CN102285678A - Method for preparing cerium oxide nano particles and antioxidation use thereof - Google Patents
Method for preparing cerium oxide nano particles and antioxidation use thereof Download PDFInfo
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Abstract
The invention discloses a method for preparing cerium oxide nano particles and antioxidation use thereof and belongs to the field of biological nano materials. The method for preparing the cerium oxide nano particles comprises: adding glacial acetic acid into aqueous solution of a cerate and sodium acetate, uniformly stirring and mixing, heating the mixed solution for 5 to 60 hours, centrifuging, washing and drying an obtained yellow precipitate, and obtaining cerium oxide nano particles. Meanwhile, based on the subunit desorption and re-polymerization of proteins, the cerium oxide nano particles are filled into cavities of apoferritin which is a spherical cavity protein by controlling the opening and closing of the shell of the spherical protein, and thus, the biocompatible nano antioxidant is obtained. The method can improve the biocompatibility of the cerium oxide nano particles, lower the cytotoxicity of the cerium oxide nano particles and improve the antioxidant activity of the cerium oxide nano particles obviously.
Description
Technical field
The present invention relates to the biological nano material.The preparation method of cerium oxide nanoparticles and anti-oxidant application thereof specifically.
Background technology
Active oxygen is meant the oxygen containing high reaction activity molecule of a class that chemical property is active in the organism, oxidation capacity is very strong, comprises ultra-oxygen anion free radical, hydroxyl radical free radical, hydrogen peroxide etc.All multifactor in the external environment, as solar exposure, ultraviolet ray, electromagnetic radiation, environmental pollution, drug abuse, smoking excessive drinking and stress are excessive etc. can cause that all active oxygen produces.An amount of active oxygen be earn a bare living healthy necessary, in case yet active oxygen is excessive, will cause lipid peroxidation, the protein damage, the DNA chain break, and cause aging or ageing-related degenerative disease such as cancer, cardiovascular disorder, cataract, sacroiliitis and Parkinsonism etc., thereby the health of serious threat body.
In recent years, many research just is being devoted to seek the natural component with strong anti-oxidant activity from the abundant animal of nature, plant, and polyphenol and the flavonoid having found extensively to be present in various vegetables, fruit, tea or the red wine can be used as antioxidant, effectively stop free radical lock reaction.Yet the antioxygenation of these natural components is compared with various antioxidases, has easy consumption, shortcomings such as can't regenerating and recycle.The world today, the nanotechnology of develop rapidly provides brand-new thinking for the research and development of novel antioxidant.Up to the present, comprise nanometer platinum, nanometer selenium, nano-cerium oxides etc. all have been proved at interior many nano particles has free radical scavenging activity.Yet the ubiquitous problem of nano material itself---biological safety but can not be ignored.
Ferritin (ferritin) is ubiquitous a kind of natural ferruginous globular protein in the organism, and this albumen is that this is dimerous by the oxide nano particles of the iron in globular protein shell and the shell.The globular protein shell is made up of 24 subunits, and its external diameter is 12nm, and the diameter of the spherical hollow space in the shell is 8nm.Contain 8 hydrophilic channels and 6 hydrophobic channels on the globular protein shell, these passages can allow medium and small ion of external environment or molecule to enter spherical hollow space inside.The ferritin that has removed iron nuclear in the shell abbreviates cavity ferritin (apoferritin) as, the spherical hollow space structure of the 8nm that the cavity ferritin is had, as the synthetic template of a kind of natural, superior nano particle, be widely used in Pd, Ag, Ni, Co, the preparation of small particle size nano particles such as CdS and ZnSe.
Summary of the invention
This preparation method that a kind of cerium oxide nanoparticles is provided, its concrete steps comprise:
In the aqueous solution of cerium salt and sodium-acetate, add Glacial acetic acid, and stirring and evenly mixing.This is afterwards with this mixed solution hydrothermal treatment consists 5～60h.At last that the gained yellow mercury oxide is centrifugal, washing and dry make cerium oxide nanoparticles.
In the above-mentioned steps, preferred condition is: with 2.74～5.48g (NH
4)
2Ce (NO
3)
6And 10～20g CH
3COONa is dissolved in 50～100ml deionized water, adds 10～50ml Glacial acetic acid then in this solution, and at room temperature stirs 1～5h.After this this mixed solution is transferred in the polytetrafluoroethyllining lining, after the sealing of stainless steel hydro-thermal still, places 200～300 ℃ of baking ovens to heat 8～24h.At last with the gained yellow mercury oxide centrifugal (1000～10000g, 10～120min) and repeatedly clean with deionized water and ethanol, dried overnight in 60 ℃ of baking ovens makes cerium oxide nanoparticles subsequently.
The present invention also provides the preparation method of a kind of biocompatibility nano-anti-oxidation agent, it is characterized in that, the cerium oxide nanoparticles that makes is mixed with apoferritin solution, add pH to 1.5～3.5 of slow acid regulator solution then, so that the subunit dissociation of apoferritin.In this solution, slowly drip alkaline solution after this again, so that the pH value of solution slowly rises to 7.0～9.0.The cerium oxide nanoparticles that finally obtains the apoferritin parcel after separation and purification is (hereinafter to be referred as AFt-CeO
2).
Cerium oxide nanoparticles is mixed with apoferritin solution, and wherein, albumen is 1: 100～1: 10000 with the ratio of the volumetric molar concentration of cerium.PH to 1.5～3.5 that add the slow acid regulator solution then, and under this pH, continue to stir 10～120min.In this solution, slowly drip alkaline solution after this again,, continue magnetic agitation 1～2h at room temperature so that the pH value of solution slowly rises to 7.0～9.0.Behind the 2h, centrifugal (8000～12500g, 4 ℃～25 ℃, 10～60min), and with the supernatant liquor collected through gel permeation chromatography (as Sephadex G-25 column chromatography) purifying, at last with the AFt-CeO behind the purifying
2The solution freeze-drying concentrates.
The median size of the cerium oxide nanoparticles that the present invention makes is generally 4～5nm less than 8nm.
The cerium oxide nanoparticles of the albumen parcel of the present invention's preparation is (hereinafter to be referred as AFt-CeO
2), learn that through the analysis of free radical detection kit its free radical scavenging activity has concentration dependent.Along with the increase of cerium oxide concentration, AFt-CeO
2Radical scavenging activity more and more stronger.And the radical scavenging activity of this nano particle and albumen composition is about 7 times of cerium oxide nanoparticles of no albumen parcel, even is higher than the activity of the natural scavenger SOD (superoxide-dismutase) of same protein concentration.In addition, intracellular anti-oxidant experiment further confirms, after the apoferritin parcel, and AFt-CeO
2The cerium oxide nanoparticles that is higher than no albumen parcel at intracellular free radical scavenging activity far away.
The cerium oxide nanoparticles of the albumen parcel of the present invention's preparation not only can improve the free radical scavenging activity of cerium oxide, but also the cytotoxicity of cerium oxide is reduced greatly.When the concentration of cerium was higher than 250uM, the cerium oxide nanoparticles cytotoxicity of no albumen parcel sharply increased.And for AFt-CeO
2Even the concentration of cerium does not still have significant cytotoxicity in 250～1000uM scope the time.
The cerium oxide nanoparticles of the albumen parcel of the present invention preparation, mainly the mode of the cell endocytic by the clathrin mediation enters cell, and the mode that this mode that enters cell and natural ferritin or apoferritin enter cell is similar.The cerium oxide nano that does not have the albumen parcel then mainly enters cell in the mode of giant cell drink.
The present invention has following advantage:
1, utilize hydrothermal method to synthesize the cerium oxide nanoparticles that median size is about 4.5nm.This particle shape rule, uniform particle diameter, good dispersity.
2, utilize subunit dissociation and polymeric method that above-mentioned cerium oxide nanoparticles is loaded in the spherical hollow space of apoferritin into.Confirm the AFt-CeO that finally obtains through the electron energy loss spectroscopy (EELS) analysis
2The average valence of middle cerium is+3.3, and this valence state (+4) than cerium in the cerium oxide of no albumen parcel is low, and the reduction of the valence state of this cerium will help AFt-CeO
2The raising of anti-oxidant activity.
3, the AFt-CeO for preparing
2In test kit experiment and intracellular free radical scavenging experiment, all show very superior anti-oxidant activity.The test kit experiment confirm, AFt-CeO
2Free radical scavenging activity be about 7 times of free radical scavenging activity of the cerium oxide of no albumen parcel, be about active 3.5 times of SOD of same protein concentration.The intracellular free radical scavenging experiment confirm of HepG2, AFt-CeO
220 times of cerium oxide that are about no albumen parcel at intracellular free radical scavenging activity.
4, cytotoxicity experiment confirms, when the concentration of cerium during greater than 250uM, the cerium oxide nanoparticles that no albumen wraps up has begun to show more intense cytotoxicity, yet for AFt-CeO
2The mixture of this albumen and nano particle is not even during between 250～1000uM, still have significant cytotoxicity in the concentration of cerium.
5, the cell endocytic experiment further confirms AFt-CeO
2Mainly the cell endocytic approach by the clathrin mediation enters cell, and the cerium oxide nanoparticles of not having the albumen parcel then mainly enters cell in the mode of giant cell drink.
Description of drawings
The preparation route map of the cerium oxide nanoparticles of Fig. 1 .Apoferritin parcel;
Fig. 2. the transmission electron microscope photo (A) of the cerium oxide nanoparticles of embodiment 1 preparation and particle diameter statistics (B);
Fig. 3. the low resolution transmission electron microscope photo (A) of the cerium oxide nanoparticles of the albumen parcel of embodiment 2 preparations, high-resolution-ration transmission electric-lens photo (B) and EDX (C);
Fig. 4. the cytotoxicity analysis of the cerium oxide nanoparticles of the cerium oxide nanoparticles of albumen parcel and no albumen parcel;
Fig. 5. utilize test kit to detect AFt-CeO
2Radical scavenging activity: (A) AFt-CeO
2The concentration of removing free radical relies on curve.(B) comparison of different substances radical scavenging activity.AFt is apoferritin among the figure, the protein concentration of used AFt and SOD and used AFt-CeO
2In protein concentration identical.And used CeO
2The cerium concentration of nano particle and AFt-CeO
2In the concentration of cerium identical;
Fig. 6 .AFt-CeO
2In intracellular free radical scavenging experiment.
Embodiment
The invention will be further described below in conjunction with embodiment, but the present invention not merely is limited among the embodiment as described below.
The cerium oxide nanoparticles of embodiment 1, Hydrothermal Preparation uniform particle diameter.
Take by weighing 2.74g (NH
4)
2Ce (NO
3)
6And 10g CH
3COONa is dissolved in the 70ml deionized water, adds the 10ml Glacial acetic acid then in this solution, and at room temperature stirs 1h.After this this mixed solution is transferred in the polytetrafluoroethyllining lining, after the sealing of stainless steel hydro-thermal still, places 220 ℃ of baking ovens to heat 12h.Centrifugal (6000g 10min) and with deionized water and ethanol repeatedly cleans, subsequently dried overnight in 60 ℃ of baking ovens with the gained yellow mercury oxide at last.
The cerium oxide nanoparticles of embodiment 2, Hydrothermal Preparation uniform particle diameter.
Take by weighing 5.48g (NH
4)
2Ce (NO
3)
6And 20g CH
3COONa is dissolved in the 140ml deionized water, adds the 20ml Glacial acetic acid then in this solution, and at room temperature stirs 1h.After this this mixed solution is transferred in the polytetrafluoroethyllining lining, after the sealing of stainless steel hydro-thermal still, places 220 ℃ of baking ovens to heat 12h.Centrifugal (10000g 20min) and with deionized water and ethanol repeatedly cleans, subsequently dried overnight in 60 ℃ of baking ovens with the gained yellow mercury oxide at last.
The cerium oxide nanoparticles of embodiment 3, Hydrothermal Preparation uniform particle diameter.
Take by weighing 1.63g Ce (NO
3)
3And 10g CH
3COONa is dissolved in the 70ml deionized water, adds the 10ml Glacial acetic acid then in this solution, and at room temperature stirs 1h.After this this mixed solution is transferred in the polytetrafluoroethyllining lining, after the sealing of stainless steel hydro-thermal still, places 220 ℃ of baking ovens to heat 24h.At last gained is precipitated that centrifugal (10000g 20min) and with deionized water and ethanol repeatedly cleans, subsequently dried overnight in 60 ℃ of baking ovens.
In the above-mentioned experiment, Ce (NO
3)
3Also can replace with other inorganic cerium salt.
Get 5ml apoferritin solution and cerium oxide nanoparticles powder mixes, albumen is 1: 5000 with the ratio of the volumetric molar concentration of cerium.Utilize the pH to 2.0 of the slow regulator solution of HC1 of 1M then, and under this pH, continue to stir 30min.In this solution, slowly drip the NaOH of 1M after this again, so that the pH value of solution slowly rises to 8.0 from 2.0.When the pH value rises to after 8.0, continue magnetic agitation 2h at room temperature.Behind the 2h, centrifugal (12500g, 4 ℃, 20min), and with the supernatant liquor collected through Sephadex G-25 pillar purifying, at last with the AFt-CeO behind the purifying
2The solution freeze-drying concentrates.
The cytotoxicity of the cerium oxide nanoparticles of albumen parcel of the present invention detects.
Utilize conventional cytotoxicity detection method (mtt assay) to detect AFt-CeO
2Cytotoxicity.Final experimental result is as shown in Figure 4: when the concentration of cerium during greater than 250uM, the cerium oxide nanoparticles of no albumen parcel has begun to show more intense cytotoxicity, yet for AFt-CeO
2The mixture of this albumen and nano particle is not even during between 250～1000uM, still have significant cytotoxicity in the concentration of cerium.
Utilize the anti-oxidant activity of the cerium oxide nanoparticles of free radical detection kit analysis albumen parcel of the present invention.
Utilization is analyzed AFt-CeO available from the superoxide-dismutase detection kit of Japanese colleague's chemistry institute
2Free radical scavenging activity, and and apoferritin, CeO
2And the radical scavenging activity of SOD compares, and experimental procedure is carried out according to the operational manual of this test kit fully.Final experimental result is as shown in Figure 5: AFt-CeO
2Free radical scavenging activity have the significant concn dependence; AFt-CeO
2Free radical scavenging activity be about 7 times of free radical scavenging activity of the cerium oxide of no albumen parcel, be about active 3.5 times of SOD of same protein concentration.
The cerium oxide nanoparticles of albumen parcel of the present invention is at intracellular anti-oxidant activity.
In two 6 orifice plates, make the initial cell density in each hole of two boards identical the HepG2 cell inoculation.After being cultured to cell density in each hole then and being about 70%, in each hole, add the CeO of different amounts
2Perhaps AFt-CeO
2(final concentration of cerium changes in 0～200uM scope in each hole), and hatched altogether 12 hours with the HepG2 cell.After 12 hours, clean each hole three times, to remove the free CeO that does not enter cell with PBS
2Perhaps AFt-CeO
2In each hole, add then and contain 600 μ M H
2O
2DMEM nutrient solution (containing 10% new-born calf serum) 2ml and continue to cultivate 12 hours.After 12 hours, PBS cleans each hole three times, adds DMEM nutrient solution (containing 10% the new-born calf serum) 2ml that contains 20 μ M DCFH-DA then in each hole, and pair cell dyes half an hour.After half an hour, clean each hole three times with PBS, collecting cell is also used the fluorescence intensity of cell in each hole of flow cytometry analysis then.Judge the content of intracellular reactive oxygen species by the height of fluorescence intensity.Fluorescence intensity is high more, illustrates that intracellular active o content is many more.As can be seen from Figure 6, AFt-CeO
2With CeO
2The removing of active oxygen all has the concentration dependence in the pair cell, but the removing ability of active oxygen will be better than the latter far away in the former pair cell.AFt-CeO
2The active oxygen of disposing cell interior 50% only needs the AFt-CeO of 6.8 μ M
2(6.8 μ M refer to AFt-CeO
2In the concentration of cerium), and CeO
2The intracellular reactive oxygen of disposing same amount then needs the CeO of 132 μ M
2
Claims (8)
1. the preparation method of a cerium oxide nanoparticles, its step comprises:
1) in the aqueous solution of cerium salt and sodium-acetate, adds Glacial acetic acid, stirring and evenly mixing;
2) with above-mentioned mixed solution hydrothermal treatment consists 5～60h, obtain yellow mercury oxide;
3) yellow mercury oxide is centrifugal, washing and dry makes cerium oxide nanoparticles.
2. the method for claim 1 is characterized in that, step 1) specifically comprises: with 2.74～5.48g (NH
4)
2Ce (NO
3)
6And 10～20g CH
3COONa is dissolved in 50～100ml deionized water, adds 10～50ml Glacial acetic acid then in this solution, and at room temperature stirs 1～5h.
3. the method for claim 1 is characterized in that step 2) specifically comprise: mixed solution is transferred in the polytetrafluoroethyllining lining, after the sealing of stainless steel hydro-thermal still, places 200～300 ℃ of baking ovens to heat 8～24h.
4. the method for claim 1 is characterized in that, step 3) specifically comprises: the gained yellow mercury oxide is centrifugal, and repeatedly clean with deionized water and ethanol, and dried overnight in 60 ℃ of baking ovens subsequently.
5. the preparation method of biocompatibility nano-anti-oxidation agent, it is characterized in that, the cerium oxide nanoparticles of method preparation is according to claim 1 mixed with apoferritin solution, pH to 1.5～3.5 that add the slow acid regulator solution then, so that the subunit dissociation of apoferritin, and then in this solution, slowly drip alkaline solution, so that the pH value of solution slowly rises to 7.0～9.0, after separation and purification, finally obtain the cerium oxide nanoparticles of apoferritin parcel.
6. method as claimed in claim 5 is characterized in that, cerium oxide nanoparticles is mixed with apoferritin solution, and wherein, albumen is 1: 100～1: 10000 with the ratio of the volumetric molar concentration of cerium.
7. method as claimed in claim 5 is characterized in that, when the mixing solutions of cerium oxide nanoparticles and apoferritin is used acid for adjusting pH, preferentially selects hydrochloric acid for use, concentration 0.1～5M.
8. method as claimed in claim 5 is characterized in that, when the mixing solutions of cerium oxide nanoparticles and apoferritin adds alkali adjusting pH, preferentially selects sodium hydroxide for use, concentration 0.1～5M.
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Cited By (8)
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|---|---|---|---|---|
| CN102849774A (en) * | 2012-01-10 | 2013-01-02 | 浙江理工大学 | Method for preparing nanometer cerium oxide by hydrothermal method |
| CN103536625A (en) * | 2013-09-27 | 2014-01-29 | 安徽师范大学 | Nanometer cerium oxide composite and preparation method thereof as well as antioxidant |
| CN104479321A (en) * | 2014-11-20 | 2015-04-01 | 苏州新区佳合塑胶有限公司 | Anti-oxidative ABS/PC plastic for automobile instruments/meters |
| CN106913906A (en) * | 2015-12-24 | 2017-07-04 | 中国科学院上海硅酸盐研究所 | A kind of antioxidation biology coating and preparation method thereof |
| CN108992712A (en) * | 2018-08-14 | 2018-12-14 | 上海市第六人民医院东院 | A kind of cerium oxide nano nerve trachea composition, nerve trachea and its preparation method and application |
| CN112295515A (en) * | 2020-11-30 | 2021-02-02 | 江南大学 | Preparation method of zinc oxide/cerium oxide hollow microspheres with inverted blueberry-shaped structures |
| CN113144287A (en) * | 2021-04-22 | 2021-07-23 | 南开大学 | Cerium oxide-based nano material for bone defect repair, preparation method thereof and cerium oxide-based composite bone scaffold |
| CN114901594A (en) * | 2019-12-26 | 2022-08-12 | 东丽株式会社 | Cerium oxide nanoparticles, dispersion, oxidizing agent, antioxidant, and method for producing cerium oxide nanoparticles |
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Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102849774A (en) * | 2012-01-10 | 2013-01-02 | 浙江理工大学 | Method for preparing nanometer cerium oxide by hydrothermal method |
| CN103536625A (en) * | 2013-09-27 | 2014-01-29 | 安徽师范大学 | Nanometer cerium oxide composite and preparation method thereof as well as antioxidant |
| CN103536625B (en) * | 2013-09-27 | 2016-01-06 | 安徽师范大学 | A kind of nanometer cerium oxide composite and preparation method thereof, antioxidant |
| CN104479321A (en) * | 2014-11-20 | 2015-04-01 | 苏州新区佳合塑胶有限公司 | Anti-oxidative ABS/PC plastic for automobile instruments/meters |
| CN106913906A (en) * | 2015-12-24 | 2017-07-04 | 中国科学院上海硅酸盐研究所 | A kind of antioxidation biology coating and preparation method thereof |
| CN106913906B (en) * | 2015-12-24 | 2020-03-17 | 中国科学院上海硅酸盐研究所 | Antioxidant biological coating and preparation method thereof |
| CN108992712A (en) * | 2018-08-14 | 2018-12-14 | 上海市第六人民医院东院 | A kind of cerium oxide nano nerve trachea composition, nerve trachea and its preparation method and application |
| CN114901594A (en) * | 2019-12-26 | 2022-08-12 | 东丽株式会社 | Cerium oxide nanoparticles, dispersion, oxidizing agent, antioxidant, and method for producing cerium oxide nanoparticles |
| CN112295515A (en) * | 2020-11-30 | 2021-02-02 | 江南大学 | Preparation method of zinc oxide/cerium oxide hollow microspheres with inverted blueberry-shaped structures |
| CN112295515B (en) * | 2020-11-30 | 2022-03-25 | 江南大学 | Preparation method of zinc oxide/cerium oxide hollow microspheres with inverted blueberry-shaped structures |
| CN113144287A (en) * | 2021-04-22 | 2021-07-23 | 南开大学 | Cerium oxide-based nano material for bone defect repair, preparation method thereof and cerium oxide-based composite bone scaffold |
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