CN108529681A - Hollow manganese dioxide nano particle and its preparation method and application - Google Patents
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Abstract
The present invention provides hollow manganese dioxide nano particles and its preparation method and application.In the method for the invention, silver nanoparticle cube is prepared first, then with silver nanoparticle cube is template, using the hollow manganese dioxide nano particle of template one-step synthesis, has the characteristics that preparation process is simple；Meanwhile having many advantages, such as stable property, size and structure-controllable by the hollow manganese dioxide nano particle obtained by the method for the present invention, and can be applied in fields such as pharmaceutical carrier, oncotherapy and magnetic resonance imagings.
Description
Technical field
The present invention relates to field of nanometer material technology, in particular to hollow manganese dioxide nano particle and preparation method thereof
And application.
Background technology
Manganese dioxide is a kind of important transition metal oxide, since it is with good redox characteristic, thus
It all has been obtained for being widely applied in the multinomial field such as battery material.
Nano-manganese dioxide also has special nano effect other than the characteristic with manganese dioxide, thus it is applied
Further extension has been obtained, such as：Manganese dioxide nano particle has strong oxidizing property in acid condition, can be had in vivo
There is the glutathione of reproducibility to degrade；Or oxygen is generated with internal hydroperoxidation, to which controllable entity tumor exists
Acidity, anoxic and redox microenvironment, the effect of chemotherapy, radiotherapy or optical dynamic therapy can be improved；Meanwhile by manganese dioxide
The manganese ion degraded and discharged can also realize magnetic resonance imaging, thus manganese dioxide nano particle is examined in nanometer medicine, disease
Disconnected and therapeutic field of tumor is with important application prospects；Further, in having due to hollow manganese dioxide nano particle
Empty porous structure is, it can be achieved that drug high-efficient carrier and targeted delivery, thus it is flat to can be used as a kind of multi-functional tumour diagnosis and treatment nanometer
Platform.
But be but rarely reported about the research of the preparation method of hollow manganese dioxide nano particle report at present, to
Limit hollow manganese dioxide nano particle further applying in tumour diagnosis and treatment field.
In view of this, special propose the present invention.
Invention content
The first object of the present invention is to provide a kind of preparation method of hollow manganese dioxide nano particle, the method
In, silver nanoparticle cube is prepared first, then with silver nanoparticle cube be template, using the hollow manganese dioxide nano of template one-step synthesis
Particle has many advantages, such as that preparation process is simple, and obtained hollow manganese dioxide nano grain structure is stablized.Its specific reaction is former
Reason is：
MnO4+3Ag+4H++3Cl=MnO2+3AgCl+2H2O
The second object of the present invention is to provide a kind of hollow manganese dioxide nano particle, the hollow nano-manganese dioxide
Particle is prepared by the method for the present invention, has many advantages, such as stable property, size and structure-controllable, and can be carried in drug
Body promotes oncotherapy effect and realizes the application of the fields such as magnetic resonance imaging.
Third object of the present invention is to provide the application of the hollow manganese dioxide nano particle；The present invention is hollow to be received
Rice manganese dioxide grain structure is stable and has multiple functions, and can further apply nano-medicament carrier, oncotherapy
In medicament and magnetic resonance imaging contrast.
In order to realize that the above-mentioned purpose of the present invention, spy use following technical scheme：
A kind of preparation method of hollow manganese dioxide nano particle, described method includes following steps：
First, silver nanoparticle cube is prepared using sulfide-polyol reduction method；Then, it is template with silver nanoparticle cube,
And potassium permanganate is restored in the dispersion liquid containing silver nanoparticle cube, obtain hollow manganese dioxide nano particle.
Optionally, in the present invention, steps are as follows for the preparation method：
(1) silver nanoparticle cube is prepared：
1. after polyalcohol agitating and heating, sulfide-polyhydric alcohol solutions are added, and be stirred；
2. being separately added into inorganic acid-polyhydric alcohol solutions and polyvinylpyrrolidone-into step 1. acquired solution
Polyhydric alcohol solutions continue to be stirred；
3. silver salt-polyhydric alcohol solutions are added into step 2. acquired solution, continue to be stirred to react；
4. 3. step is removed into supernatant after the centrifugation of gained mixed solution, and by the sediment undergoes washing being collected into get to
Then silver nanoparticle cube is scattered in solution, silver nanoparticle cube dispersion liquid is obtained；
(2) hollow manganese dioxide nano particle preparation：
1. silver nanoparticle cube dispersion liquid is stirred with potassium permanganate；
2. polyallylamine hydrochloride solution is added into step 1. gained mixed solution, continue to be stirred；
3. by supernatant is removed after step 2. acquired solution centrifugation to get hollow manganese dioxide nano particle.
Optionally, in the present invention, the sulfide is one in vulcanized sodium, NaHS, potassium sulfide or potassium bisulfide
Kind or several mixtures.
Optionally, in the present invention, the polyalcohol is in ethylene glycol, 1,2-PD, 1,3-PD or glycerine
One or more of mixtures；
Optionally, in the present invention, the inorganic acid is the mixture of one or more of hydrochloric acid, nitric acid or sulfuric acid；
Optionally, in the present invention, the silver salt is the mixed of one or more of silver nitrate, Silver Trifluoroacetate or silver acetate
Close object.Optionally, described that the sediment undergoes washing being collected into specially is respectively adopted to acetone, the progress of second alcohol and water in the present invention
Cleaning.
Meanwhile the present invention also provides a kind of hollow manganese dioxide nano particle, the hollow manganese dioxide nano particles
It is prepared by the method for the invention.
Optionally, in the present invention, the hollow manganese dioxide nano particle is hollow porous structure, and can be used as and receive
Rice pharmaceutical carrier, the drug or ancillary drug for the treatment of cancer, or used as magnetic resonance imaging contrast.
Further, the application the present invention also provides the hollow manganese dioxide nano particle in pharmaceutical carrier.
Further, it is being prepared for the application in treating cancer drug or ancillary drug the present invention also provides described.
Further, the present invention also provides the hollow manganese dioxide nano particles to be answered in magnetic resonance imaging contrast
With.
Compared with prior art, beneficial effects of the present invention are：
(1) it in the present invention, uses silver cube for template, hollow manganese dioxide nano is synthesized by a stage reduction method
Grain, preparation method simple and effective, and remove template without additional step, you can prepare hollow the two of size and structure-controllable
Manganese oxide nano granule；
(2) preparation method of the present invention is simple and easy to do, and hollow manganese dioxide nano is prepared convenient for extensive, industrialized
Grain；
(3) hollow cavity of hollow manganese dioxide nano particle can be used for drug loading, thus can realize the efficient of drug
The internal transmission of targeting；
(4) hollow manganese dioxide nano particle can with the hydroperoxidation in tumor tissues and generate oxygen, can be with
The hydrogen ion and glutathione in tumor tissues are consumed, so as to anoxic, acidity existing for modulate tumor and redox micro-loop
Oncotherapy effect can be improved in border；
(5) manganese ion that hollow manganese dioxide nano particle is released by degradation, can also realize magnetic resonance imaging,
Thus hollow manganese dioxide nano particle is with important application prospects in nanometer medicine, medical diagnosis on disease and therapeutic field of tumor.
Description of the drawings
In order to more clearly explain the embodiment of the invention or the technical proposal in the existing technology, to embodiment or will show below
There is attached drawing needed in technology description to be briefly described.
Fig. 1 is the transmission electron microscope picture of silver nanoparticle cube；
Fig. 2 is the transmission electron microscope picture of hollow manganese dioxide nano particle；
Fig. 3 is the oxygen release profiles of hollow manganese dioxide nano particle.
Specific implementation mode
Embodiment of the present invention is described in detail below in conjunction with embodiment, but those skilled in the art will
Understand, the following example is merely to illustrate the present invention, and is not construed as limiting the scope of the invention.It is not specified in embodiment specific
Condition person carries out according to conventional conditions or manufacturer's recommended conditions.Reagents or instruments used without specified manufacturer is
The conventional products that can be obtained by commercially available purchase.
Since the preparation method of existing nano-manganese dioxide is difficult to control effectively to the size and structure of nano particle,
To limit application of the nano-manganese dioxide in biological medicine, thus, primary and foremost purpose of the invention is just to provide a kind of energy
Enough control the preparation method of the hollow nano-manganese dioxide of nanoparticle size and structure, the method for the present invention basic step and reaction
Mechanism is as follows：First, it assists polyol reduction method to prepare silver nanoparticle cube by sulfide, then with silver nanoparticle cube is template,
Polyallylamine hydrochloride is stabilizer, and potassium permanganate is oxidant, to look unfamiliar long manganese dioxide shell in silver nanoparticle cubic table,
In the process, silver nanoparticle cube is aoxidized, and is formed chlorination silver nano-grain and is removed by centrifugation, products therefrom is hollow two
Manganese oxide nano granule.
Further, specific preparation process of the invention can be as follows：
(1) silver nanoparticle cube is prepared：
1. after polyalcohol agitating and heating, sulfide-polyhydric alcohol solutions are added, and be stirred；
In this step, first polyalcohol can be added in round-bottomed flask, then, the magnetic force in 140~150 DEG C of oil bath
After the temperature of polyalcohol reaches oil bath temperature under agitation, sulfide-polyhydric alcohol solutions are added in agitating and heating, after
It is continuous to be stirred 2~10min；
Further, the polyalcohol is ethylene glycol, diethylene glycol, 1,2-PD, 1,3-PD or glycerine
One or more of mixed solution；Preferably, in the present invention, the polyalcohol is ethylene glycol, and the ethylene glycol solution
It may further be used in other steps of silver nanoparticle cube preparation；
Meanwhile the sulfide is the mixed of one or more of vulcanized sodium, NaHS, potassium sulfide or potassium bisulfide
Close object, it is preferred that the sulfide is NaHS；
Meanwhile the mixture that the inorganic acid is one or more of hydrochloric acid, nitric acid or sulfuric acid, it is preferred that the nothing
Machine acid is hydrochloric acid；
Meanwhile the mixture that the silver salt is one or more of silver nitrate, Silver Trifluoroacetate or silver acetate, preferably
, the silver salt is Silver Trifluoroacetate；A concentration of 3~8mM of sulfide in the sulfide-polyhydric alcohol solutions；Meanwhile institute
The volume ml ratio for stating polyalcohol and sulfide-polyhydric alcohol solutions is (1~5)：(0.02~0.06)；
2. being separately added into hydrochloric acid-polyhydric alcohol solutions and polyvinylpyrrolidone-polyalcohol into step 1. solution
Solution continues to be stirred 2~10min；
In this step, in described two kinds of solution, polyalcohol used is ethylene glycol, 1,2-PD, 1,3-PD
Or the mixed solution of one or more of glycerine；Preferably, the polyalcohol is ethylene glycol；
Meanwhile in this step, a concentration of 3~8mM of hydrochloric acid-polyhydric alcohol solutions, hydrochloric acid-polyhydric alcohol solutions and step are 1.
The ratio of the volume ml of middle polyalcohol is (0.5~1)：(3~5)；
And/or in this step, a concentration of 20~50mg/ml of polyvinylpyrrolidone-polyhydric alcohol solutions, polyethylene
The ratio of the volume ml of base pyrrolidones-polyhydric alcohol solutions and hydrochloric acid-polyhydric alcohol solutions is (1.25~1.75)：(0.5
~1)；
3. Silver Trifluoroacetate-polyhydric alcohol solutions are added into step 2. acquired solution, continue to be stirred to react；
In this step, in the Silver Trifluoroacetate-polyhydric alcohol solutions, the polyalcohol be ethylene glycol, 1,2-PD,
The mixed solution of one or more of 1,3-PD or glycerine；Preferably, the polyalcohol is ethylene glycol；
Meanwhile in this step, a concentration of 240~282mM of the Silver Trifluoroacetate-polyhydric alcohol solutions, trifluoracetic acid
Silver-polyhydric alcohol solutions and step 1. in the ratio of volume ml of polyalcohol be (0.4~1.2)：(3~5)；
Meanwhile 3. step needs to be stirred to react 45~60min, during the reaction, need to keep the temperature under the conditions of oil bath anti-
It answers, reaction temperature is controlled at 140~150 DEG C；
4. 3. step is removed into supernatant after the centrifugation of gained mixed solution, and by the sediment undergoes washing being collected into get to
Silver nanoparticle cube, and be scattered in solution, obtain silver nanoparticle cube dispersion liquid；
In this step, be by step 3. gained comprising target silver nanoparticle cube mixed solution speed conditions be 1000~
Under conditions of 1200r/m, 10~15min is centrifuged；Then, supernatant is removed, respectively with acetone, ethyl alcohol and ultra-pure water to collecting
Sediment cleaned；Finally, the silver nanoparticle cube after purification is dispersed in ultra-pure water, it is spare；
Wherein, the ultra-pure water and step 1. in the ratio of volume ml of polyalcohol be (1~2)：(1~2)；
The step of prepared by silver nanoparticle cube (1) mainly utilizes sulfide to cooperate with polyalcohol, and the side by restoring silver salt
Method prepares silver nanoparticle cube, and the template that prepared silver nanoparticle cube is prepared as hollow manganese dioxide in a subsequent step is come
It uses.
(2) hollow manganese dioxide nano particle preparation：
1. silver nanoparticle cube dispersion liquid is stirred with potassium permanganate；
This step can preferably carry out under the conditions of magnetic agitation, and be stirred 3~5min；
Wherein, the ratio of the quality milligram number of the volume ml of silver nanoparticle cube dispersion liquid used and potassium permanganate is (5
~10)：(21~25)；
2. polyallylamine hydrochloride solution is added into step 1. gained mixed solution, continue to be stirred 20~30min；
In this step, the polyallylamine hydrochloride solution is preferably acrylamide salts acid salt aqueous solution；Further,
A concentration of 30~50mg/ml of the acrylamide salts acid salt aqueous solution；Meanwhile acrylamide salts acid salt aqueous solution and silver nanoparticle
The ratio of the volume ml of cube dispersion liquid is (0.5~1)：(5~10)；
3. by supernatant is removed after step 2. acquired solution centrifugation to get hollow manganese dioxide nano particle；
It is by acquired solution under 8500~9000rpm centrifugal conditions, then 10~15min of centrifugation is removed in this step
Supernatant is removed, gained precipitation is collected to get the hollow manganese dioxide nano particle of product.
The step of hollow manganese dioxide nano particle preparation (2) is the surface reduction permanganic acid in silver nanoparticle cube template
Potassium so that manganese dioxide can look unfamiliar length in silver nanoparticle cubic table, and obtains hollow manganese dioxide particle；Meanwhile
In this reduction process, the silver nanoparticle cube as template can be aoxidized, and is formed chlorination silver nano-grain and is removed by centrifugation, because
And the step of being removed to avoid further template, the efficiency of preparation is improved, reaction principle is as follows：MnO4+3Ag+4H++3Cl
=MnO2+3AgCl+2H2O。
There are following features by the hollow nano-manganese dioxide particle obtained by the method for the present invention：
(1) manganese dioxide nano particle is hollow porous structure, can be used as efficient nano-medicament carrier；Thus, this hair
Bright hollow manganese dioxide nano can be further used as nano-medicament carrier and apply；
(2) manganese dioxide nano particle can with the hydroperoxidation in tumor tissues and generate oxygen, can also consume
Hydrogen ion in tumor tissues and glutathione can be improved swollen so as to modulate tumor anoxic, acidity and redox microenvironment
Tumor treatment effect；Thus, the hollow nano-manganese dioxide particle of the present invention can also be further used for preparing the drug for the treatment of cancer or
Person's ancillary drug；
(3) magnetic resonance imaging may be implemented in the manganese ion discharged by manganese dioxide nano pellet degradation；Thus, the present invention
Hollow nano-manganese dioxide particle can also be further used as the contrast agent of magnetic resonance imaging and use.
Embodiment 1
(1) preparation of silver nanoparticle cube
1. 5mL ethylene glycol is added in 100mL round-bottomed flasks, it is placed in magnetic agitation in 150 DEG C of oil bath and heats.It waits for
After ethylene glycol temperature reaches 150 DEG C, NaHS-ethylene glycol solution of a concentration of 3mM of 0.06mL is injected immediately；
2. after 2min, the hydrochloric acid-ethylene glycol solution and a concentration of 20mg/mL of 1.25mL of 0.5mL a concentration of 3mM is added
Polyvinylpyrrolidone-ethylene glycol solution；
3. after 2min, Silver Trifluoroacetate-ethylene glycol solution of a concentration of 282mM of 0.4mL is added.Keep reaction molten later
Liquid temperature is 150 DEG C of reaction 45min；
4. obtained silver nanoparticle cube is centrifuged 10min by 10000rpm, after removing supernatant, acetone, second are used respectively
Alcohol and ultra-pure water are respectively washed 1 time, and silver nanoparticle cube is obtained, and projection electron microscope is as shown in Figure 1；
Finally, the silver nanoparticle cube of purification is dispersed in 5mL ultra-pure waters, it is spare；
(2) preparation of hollow manganese dioxide nano particle
1. under magnetic stirring, 5mL silver nanoparticles cube-aqueous dispersions are mixed with 21mg potassium permanganate；
2. after stirring 5min, the polyallylamine hydrochloride that a concentration of 50mg/mL of 0.5mL are added into above-mentioned solution is water-soluble
Liquid；
3. after stirring 30min, 10min is centrifuged under the rotating speed of 8500rpm, remove supernatant to get to hollow titanium dioxide
Manganese nano particle, transmission electron microscope picture are as shown in Figure 2.
Embodiment 2
In order to simulate, there are hydrogen peroxide, acid microenvironments in tumor tissues, by the hollow manganese dioxide in embodiment 1
Nano particle is mixed with the phosphate buffer solution (PBS) of 0.03% hydrogen peroxide, pH=6.4, with diphenyl -1 4,7-,
10- o-phenanthrolines ruthenium complex (Ru (dpp)3Cl2) fluorescence probe detects hollow manganese dioxide nano particle and acid peroxidating
The oxygen that hydrogen solution reaction generates.
Testing result as shown in Figure 3 it is found that with the reaction time increase, what hollow manganese dioxide nano particle generated
Amount of oxygen increases, the manganese ion that the oxygen of generation can improve the micro-environmental hypoxia of tumour, while release can generate magnetic resonance at
As signal, it can be used for magnetic resonance imaging, to the Precise Diagnosis that can realize tumour and efficiently treatment.
Preparation method of the present invention is simple and easy to do, and hollow manganese dioxide particle is prepared convenient for extensive, industrialized；Meanwhile
Obtained hollow manganese dioxide particle has hollow structure, and can prepare cancer treatment drugs or auxiliary in pharmaceutical carrier
It helps the fields such as drug and the contrast agent of magnetic resonance imaging to apply, and good effect can be obtained.
Although illustrate and describing the present invention with specific embodiment, it will be appreciated that without departing substantially from the present invention's
Many other change and modification can be made in the case of spirit and scope.It is, therefore, intended that in the following claims
Including belonging to all such changes and modifications in the scope of the invention.
Claims (10)
1. a kind of preparation method of hollow manganese dioxide nano particle, which is characterized in that described method includes following steps：
First, silver nanoparticle cube is prepared using sulfide-polyol reduction method；Then, it is template with silver nanoparticle cube, and
Potassium permanganate is restored in dispersion liquid containing silver nanoparticle cube, obtains hollow manganese dioxide nano particle.
2. preparation method according to claim 1, which is characterized in that steps are as follows for the preparation method：
(1) silver nanoparticle cube is prepared：
1. after polyalcohol agitating and heating, sulfide-polyhydric alcohol solutions are added, and be stirred；
2. being separately added into inorganic acid-polyhydric alcohol solutions into step 1. acquired solution and polyvinylpyrrolidone-being polynary
Alcoholic solution continues to be stirred；
3. silver salt-polyhydric alcohol solutions are added into step 2. acquired solution, continue to be stirred to react；
4. by supernatant is removed after the step 3. centrifugation of gained mixed solution, and the sediment undergoes washing being collected into is received to get to silver
Then meter Li Fang is scattered in solution, silver nanoparticle cube dispersion liquid is obtained；
(2) hollow manganese dioxide nano particle preparation：
1. silver nanoparticle cube dispersion liquid is stirred with potassium permanganate；
2. polyallylamine hydrochloride solution is added into step 1. gained mixed solution, continue to be stirred；
3. by supernatant is removed after step 2. acquired solution centrifugation to get hollow manganese dioxide nano particle.
3. preparation method according to claim 1 or 2, which is characterized in that the sulfide be vulcanized sodium, NaHS,
The mixture of one or more of potassium sulfide or potassium bisulfide.
4. preparation method according to claim 1 or 2, which is characterized in that the polyalcohol be ethylene glycol, diethylene glycol,
The mixture of one or more of 1,2-PD, 1,3-PD or glycerine；
Optionally, the inorganic acid is the mixture of one or more of hydrochloric acid, nitric acid or sulfuric acid；
Optionally, the silver salt is the mixture of one or more of silver nitrate, Silver Trifluoroacetate or silver acetate.
5. preparation method according to claim 2, which is characterized in that described to divide the sediment undergoes washing being collected into be specific
Not Cai Yong acetone, second alcohol and water cleaned.
6. a kind of hollow manganese dioxide nano particle, which is characterized in that the hollow manganese dioxide nano particle is wanted by right
Any one of 1-5 the methods are asked to be prepared.
7. hollow manganese dioxide nano particle according to claim 6, which is characterized in that the hollow manganese dioxide nano
Particle is hollow porous structure, and can be used as nano-medicament carrier, the drug or ancillary drug for the treatment of cancer, or as magnetic
Resonance image-forming contrast agent uses.
8. application of the hollow manganese dioxide nano particle of claim 6 or 7 in pharmaceutical carrier.
9. the hollow manganese dioxide nano particle of claim 6 or 7 is being prepared in cancer treatment drugs or ancillary drug
Application.
10. application of the hollow manganese dioxide nano particle of claim 6 or 7 in magnetic resonance imaging contrast.
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109796047A (en) * | 2019-03-06 | 2019-05-24 | 东华大学 | A kind of hollow manganese dioxide nano particle and preparation method thereof |
| CN110921712A (en) * | 2019-12-11 | 2020-03-27 | 西京学院 | MnO (MnO)2Nano cage and preparation method and application thereof |
| WO2020259489A1 (en) * | 2019-06-26 | 2020-12-30 | 浙江大学 | Silk fibroin/manganese dioxide composite microsphere drug carrier having core-shell structure and preparation method therefor |
| CN113244409A (en) * | 2021-05-27 | 2021-08-13 | 浙江大学 | Nano particles with synergistic enhancement effects of active oxygen scavenging and anti-inflammatory effects |
| CN113493223A (en) * | 2020-04-03 | 2021-10-12 | 长春可研生物科技有限公司 | Preparation method and application of hollow manganese dioxide nanospheres |
| CN113814397A (en) * | 2021-10-21 | 2021-12-21 | 上海应用技术大学 | Porous Ag @ Cu2O nano cell material and preparation method and application thereof |
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| CN109796047A (en) * | 2019-03-06 | 2019-05-24 | 东华大学 | A kind of hollow manganese dioxide nano particle and preparation method thereof |
| CN109796047B (en) * | 2019-03-06 | 2021-06-11 | 东华大学 | Hollow manganese dioxide nano-particles and preparation method thereof |
| WO2020259489A1 (en) * | 2019-06-26 | 2020-12-30 | 浙江大学 | Silk fibroin/manganese dioxide composite microsphere drug carrier having core-shell structure and preparation method therefor |
| CN110921712A (en) * | 2019-12-11 | 2020-03-27 | 西京学院 | MnO (MnO)2Nano cage and preparation method and application thereof |
| CN110921712B (en) * | 2019-12-11 | 2022-06-07 | 西京学院 | MnO (MnO)2Nano cage and preparation method and application thereof |
| CN113493223A (en) * | 2020-04-03 | 2021-10-12 | 长春可研生物科技有限公司 | Preparation method and application of hollow manganese dioxide nanospheres |
| CN113244409A (en) * | 2021-05-27 | 2021-08-13 | 浙江大学 | Nano particles with synergistic enhancement effects of active oxygen scavenging and anti-inflammatory effects |
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| CN113814397B (en) * | 2021-10-21 | 2023-08-29 | 上海应用技术大学 | Porous Ag@Cu 2 O nano cell material and preparation method and application thereof |
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