CN110104689A - A kind of hollow manganese dioxide nano particle and preparation method thereof - Google Patents

A kind of hollow manganese dioxide nano particle and preparation method thereof Download PDF

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CN110104689A
CN110104689A CN201910238751.XA CN201910238751A CN110104689A CN 110104689 A CN110104689 A CN 110104689A CN 201910238751 A CN201910238751 A CN 201910238751A CN 110104689 A CN110104689 A CN 110104689A
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manganese dioxide
hollow
acid
nano particle
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CN110104689B (en
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王梅云
陈丽娟
白岩
魏巍
高海燕
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Henan Provincial Peoples Hospital
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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
    • B82Y40/00—Manufacture or treatment of nanostructures
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G45/00—Compounds of manganese
    • C01G45/02—Oxides; Hydroxides
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2002/00—Crystal-structural characteristics
    • C01P2002/80—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70
    • C01P2002/85—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70 by XPS, EDX or EDAX data
    • 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
    • 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
    • C01P2004/04—Particle morphology depicted by an image obtained by TEM, STEM, STM or AFM
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/60—Particles characterised by their size
    • C01P2004/62—Submicrometer sized, i.e. from 0.1-1 micrometer

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Nanotechnology (AREA)
  • Organic Chemistry (AREA)
  • Physics & Mathematics (AREA)
  • Condensed Matter Physics & Semiconductors (AREA)
  • General Physics & Mathematics (AREA)
  • Manufacturing & Machinery (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Medicines Containing Antibodies Or Antigens For Use As Internal Diagnostic Agents (AREA)
  • Inorganic Compounds Of Heavy Metals (AREA)

Abstract

The invention discloses a kind of hollow manganese dioxide nano particles and preparation method thereof, its main feature is that restoring potassium permanganate in such a way that the environment of aqueous hydrochloric acid solution uses and once feeds intake or repeatedly feed intake reproducibility organic acid citric acid obtains the hollow nanostructures.The hollow manganese dioxide nano particle preparation is simple, has many advantages, such as that stable property, size and structure are uniform controllable, surface is rich in carboxyl, and can apply in fields such as targeting modification, pharmaceutical carrier and magnetic resonance imagings.

Description

A kind of hollow manganese dioxide nano particle and preparation method thereof
Technical field
The present invention relates to technical field of nano material, and in particular to arrives a kind of hollow manganese dioxide nano particle and its system Preparation Method.
Background technique
Manganese dioxide (MnO2) be widely applied due to characteristics such as special optics, calorifics, chemistry and biologies. Wherein, because it is with high theoretical capacitor, low toxicity, synthesis condition is mild and storage capacity is big, at low cost and be widely studied application Make the material of manganeisen in steel industry, the oxidant and catalyst of chemical industry, the positive electrode active materials of battery industry, Bio-medical magnetic resonance contrast's agent material etc..The manganese dioxide of Nano grade other than the characteristic with transition metal oxide, It is provided simultaneously with nano effect.Therefore, in the past few decades, the manganese bioxide material of different-shape reports that such as film-form is received in succession Popped rice, nanosphere, nanometer sheet, nano particle, nano wire, nanometer rods, nanotube, hollow nanospheres, hollow meso-porous nano ball etc.. Especially in field of biomedicine, nanometer electrode manganese dioxide particle passes through the high-permeability and retention effect of solid tumor The passive target or targeting ligand of (enhanced permeability and retention effect) EPR effect are modified Active targeting act on tumour accumulation.Using manganese dioxide there is strong oxidizing property in acid condition, there is reduction in vivo Property glutathione degradation, or generate oxygen, active oxygen or singlet oxygen with the hydroperoxidation at internal (tumour) position Etc. characteristics, be often used to improve the research of the microenvironments such as tumour weak acid, anoxic in field of biomedicine, the active oxygen for reacting generation can Reach chemicotherapy enhanced sensitivity, the effect of optical dynamic therapy and the research for being used for oncotherapy；The release of manganese dioxide degradation simultaneously two Valence manganese ion (Mn2+) magnetic resonance imaging may be implemented, it is equally used for the research of internal magnetic resonance imaging diagnosis, thus nanoscale two Manganese oxide is with important application prospects in the diagnosis and treatment field of tumour.Further, since hollow manganese dioxide nano particle has There is unique hollow structure, can be used as a kind of pharmaceutical carrier, realize drug delivery, the realization of multi-functional diagnostic and therapeutic system is provided One important supplement.The hollow structure of the preparation method multiplicity of hollow nano-manganese dioxide, document and patent report needs more Hard or soft mode plate material participates in reaction, or the complicated ingredient without template.
Lauryl sodium sulfate (SDS) and mistake are needed by hollow manganese dioxide nano structure prepared by template of polyaniline Ammonium sulfate (APS) will increase the possibility for introducing toxic materials if being used for bio-medical material；Publication No. CN108529681A, patent name are that the patent of invention of " hollow manganese dioxide nano particle and its preparation method and application " is announced One kind is template with silver nanoparticle cube, using the method for the hollow manganese dioxide particle of Template synthesis, the two of this method synthesis Manganese oxide particle stable structure, size and structure-controllable, but the mode for first having to preparation template increases and introduces the general of impurity Rate and preparation step is slightly complicated.
Currently, the rare report of research of the preparation method of hollow manganese dioxide nano particle is prepared about template-free method, from And it is limited in field of biomedicine, drug targeting transmits, and tumour diagnosis and treatment etc. are further applied.
Summary of the invention
The present invention is a kind of hollow manganese dioxide nano particle and preparation method thereof, it cures mechanism using Ostwald, right Manganese dioxide colloidal solid is generated under conditions of reduction in the potassium permanganate with oxidisability, when the middle part particle of aggregation is big When small or density is smaller, by maturing process, inside will cavity；This method is without template and water dispersion, opposite preparation process Simply, obtained hollow manganese dioxide nano grain structure has many advantages, such as safety, stable structure.
The present invention realizes that above-mentioned purpose uses following technical scheme:
A kind of hollow manganese dioxide nano particle and preparation method thereof, it is by reproducibility organic acid in inorganic acid aqueous solution In the environment of the method manganese dioxide reduction presoma that once feeds intake or repeatedly feed intake, then after centrifugation and water purifying To hollow manganese dioxide nano particle.
The step of manganese dioxide presoma once feeds intake is to put into quantitative manganese dioxide forerunner's body disposable Into inorganic acid solution, then it is stirred；Then reproducibility organic acid is added, continues stirring to generation and precipitates, it then will be molten Liquid carries out centrifugally operated, and gained precipitating carries out water purifying.
The step of manganese dioxide presoma feeds intake three times is to be divided into quantitative manganese dioxide presoma equal Three parts；First part of manganese dioxide presoma is put into inorganic acid and is stirred, reproducibility organic acid is then added, stirring is extremely Solution clarification；Then second part of manganese dioxide presoma is added to continue to stir, until third part is added after solution stirring clarification Manganese dioxide presoma, then stirring to precipitating generates；Then solution is subjected to centrifugally operated, gained precipitating carries out water purifying and is It can.
The manganese dioxide presoma is potassium permanganate.
The reproducibility organic acid is oxalic acid, formic acid, vitamin C, citric acid or glucose.
The inorganic acid is hydrochloric acid, nitric acid or sulfuric acid.
A kind of preparation method of manganese dioxide nano particle, wherein the manganese dioxide presoma is potassium permanganate, institute The reproducibility organic acid stated is citric acid, and the inorganic acid is hydrochloric acid.
A kind of manganese dioxide nano particle, it as nano-medicament carrier carry out using.
A kind of manganese dioxide nano particle, it realizes by the response to hydrogen peroxide, acidity PH and is used as magnetic resonance imaging The application of contrast medium.
The present invention cures mechanism using classical Ostwald, for the potassium permanganate with oxidisability reduction condition The interface of generation manganese dioxide colloidal solid in lower, solid and liquid reaches chemical balance.However the size of crystal grain is not Uniformly, small crystals has higher solubility due to surface energy with higher.Inside solution, solute can be from highly concentrated Regional diffusion is to the lower region of concentration.Which results in being completely dissolved for small crystals, big crystal is constantly grown up.Due to concentration This process caused by poor is related to material transport, therefore can be used to manufacture hollow space inside aggregates of nanoparticles.When When the granular size or smaller density at the middle part of aggregation, by maturing process, inside will cavity.
The present invention is a kind of no template, and water dispersion and the simple method of ingredient prepare a kind of hollow manganese dioxide nano ball, Preparation method is simple, and raw material minuent good biocompatibility.The hollow manganese dioxide nano ball that used composition prepares Surface is rich in carboxyl, is the further covalent modification of hollow manganese dioxide nano ball, targeting coupling provides the foundation, further rich The rich function of the manganese dioxide.
The present invention has the advantages that by adopting the above technical scheme
1, in the present invention, using, without method for preparing template, passing through a step or three stage reduction methods synthesis hollow two under room temperature Manganese oxide nano granule, reaction condition is mild, and preparation method is simple and efficient；
2, resulting hollow manganese dioxide nano ball surface is rich in carboxyl (- COOH), is conducive to covalent modification and further function Energyization；
It 3, the use of reaction dissolvent and purification solvent is water, the ingredient for participating in reaction is compound potassium permanganate, organic acid (citric acid), inorganic acid (hydrochloric acid), ingredient is simple, at low cost, prepares hollow manganese dioxide nano convenient for extensive, industrialized Particle.
Detailed description of the invention:
Fig. 1 is the topography scan electron microscope that secondary batching method prepares manganese dioxide.
Fig. 2 is the electron microscope of hollow manganese dioxide.
Wherein Fig. 2A is the topography scan electron microscope (100.0kX) of hollow manganese dioxide；Fig. 2 B is hollow manganese dioxide Whole topography scan electron microscope (50.0kX).
Fig. 3 is the microscopic comparison of hollow manganese dioxide and single hollow manganese dioxide.
Wherein Fig. 3 A is the transmission electron microscope picture of hollow manganese dioxide；Fig. 3 B is the transmission electron microscope of single hollow manganese dioxide Figure.
Fig. 4 is the topography scan electron microscope that a feeding method prepares hollow manganese dioxide.
Fig. 5 is the microscopic comparison of sea urchin shape non-hollow manganese dioxide.
Wherein, Fig. 5 A is the transmission electron microscope picture of sea urchin shape non-hollow manganese dioxide；Fig. 5 B is sea urchin shape non-hollow titanium dioxide The transmission electron microscope picture of manganese.
Fig. 6 is the full spectrogram of X-ray photoelectron spectroscopic analysis (XPS), the manganese (Mn2p) point of hollow manganese dioxide of the invention Spectrogram, carbon (C1s) open score figure, nitrogen (N1s) open score figure comparison diagram.
Wherein, Fig. 6 A is X-ray photoelectron spectroscopic analysis (XPS) full spectrogram of hollow manganese dioxide of the invention；Fig. 6 B For X-ray photoelectron spectroscopic analysis manganese (Mn2p) open score figure of hollow manganese dioxide of the invention；Fig. 6 C is of the invention hollow X-ray photoelectron spectroscopic analysis carbon (C1s) open score figure of manganese dioxide；Fig. 6 D is the X-ray of hollow manganese dioxide of the invention XPS Analysis nitrogen (N1s) open score figure.
Fig. 7 is hollow manganese dioxide acid degradation magnetic resonance signal response diagram under different solutions environment of the invention.
Specific embodiment
Below with reference to embodiment, the present invention will be further described.
A kind of hollow manganese dioxide nano particle and preparation method thereof, it is by reproducibility organic acid in inorganic acid aqueous solution In the environment of the method manganese dioxide reduction presoma that once feeds intake or repeatedly feed intake, then after centrifugation and water purifying To hollow manganese dioxide nano particle.
The present invention implements the main agents used and instrument: potassium permanganate, citric acid, hydrochloric acid；200kV high-resolution transmission electricity Sub- microscope (JEM-2100), FEI:Quanta 250FEG scanning electron microscope match silent winged ThermofisheriCAP Qc ICP-MS inductivity coupled plasma mass spectrometry, 1.5T Siemens Siemens magnetic resonance scanner.
Embodiment 1
It is fed intake twice to potassium permanganate and prepares manganese dioxide nano particle.
By 80mg potassium permanganate (K2MnO4) it is added to 0.1mol, in hydrochloric acid (HCl) solution of 80mL, solution is purple, stirs It mixes 2 minutes, the citric acid of 168mg (0.1mol) is then added；After ten minutes, solution colour becomes claret solution from purple, It stirring the 15th minute, solution becomes brown color, continuously adds 80mg potassium permanganate, and solution became claret after 1 minute, with There is precipitating to generate, continues stirring 5 minutes；Above-mentioned reaction solution is centrifuged, the gained precipitating deionized water of 5-10 parts by weight Purifying, in triplicate.As shown in Figure 1, the manganese dioxide nano even particle size that such method is prepared, but assemble seriously, Fail into hollow pattern, shows that reaction process does not complete maturing process.
Embodiment 2
It is fed intake three times to potassium permanganate and prepares manganese dioxide nano particle.
By 80mg potassium permanganate (K2MnO4) it is added to 0.1mol, in hydrochloric acid (HCl) solution of 80mL, solution is purple, stirs It mixes 2 minutes, the citric acid of 168mg (0.1mol) is then added；After twenty minutes, solution colour becomes khaki from purple, stirring 30th minute, 80mg potassium permanganate is continuously added, solution becomes claret after 1 minute, has precipitating to generate immediately, stirring the 40th Minute, reaction system solution is in brown；60th minute, 80mg potassium permanganate was added in third time, there is brown precipitate generation immediately, after Continuous stirring 5 minutes；Above-mentioned reaction solution is centrifuged (2000rpm, 20min), the gained precipitating deionized water of 5-10 parts by weight Purifying, in triplicate to get hollow manganese dioxide nano ball, yield 44%.The hollow manganese dioxide nano particle of gained is such as schemed Shown in 2 (A) and 2 (B), pattern is uniform, even particle size distribution, in 200-300nm or so, and is in hollow structure.Such as Fig. 3 (A) and Shown in the high resolution scanning electron microscope of 3 (B), by light transmittance difference, it was similarly observed that the manganese dioxide nano of the method preparation Grain graininess is uniform, is in hollow shape, wall thickness about 50nm or so.
Embodiment 3
Manganese dioxide nano particle is prepared in the form of once feeding intake to potassium permanganate.
By 240mg potassium permanganate (K2MnO4) it is added to 0.1mol, in hydrochloric acid (HCl) solution of 80mL, solution is purple, Then the citric acid of 168mg (0.1mol) is added in stirring 2 minutes；After 7 minutes, solution is precipitated in claret；The reaction was continued 15 points Clock, claret precipitating become brown precipitate, above-mentioned reaction solution are centrifuged, and the deionized water of gained precipitating 5-10 parts by weight is pure Change, in triplicate to get hollow manganese dioxide nano ball, yield 37%.
Embodiment 4
It feeds intake to potassium permanganate progress four times and prepares manganese dioxide nano particle.
By 80mg potassium permanganate (K2MnO4) be added in hydrochloric acid (HCl) solution of 0.1mol, solution is purple, stirs 2 points Then the citric acid of 168mg (0.1mol) is added in clock；After twenty minutes, solution colour becomes khaki from purple, stirs the 30th point Clock continuously adds 80mg potassium permanganate, and solution becomes claret after 1 minute, has precipitating to generate immediately, stirs the 40th minute, Reaction system solution is in brown；60th minute, 80mg potassium permanganate was added in third time, has brown precipitate generation immediately, continues to stir It mixes 50 minutes 1 hour solution and gradually becomes brown clarification, the 4th addition 80mg potassium permanganate, solution shows claret immediately, exists side by side Become brown precipitate；Above-mentioned reaction solution is centrifuged, gained precipitating is purified with the deionized water of 5-10 parts by weight, repeats three It is secondary, products therefrom, as shown in figure 5, manganese dioxide sea urchin shape spherical in shape, and partial size increases, in 300-350nm or so.
Detection
X-ray photoelectron spectroscopic analysis is carried out to hollow manganese dioxide nano particle prepared by embodiment 2 in the present invention (XPS) it tests, analyzes the surface functional groups of the hollow manganese dioxide nano particle and the surface-element analysis after functionalization.Fig. 6 A Shown in the full spectrogram of X-ray photoelectron spectroscopic analysis, hollow manganese dioxide nano particle surface-element composition have manganese (Mn2p), Carbon (C1s), oxygen (O1s).Carbon (C1s) open score figure, which is shown, in Fig. 6 C has-C-OH ,-C=O ,-C-C in the Hollow Nanoparticles, Show manganese dioxide surface functional group；It is further reacted, is obtained shown in Fig. 6 A with model protein glucose oxidase GOD-MnO2The full spectrogram of XPS, by compared with the hollow manganese dioxide nano particle before functionalization, the enhancing of the carbon peak (C1s), There is the peak new nitrogen (N1s).- N-C=O in the peak nitrogen shown in Fig. 6 D (N1s) open score figure, the peak-C-N/N-H show that albumen success is even Join and be supported on manganese dioxide surface.
The concentration of manganese ion in hollow manganese dioxide nano particle, 1mg/ml are measured with the method for elemental analysis ICP-MS MnO2The content of middle Mn is 50.3%, prepares a series of aqueous solutions with different manganese ions in embodiment.Solution allocation side Method is as follows: the simulation slightly sour environment of tumour, using the acidic buffer solution of pH6.4-pH6.5, by the hollow titanium dioxide in embodiment 2 Manganese nano particle is mixed with above-mentioned solution, and 10 μM of hydrogen peroxide (H is added2O2)；Various concentration MnO is used simultaneously2PH7.4 (H2O2) and H2O solution is as control.At room temperature, applying clinical 1.5T magnetic resonance scanner (Siemens, magnetic field strength 1.5T, spin-echo sequence: TR=16ms, TE=2.5ms) it measures the external relaxivity of different manganese ion solution and images effect Fruit, wherein manganese (Mn2+) concentration sequence are as follows: 1,0.5,0.25,0.125,0.0625, H2O solution is adopted on 1.5T magnetic resonance device With T1 weighted imaging, obtain the relaxation time and ROI signal is as shown in Figure 7: compared with pure water, the serial solution is in pH6.5 (H2O2), trend is remarkably reinforced in T1 signal；pH7.4(H2O2) and H2O has same trend.The MnO of same concentrations2, pH6.5 (H2O2) response signal with higher, illustrate the acid and hydrogen peroxide responsiveness of manganese dioxide, and for tumour enhancing imaging Possible prospect.
Preparation method of the present invention is simple and feasible, easy, and technique is repeatable, convenient for hollow manganese dioxide nano is mass produced Particle.The above is only presently preferred embodiments of the present invention, is not intended to limit the present invention in any form, although this Invention has been disclosed in a preferred embodiment above, and however, it is not intended to limit the invention, any person skilled in the art, It does not depart from spirit of that invention and technical proposal scope, when the technology contents using the disclosure above are modified or are modified It is right according to the technical essence of the invention for the equivalent embodiment of equivalent variations, but without departing from the technical solutions of the present invention Any simple modification, equivalent change and modification made by above embodiments, all of which are still within the scope of the technical scheme of the invention.

Claims (9)

1. a kind of hollow manganese dioxide nano particle and preparation method thereof, it is characterised in that: it is by reproducibility organic acid in nothing The method manganese dioxide reduction presoma for once feeding intake in the environment of machine aqueous acid or repeatedly feeding intake, then by centrifugation and water Hollow manganese dioxide nano particle is obtained after purifying.
2. a kind of hollow manganese dioxide nano particle according to claim 1 and preparation method thereof, it is characterised in that: described Manganese dioxide presoma the step of once feeding intake be that quantitative manganese dioxide forerunner's body disposable is put into inorganic acid solution In, then it is stirred；Then reproducibility organic acid is added, continues stirring to precipitating is generated, solution is then subjected to centrifugation behaviour Make, gained precipitating carries out water purifying.
3. a kind of hollow manganese dioxide nano particle according to claim 1 and preparation method thereof, it is characterised in that: described Manganese dioxide presoma the step of feeding intake three times be that quantitative manganese dioxide presoma is divided into equal three parts；By first Part manganese dioxide presoma, which is put into inorganic acid, to be stirred, and reproducibility organic acid is then added, and stirring to solution is clarified；So Second part of manganese dioxide presoma is added afterwards to continue to stir, until third part manganese dioxide forerunner is added after solution stirring clarification Body, then stirring to precipitating generates；Then solution is subjected to centrifugally operated, gained precipitating carries out water purifying.
4. according to described in any item a kind of hollow manganese dioxide nano particles of Claims 2 or 3 and preparation method thereof, feature Be: the manganese dioxide presoma is potassium permanganate.
5. a kind of hollow manganese dioxide nano particle according to claim 4 and preparation method thereof, it is characterised in that: described Reproducibility organic acid be oxalic acid, formic acid, vitamin C, citric acid or glucose.
6. a kind of hollow manganese dioxide nano particle according to claim 5 and preparation method thereof, it is characterised in that: described Inorganic acid be hydrochloric acid, nitric acid or sulfuric acid.
7. a kind of hollow manganese dioxide nano particle according to claim 6 and preparation method thereof, it is characterised in that: described Manganese dioxide presoma be potassium permanganate, the reproducibility organic acid be citric acid, the inorganic acid be hydrochloric acid.
8. a kind of manganese dioxide nano particle as claimed in claim 7, it is characterised in that: it is carried out as nano-medicament carrier It uses.
9. a kind of manganese dioxide nano particle as claimed in claim 7, it is characterised in that: it passes through to hydrogen peroxide, acidity The application as magnetic resonance imaging contrast agent is realized in the response of PH.
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CN113083289A (en) * 2021-04-08 2021-07-09 江苏治水有数环保科技有限公司 Preparation method of moisture-proof efficient ozonolysis agent
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Publication number Priority date Publication date Assignee Title
CN110921712A (en) * 2019-12-11 2020-03-27 西京学院 MnO (MnO)2Nano cage and preparation method and application thereof
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CN113083289A (en) * 2021-04-08 2021-07-09 江苏治水有数环保科技有限公司 Preparation method of moisture-proof efficient ozonolysis agent
CN113716612A (en) * 2021-05-11 2021-11-30 山东精工电子科技有限公司 Synthesis method of manganese dioxide hollow sphere structure

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