Hollow MnO2 composite nanomaterial, preparation method and application thereof

A composite nanomaterial and hollow technology, which is applied in the field of biomedicine, can solve the problems of complex synthesis steps, uncontrollable morphology of MnO2 materials, and difficulty in mass synthesis.

Active Publication Date: 2017-11-17
SUZHOU UNIV
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  • Abstract
  • Description
  • Claims
  • Application Information

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Problems solved by technology

The previously reported MnO 2 Nanostructures are mostly nanoparticles, nanosheets or nanocomposites combined with nanomaterials, which cannot achieve effective drug loading and precise control of drug release
[0004] Currently, there have been reports in the literature based on MnO 2 The nanocomposite is used for the treatment of cancer, but it has the following disadvantages: (1) the synthesis steps are relatively complicated, and it is difficult to carry out large-scale synthesis
(2) Synthetic MnO 2 The shape of the material is uncontrollable, which is not conducive to the repetition of experiments
(3) Synthetic MnO 2 Most of the materials are compounded with other inorganic materials, which is not conducive to the metabolism of materials out of the body
However, it has not been reported to prepare a synthetic method that is simple, can be produced in large quantities, has good reproducibility, is easy to metabolize, and uses the particle to prepare imaging diagnostic and therapeutic agents for cancer at the same time.

Method used

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  • Hollow MnO2 composite nanomaterial, preparation method and application thereof
  • Hollow MnO2 composite nanomaterial, preparation method and application thereof
  • Hollow MnO2 composite nanomaterial, preparation method and application thereof

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preparation example Construction

[0035] The invention provides a hollow MnO 2A method for preparing a composite nanomaterial, comprising the steps of:

[0036] a) dissolving ethyl orthosilicate in a mixed solution of ethanol and alkaline aqueous solution, and hydrolyzing to obtain solid silica nanoparticles;

[0037] b) Mix the aqueous solution of the solid silica nanoparticles with the potassium permanganate solution, perform a reduction reaction and then etch to obtain a hollow MnO 2 nanoparticles;

[0038] c) the hollow MnO 2 The surface of nanoparticles was sequentially modified with polyacrylamine hydrochloride layer, polyacrylic acid layer and aminated polyethylene glycol layer to obtain hollow MnO 2 composite nanomaterials.

[0039] The preparation method provided by the present invention is simple, using solid silica spheres as a template, a large amount of materials with controllable hollow structures can be obtained in one experiment, and has simple synthesis steps, good repeatability and high y...

Embodiment 1

[0065] Embodiment 1: prepare hollow MnO 2 Material (H-MnO 2 -PEG):

[0066] (1) Mix and stir 14 mL of ethanol, 2 mL of water and 500 μL of ammonia water (30%), slowly add 100 μL of tetraethyl orthosilicate dropwise in a water bath at 45°C for 2 hours, and then wash with water three times to obtain solid silica nanoparticles (sSiO 2 ).

[0067] (2) 40mg of sSiO 2 Dispersed in 10 mL of water, an aqueous solution of potassium permanganate (300 mg) was added dropwise to the solution under ultrasonic conditions, after stirring for 12 h, the precipitate was obtained by centrifugation at 14800 rpm, washed three times with water and redispersed in water.

[0068] (3) Dissolve the material obtained in (2) in 2mol / L Na 2 CO 3 In aqueous solution, react at 60°C for 12h to obtain hollow mesoporous silica particles (H-MnO 2 ) and washed three times with water.

[0069] (4) Disperse 10 mL of polyallylamine hydrochloride (PAH, MW=15000) polymer solution (5 mg / mL) in a serum bottle, and...

Embodiment 2

[0077] Example 2: H-MnO 2 - Large-scale synthesis experiment of PEG nanoparticles

[0078] In order to further study the synthesis yield and repeatability of the material, the following experiments were designed:

[0079] According to the synthesis step (1) in the embodiment case 1, obtain 2g sSiO 2 And it was dispersed in 300 mL of water, and an aqueous solution of potassium permanganate (15 g) was added dropwise to the water under ultrasonic conditions. After stirring for 12 h, the precipitate was obtained by centrifugation at 14800 rpm, washed with water three times and dissolved in 2mol / L Na 2 CO 3 In aqueous solution, react at 60°C for 12h to obtain hollow mesoporous MnO 2 Particles (H-MnO 2 ) and washed three times with water.

[0080] Figure 6 It is the H-MnO synthesized on a large scale in Example 2 of the present invention 2 -TEM image of PEG material; in Figure 6 According to the experimental results, it can be found that 6g of material can be obtained in ...

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Abstract

The invention provides a hollow manganese dioxide (MnO2) composite nanomaterial, a preparation method and application thereof. The method comprises the steps that manganese dioxide is dissolved into an ethyl alcohol and basic solution mixed solution, and hydrolysis is performed to obtain silicon dioxide nano-particles; a water solution of the silicon dioxide nano-particles is mixed with a potassium permanganate solution, a reduction reaction is performed, etching is performed, and hollow MnO2 nano-particles are obtained; the surfaces of the hollow MnO2 nano-particles are modified by a Polypropylene amine hydrochloride layer, a polyacrylic acid layer and an aminated polyethylene glycol layer in sequence, and the hollow MnO2 composite nanomaterial is obtained. According to the method, a large number of MnO2 composite nano-materials with the controllable morphology and hollow structures can be obtained through one experiment, and the repeatability is good; the good water solubility and biocompatibility are achieved, drugs are efficiently loaded and released particularly at a tumor site; the MnO2 composite nanomaterial is combined with anti-PD-L1 for use, original tumors can be efficiently killed, and growth far-end tumors can be obviously restrained.

Description

technical field [0001] The invention relates to the technical field of biomedicine, in particular to a hollow MnO 2 Composite nanomaterials, their preparation methods and their applications. Background technique [0002] Cancer is one of the major malignant diseases that threaten human health. Although a large amount of human, material and financial resources have been invested in the prevention and treatment of cancer for decades since the 1950s, the progress made by human beings in this regard is very limited. [0003] In recent years, manganese dioxide (MnO 2 ) nanostructures have attracted considerable attention as a class of tumor microenvironment (TME)-responsive theranostics. The study found that MnO 2 The H present in the TME of the nanostructure + Or glutathione (GSH) can be decomposed under the condition of Mn produced 2+ The ions significantly enhance T1 magnetic resonance imaging, which can be used for tumor-specific imaging and detection. At the same time...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): A61K31/704A61K47/02A61K49/08A61K49/00A61P35/00
CPCA61K31/704A61K47/02A61K49/0036A61K49/005A61K49/08
Inventor 刘庄杨光保
Owner SUZHOU UNIV
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