4Or SeO2Obtaining stable elemental selenium; chinese patent No. 2010 (CN 101759159A) discloses reduction of selenium dioxide or selenite with sodium borohydride, a strong reducing agent, to obtain elemental selenium; the Chinese patent (CN 104310319A) in 2013 discloses reduction of selenite with glucose solutionThe nano elemental selenium is obtained; the Chinese patent (CN 104310319A) in 2015 uses sodium thiosulfate pentahydrate to reduce selenite to prepare nano-selenium. Then, researchers adopt biological reducing agents to prepare the nano elemental selenium. For example, CN 105154474A discloses that Chlorella is used for reducing selenite to prepare nano elemental selenium; the 2016 Chinese patent (CN 106539092A) discloses that vitamin C is used for reducing sodium selenite to prepare green alga polyglucosized nano-selenium in the presence of green alga polysaccharides, and the 2019 Chinese patent (109528757A) still uses vitamin C for reducing sodium selenite to prepare poria cocos oligosaccharide functionalized nano-selenium in the presence of poria cocos oligosaccharides. In conclusion, the nano-selenium is mainly prepared by reducing an inorganic selenium compound by using a reducing agent.
Disclosure of Invention
The invention solves the technical problem of providing a method for preparing the amorphous nano elemental selenium with biological activity, which is environment-friendly and strong in operability, and is characterized in that the method is realized by the self-oxidation-reduction reaction of raw materials. By adjusting the pH value of the selenosulfate solution to be acidic, the selenosulfate can generate self oxidation reduction reaction in the presence of stabilizers such as protein or polysaccharide and the like to prepare the amorphous nano selenium with bioactivity, and the amorphous nano selenium can be used for inhibiting the proliferation of tumor cells.
The invention adopts the following technical scheme for solving the technical problems, and the preparation method of the amorphous nano-selenium with bioactivity is characterized by comprising the following specific processes: adding a stabilizer solution into a selenosulfate solution, wherein the feeding molar ratio of selenosulfate to the stabilizer is 1: 2-1: 30, stirring and mixing uniformly, adding a dilute acid solution to adjust the pH value of a mixed system to be 2-6 so as to decompose selenosulfate, placing reaction liquid for 8-24 hours under the protection of nitrogen, then centrifugally washing to remove supernatant, drying precipitates to obtain amorphous nano selenium which is stable, has uniform particle size distribution and has anti-tumor activity, wherein the stabilizer is protein or polysaccharide, the protein is bovine serum albumin, human serum albumin, bovine hemoglobin, human hemoglobin, pepsin or trypsin, and the polysaccharide is galactose or chitosan.
Preferably, the selenosulfate solution is an aqueous solution of soluble selenosulfates, and the soluble selenosulfates are one or more of sodium selenosulfate, potassium selenosulfate or zinc selenosulfate.
Preferably, the selenosulfate is obtained from a commercially available source or the selenosulfate solution is freshly prepared as follows:
the method I comprises the following steps: adding 0.7-1.4 g of selenium powder into 0.02-1 mol/L of sulfite aqueous solution, wherein the sulfite is sodium sulfite, potassium sulfite or zinc sulfite, heating to 80-100 ℃ under the protection of nitrogen, heating under stirring for reflux reaction for 4-8 h, keeping the solution temperature at 80-100 ℃, closing and heating after the reaction is finished, naturally cooling the solution to 40-70 ℃, filtering unreacted selenium powder for recycling, and finally preparing selenosulfate solution;
method II: the method comprises the steps of dispersing selenite, sulfite and a reducing agent in deionized water according to a molar ratio of 1 (2-8) to (1-5), stirring and mixing uniformly at room temperature to obtain a selenosulfate solution, wherein the selenite is sodium selenite, potassium selenite or zinc selenite, the sulfite is sodium sulfite, potassium sulfite or zinc sulfite, and the reducing agent is sodium borohydride, mercaptoethanol, vitamin C, metallothionein or ascorbic acid.
Preferably, the dilute acid solution is a hydrochloric acid solution, a sulfuric acid solution or a nitric acid solution, and the molar concentration of the dilute acid solution is 0.1-3 mol/L.
Preferably, the drying process of the precipitate is freeze drying or drying at 30-40 ℃.
Preferably, the concentration of the stabilizer solution is 0.5-5.0 g/L.
Preferably, in the preparation process of the amorphous nano-selenium, the reaction solution is placed at room temperature for 12 hours or at 80 ℃ for 24 hours under the protection of nitrogen, and then centrifuged and washed at 10000-12000 rpm for 20-40 min to remove the supernatant.
The invention relates to application of amorphous nano-selenium with bioactivity in preparing antitumor drugs.
The invention relates to an application of amorphous nano-selenium with biological activity in preparing a medicament for inhibiting tumor cell proliferation, wherein the tumor cell is a human liver cancer cell (HepG 2), a human breast cancer cell (MCF-7), a human cervical cancer cell (HeLa), a human esophagus cancer cell (kyse 30) or a human lung cancer cell (A549).
Compared with the prior art, the invention has the following beneficial effects: 1. the method can synthesize the amorphous nano-selenium with anti-tumor bioactivity and uniform particle size distribution, has good stability, is environment-friendly in the production process, and has the conversion rate of the amorphous nano-selenium generated under proper conditions averagely reaching 76 percent (calculated by selenium powder); 2. the amorphous nano-selenium with bioactivity has bioactivity for resisting various tumors such as HepG2, MCF-7, HeLa or A549 and the like, has low toxic and side effects on normal cells, and can be further used for preparing antitumor drugs for inhibiting tumor cell proliferation.
Drawings
FIG. 1 is a TEM photograph of amorphous nano-selenium prepared in example 1;
FIG. 2 is an X-ray diffraction pattern of amorphous nano-selenium obtained in example 1;
FIG. 3 is a photoelectron spectrum of amorphous nano-selenium prepared in example 1;
FIG. 4 shows the measurement of the antitumor bioactivity of the amorphous nano-selenium prepared in example 1;
FIG. 5 is a TEM photograph of amorphous nano-selenium prepared in example 2;
FIG. 6 is an X-ray diffraction pattern of amorphous nano-selenium obtained in example 2;
FIG. 7 is a photoelectron spectrum of amorphous nano-selenium prepared in example 2;
FIG. 8 shows the measurement of the antitumor bioactivity of the amorphous nano-selenium prepared in example 2;
FIG. 9 is a TEM photograph of amorphous nano-selenium prepared in example 3;
FIG. 10 is an X-ray diffraction pattern of amorphous nano-selenium obtained in example 3;
FIG. 11 is a spectrum of amorphous nano-selenium produced in example 3;
FIG. 12 shows the measurement of the antitumor bioactivity of the amorphous nano-selenium prepared in example 3.
Detailed Description
The present invention is described in further detail below with reference to examples, but it should not be construed that the scope of the above subject matter of the present invention is limited to the following examples, and that all the technologies realized based on the above subject matter of the present invention belong to the scope of the present invention.
Example 1
(1) Preparing 0.4mol/L sodium sulfite solution, 4g/L bovine serum albumin solution and 0.1mol/L hydrochloric acid solution;
(2) dispersing 0.7g of black selenium powder into 50mL of the sodium sulfite solution, then adding double distilled water until the total reaction volume is 250mL, reacting the mixed system at 95 ℃ for 6 hours, performing suction filtration after the reaction is finished to obtain a supernatant, and adding 50mL of the bovine serum albumin solution into the filtrate to obtain a reaction system;
(3) adjusting the pH value of the reaction system to 4.0 by using the hydrochloric acid solution, gradually changing the reaction system to be orange red, then placing the reaction solution at 25 ℃ for 12h or at 80 ℃ for 24h, centrifuging at 13500r/min, washing the precipitate by using double distilled water, and freeze-drying to obtain an amorphous nano-selenium sample for later use. Observing the prepared nano selenium sample under a transmission electron microscope, and measuring and calculating the average grain diameter of the nano selenium to be about 15 nm; the nano selenium particles obtained by the analysis of an X-ray diffractometer are in an amorphous state, and the energy spectrum analysis proves that the amorphous nano particles are elemental selenium.
(4) This example examines the antitumor bioactivity of amorphous nano-selenium, and the test results are shown in fig. 4.
Example 2
(1) Preparing 0.4mol/L sodium sulfite solution, 4g/L galactose solution and 0.1mol/L hydrochloric acid solution;
(2) dispersing 0.7g of black selenium powder into 50mL of the sodium sulfite solution, then adding double distilled water until the total reaction volume is 250mL, reacting the mixed system at 95 ℃ for 6 hours, after the reaction is finished, performing suction filtration to obtain a supernatant, and adding 50mL of the galactose solution into the filtrate to obtain a reaction system;
(3) adjusting the pH value of the mixed system to 3.0 by using the hydrochloric acid solution, gradually changing the reaction system to be orange red, then placing the reaction solution at 25 ℃ for 12h or at 80 ℃ for 24h, centrifuging at 13000r/min, washing the precipitate by using double distilled water, and freeze-drying to obtain an amorphous nano-selenium sample for later use. Observing the nano-selenium sample suspension under a transmission electron microscope, and measuring and calculating the average particle size of the nano-selenium to be about 25 nm; the nano selenium particles are analyzed to be in an amorphous state by an X-ray diffractometer, and the amorphous nano particles are verified to be elemental selenium by photoelectron spectroscopy analysis.
(4) This example examines the antitumor bioactivity of amorphous nano-selenium, and the test results are shown in fig. 8.
Example 3
(1) Preparing 0.4mol/L sodium sulfite solution, 4g/L human serum albumin solution and 0.1mol/L hydrochloric acid solution;
(2) dispersing 0.7g of black selenium powder into 50mL of the sodium sulfite solution, then adding double distilled water until the total reaction volume is 250mL, reacting the mixed system at 95 ℃ for 6 hours, performing suction filtration to obtain a supernatant after the reaction is finished, and adding 50mL of the human serum albumin into the filtrate to obtain a reaction system;
(3) and (3) adjusting the pH value of the mixed system to 3.5 by using the hydrochloric acid solution, gradually changing the reaction system to be orange red, then placing the reaction solution at 25 ℃ for 12h or at 80 ℃ for 24h, centrifuging at 10000r/min, washing and precipitating by using double distilled water, and freeze-drying to obtain an amorphous nano selenium sample for later use. Observing the nano-selenium sample under a transmission electron microscope, and measuring and calculating the average particle size of the nano-selenium to be about 250 nm; the nano selenium particles are analyzed to be in an amorphous state by an X-ray diffractometer, and the amorphous nano particles are verified to be elemental selenium by photoelectron spectroscopy analysis.
(4) This example examines the antitumor bioactivity of amorphous nano-selenium, and the test structure is shown in fig. 12.
The foregoing embodiments illustrate the principles, principal features and advantages of the invention, and it will be understood by those skilled in the art that the invention is not limited to the foregoing embodiments, which are merely illustrative of the principles of the invention, and that various changes and modifications may be made therein without departing from the scope of the principles of the invention.
Claims (9)
1. The preparation method of the amorphous nano-selenium with bioactivity is characterized by comprising the following specific steps: adding a stabilizer solution into a selenosulfate solution, wherein the feeding molar ratio of selenosulfate to the stabilizer is 1: 2-1: 30, stirring and mixing uniformly, adding a dilute acid solution to adjust the pH value of a mixed system to be 2-6 so as to decompose selenosulfate, placing reaction liquid for 8-24 hours under the protection of nitrogen, then centrifugally washing to remove supernatant, drying precipitates to obtain amorphous nano selenium which is stable, has uniform particle size distribution and has anti-tumor activity, wherein the stabilizer is protein or polysaccharide, and the protein is bovine serum albumin, human serum albumin, bovine hemoglobin, human hemoglobin, pepsin or trypsin, and the polysaccharide is galactose or chitosan.
2. The method of claim 1, wherein the bioactive amorphous form of nano-selenium is selected from the group consisting of: the selenosulfate solution is an aqueous solution of soluble selenosulfates, and the soluble selenosulfates are one or more of sodium selenosulfate, potassium selenosulfate or zinc selenosulfate.
3. The method of claim 1, wherein the bioactive amorphous form of nano-selenium is selected from the group consisting of: the selenosulfate is from a commercial source, or the selenosulfate solution is freshly prepared according to the following method:
the method I comprises the following steps: adding 0.7-1.4 g of selenium powder into 0.02-1 mol/L of sulfite aqueous solution, wherein the sulfite is sodium sulfite, potassium sulfite or zinc sulfite, heating to 80-100 ℃ under the protection of nitrogen, heating under stirring for reflux reaction for 4-8 h, keeping the solution temperature at 80-100 ℃, closing and heating after the reaction is finished, naturally cooling the solution to 40-70 ℃, filtering unreacted selenium powder for recycling, and finally preparing selenosulfate solution;
method II: the method comprises the steps of dispersing selenite, sulfite and a reducing agent in deionized water according to a molar ratio of 1 (2-8) to (1-5), stirring and mixing uniformly at room temperature to obtain a selenosulfate solution, wherein the selenite is sodium selenite, potassium selenite or zinc selenite, the sulfite is sodium sulfite, potassium sulfite or zinc sulfite, and the reducing agent is sodium borohydride, mercaptoethanol, vitamin C, metallothionein or ascorbic acid.
4. The method of claim 1, wherein the bioactive amorphous form of nano-selenium is selected from the group consisting of: the diluted acid solution is hydrochloric acid solution, sulfuric acid solution or nitric acid solution, and the molar concentration of the diluted acid solution is 0.1-3 mol/L.
5. The method of claim 1, wherein the bioactive amorphous form of nano-selenium is selected from the group consisting of: the drying process of the precipitate adopts freeze drying or drying at 30-40 ℃.
6. The method of claim 1, wherein the bioactive amorphous form of nano-selenium is selected from the group consisting of: the concentration of the stabilizer solution is 0.5-5.0 g/L.
7. The method of claim 1, wherein the bioactive amorphous form of nano-selenium is selected from the group consisting of: in the preparation process of the amorphous nano selenium, the reaction solution is placed at room temperature for 12 hours or at 80 ℃ for 24 hours under the protection of nitrogen, and then is centrifugally washed at 10000-12000 rpm for 20-40 min to remove supernatant.
8. The use of the bioactive amorphous nano-selenium prepared by the method of any one of claims 1 to 7 in the preparation of an anti-tumor medicament.
9. An application of the bioactive amorphous nano-selenium in the preparation of a drug for inhibiting tumor cell proliferation, wherein the tumor cell is a human liver cancer cell (HepG 2), a human breast cancer cell (MCF-7), a human cervical cancer cell (HeLa), a human esophageal cancer cell (kyse 30) or a human lung cancer cell (A549).
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN115771883A (en) * | 2022-11-28 | 2023-03-10 | 淮阴工学院 | Application of protease A extracted from saccharomyces cerevisiae fermentation liquor in morphology control and stability influence synthesis of nano-selenium by chemical method |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN115771883A (en) * | 2022-11-28 | 2023-03-10 | 淮阴工学院 | Application of protease A extracted from saccharomyces cerevisiae fermentation liquor in morphology control and stability influence synthesis of nano-selenium by chemical method |
| CN115771883B (en) * | 2022-11-28 | 2024-02-23 | 淮阴工学院 | Application of protease A extracted from saccharomyces cerevisiae fermentation liquor in influence of morphology control and stability of nano-selenium synthesized by chemical method |
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Application publication date: 20201225 |