CN115177735A - Nanocomposite with double nanoenzyme activities and preparation method and application thereof - Google Patents
Nanocomposite with double nanoenzyme activities and preparation method and application thereof Download PDFInfo
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- CN115177735A CN115177735A CN202210710019.XA CN202210710019A CN115177735A CN 115177735 A CN115177735 A CN 115177735A CN 202210710019 A CN202210710019 A CN 202210710019A CN 115177735 A CN115177735 A CN 115177735A
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- nano
- composite material
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- noble metal
- nano composite
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- QYIGOGBGVKONDY-UHFFFAOYSA-N 1-(2-bromo-5-chlorophenyl)-3-methylpyrazole Chemical compound N1=C(C)C=CN1C1=CC(Cl)=CC=C1Br QYIGOGBGVKONDY-UHFFFAOYSA-N 0.000 description 1
- YLZOPXRUQYQQID-UHFFFAOYSA-N 3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)-1-[4-[2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidin-5-yl]piperazin-1-yl]propan-1-one Chemical compound N1N=NC=2CN(CCC=21)CCC(=O)N1CCN(CC1)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F YLZOPXRUQYQQID-UHFFFAOYSA-N 0.000 description 1
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- Medicines Containing Antibodies Or Antigens For Use As Internal Diagnostic Agents (AREA)
Abstract
The invention belongs to the technical field of nano materials, and particularly relates to a nano composite material with double nano enzyme activities, and a preparation method and application thereof. The nano composite material comprises noble metal nano particles and bismuth telluride particles embedded in the noble metal nano particles, and the particle size of the nano composite material is less than 50nm. The bismuth telluride increases the enzyme activity of the noble metal nanoparticles, the prepared nano composite material has catalase-like and glucolase-like dual nano enzyme activity, the catalase-like activity can obviously improve the anaerobic state of a tumor area, and the glucose oxidase-like activity can consume glucose in the tumor area and reduce the energy supply of tumor cells. The enrichment effect of the nano composite material with the ultra-small particle size enables the nano composite material to show good in-vitro CT/Photoacoustic (PAI) bimodal imaging effect, and an anti-tumor treatment system integrating radiotherapy, photothermal therapy and immunotherapy can be realized.
Description
Technical Field
The invention belongs to the technical field of nano materials, and particularly relates to a nano composite material with double nano enzyme activities, and a preparation method and application thereof.
Background
The nano enzyme has the characteristics of high catalytic efficiency, stability, economy and large-scale preparation, and is widely applied to the fields of medicine, chemical industry, food, agriculture, environment and the like. Research on nanoenzymes has rapidly become an active area of research in recent years. Among them, the most studied and well-defined nanoenzymes are gold nanoparticles, which can have catalase-like activity, consume excessive hydrogen peroxide in the tumor microenvironment, generate oxygen and improve the hypoxic state of tumor cells. Meanwhile, the gold nano enzyme also has the activity similar to glucose oxidase, can consume glucose in tumor cells, and generates gluconic acid and hydrogen peroxide. Meanwhile, bi has been reported 3+ 、Pt 2+ 、Ag + And Hg 2+ When the modified gold nano enzyme is modified together with the gold nano enzyme, the enzyme activity of the gold nano enzyme can be greatly enhanced.
The imaging potential of nanomaterials is another important function, and materials with integrated imaging and therapeutic functions are the focus of research. Among many imaging methods, computed Tomography (CT) shows the advantages of infinite penetration depth, excellent spatial resolution, and fast imaging capability. The contrast-enhanced CT has the advantages of high resolution, no limitation of tissue penetration, capability of performing three-dimensional visualization on interested tissues and the like, and plays an important role in clinical diagnosis of various diseases. Currently, CT contrast agents can be divided into two major classes, small molecule agents (iodinated molecules and lanthanide chelates) and nanostructures containing elements with high atomic numbers. Bismuth (Bi, Z = 83) and gold (Au, Z = 79) elements have higher X-ray attenuation coefficients than iodine elements, and have more sensitive CT imaging capabilities. Bismuth is also one of the well-known bio-safety elements and the cheapest heavy metal element. Therefore, both elements are ideal elements for constructing a high performance CT contrast agent. In recent years, various Bi-based and Au-based nanomaterials have been developed as a new generation of CT materials.
Photoacoustic imaging (PAI), an emerging hybrid technology for real-time molecular imaging for preclinical studies, has recently expanded to the clinical setting. The photoacoustic imaging can utilize hemoglobin as an endogenous contrast agent to monitor the hypoxia state of a tumor area in real time, and compared with the traditional methods such as an oxygen needle electrode and BOLD magnetic resonance, the photoacoustic imaging can be a noninvasive method with lower cost and easier acquisition of tumor oxygenation state information.
Many related studies report that the energy supply of tumor cells is reduced by improving the hypoxia state of a tumor area or consuming glucose in the tumor cells through gold nanoenzymes, but the research that the hypoxia state of the tumor area is improved and the glucose in the tumor cells is consumed is combined on a nano system platform, and the simultaneous realization of the activities of the two nanoenzymes is not reported.
Disclosure of Invention
The present invention has been made to solve at least one of the above-mentioned problems occurring in the prior art. Therefore, the invention provides a nano composite material with double nano enzyme activities, and the nano composite material simultaneously has double nano enzyme activities of catalase-like enzyme and glucose oxidase-like enzyme.
The invention also provides a preparation method and application of the nano composite material with double nano enzyme activities.
In a first aspect of the invention, a nano composite material with dual nanoenzyme activities is provided, which comprises noble metal nanoparticles and bismuth telluride particles embedded in the noble metal nanoparticles, wherein the particle size of the nano composite material is less than 50nm.
According to the first aspect of the present invention, at least the following advantageous effects are obtained:
the bismuth telluride increases the enzymatic activity of the noble metal nanoparticles, the nanocomposite has catalase-like and glucolase-like dual nanoenzyme activities, the catalase-like activity can obviously improve the hypoxia state of a tumor region, and the glucose-like oxidase can consume glucose in the tumor region and reduce the energy supply of tumor cells, so that the growth of the tumor cells is effectively inhibited; the particle size of the nano composite material is less than 50nm, so that phagocytosis of a liver endothelial reticulum system can be better avoided, more nano particles can be accumulated in tumors through blood circulation, and the anti-tumor effect is effectively enhanced. And the enrichment effect of the nano composite material with ultra-small particle size enables the nano composite material to show good in-vitro CT/Photoacoustic (PAI) bimodal imaging effect, and can realize an anti-tumor treatment system integrating radiotherapy, photothermal therapy and immunotherapy.
Preferably, the particle size of the nanocomposite is < 30nm, more preferably < 10nm.
Preferably, the noble metal nanoparticles comprise at least one of gold, palladium or platinum nanoparticles.
Preferably, the particle size of the bismuth telluride particles is 1 to 10nm, more preferably 1 to 5nm, and further preferably 1 to 2nm.
Preferably, the noble metal nanoparticles have a particle size of 5 to 20nm, more preferably 8 to 15nm, and even more preferably 8 to 10nm.
Preferably, the molar ratio of the noble metal nanoparticles to the bismuth telluride is 1-4: 1, more preferably 1 to 3:1, further preferably 2:1.
in a second aspect of the present invention, a method for preparing the above nanocomposite material with dual nanoenzyme activity is provided, comprising the following steps: and mixing the bismuth telluride, the noble metal salt and the reducing agent, and reacting to obtain the nano composite material.
Preferably, the molar ratio of the bismuth telluride to the noble metal salt is 1:0.05 to 2, more preferably 1:0.05 to 0.50, more preferably 1:0.05 to 0.16.
Preferably, the noble metal salt comprises at least one of chloroauric acid, gold trichloride, sodium chloroaurate, potassium chloroaurate, ammonium chloroaurate, chloroplatinic acid, potassium chloroplatinate, chloropalladic acid, sodium chloropalladate and potassium chloropalladate.
Preferably, the reducing agent comprises at least one of sodium borohydride and sodium citrate.
Preferably, the molar ratio of the noble metal salt to the reducing agent is 1:5 to 50, more preferably 1:10 to 30.
Preferably, the temperature of the reaction is 30 to 90 ℃, more preferably 30 to 60 ℃, and further preferably 30 to 40 ℃; the reaction time is 6-12 h.
Preferably, the preparation method of the nanocomposite comprises the following steps: and mixing the bismuth telluride dispersion liquid with a noble metal salt solution, adding a reducing agent solution, and reacting to obtain the nano composite material.
Preferably, the solvents of the bismuth telluride dispersion liquid, the noble metal salt solution and the reducing agent solution are common solvents in the field, and independently comprise at least one of water, ethanol, propanol and ethylene glycol.
Preferably, the mass-volume ratio concentration of bismuth telluride to the solvent in the bismuth telluride dispersion is 1mg:1 to 2mL, more preferably 1mg: 1-1.5 mL, such as 1mg:1mL.
Preferably, the concentration of the noble metal salt solution is 30 to 50mM, more preferably 40 to 50mM, and still more preferably 48.54mM.
Preferably, the concentration of the reducing agent solution is 0.1 to 0.5M, more preferably 0.1 to 0.2M.
Preferably, the reaction also comprises a post-treatment step after the reaction is finished, and the post-treatment step comprises washing, filtering and drying treatment.
Preferably, the preparation method of bismuth telluride comprises the following steps: mixing bismuth salt, a tellurium simple substance and a reducing agent, and reacting to obtain the bismuth telluride.
Preferably, the molar ratio of the bismuth salt to the tellurium simple substance to the reducing agent is 1:0.5 to 2:1 to 4, more preferably 1: 0.5-1.5: 1 to 3; further preferably 1:0.9 to 1.3:1.2 to 2.6.
Preferably, the bismuth salt includes at least one of bismuth nitrate, bismuth chloride, bismuth sulfate, bismuth formate, and bismuth acetate.
Preferably, the preparation method of the bismuth telluride comprises the following steps:
mixing the tellurium simple substance and a reducing agent solution, and reacting to obtain a mixed solution;
and adding the mixed solution into a bismuth salt solution to react to obtain the bismuth telluride.
Preferably, the concentration of the reducing agent solution is 0.1 to 1M, more preferably 0.1 to 0.5M, and still more preferably 0.19 to 0.4M.
Preferably, the bismuth salt solution has a concentration of 2 to 20mM, more preferably 6 to 20mM, and still more preferably 6 to 16mM.
Preferably, the temperature of the mixed reaction of the tellurium elementary substance and the reducing agent is 50-150 ℃; more preferably 60 to 90 ℃; when the color of the reaction system solution becomes purple, the reaction is finished.
Preferably, the reaction time of the mixed solution and the bismuth salt solution is 10-60 min, more preferably 5-30 min; the reaction temperature is 30 to 100 ℃, more preferably 30 to 90 ℃, and still more preferably 30 to 40 ℃.
Preferably, the mixed solution and the bismuth salt solution further comprise a post-treatment step after the reaction is finished, and the post-treatment step comprises at least one of washing, filtering and drying.
Preferably, the solvent of the reducing agent solution and the bismuth salt solution is a solvent commonly used in the field, and independently comprises at least one of water, ethanol, propanol and glycol.
Preferably, the reducing agent is of the kind described hereinbefore.
In a third aspect of the invention, an application of the nanocomposite material in preparing an antitumor drug is provided.
In a fourth aspect of the present invention, the application of the above nanocomposite material in CT imaging and/or photoacoustic imaging is proposed.
Compared with the prior art, the invention has the following beneficial effects:
the nano composite material has smaller and uniform particle size, the particle size is less than 10 nanometers, the phagocytosis of a liver endothelial reticulum system can be better avoided, more nano particles can be accumulated in tumors through blood circulation, and the anti-tumor effect is enhanced. The nano composite material has double nano enzyme activities and can improve the hypoxia state of a tumor area; the energy supply of tumor cells can be consumed, the doping of the bismuth element can improve the enzyme activity of noble metal nanoparticles (such as gold nanoenzyme) to a greater extent, improve the hypoxic of a tumor area and consume the energy supply of the tumor cells to a greater extent, can effectively inhibit the tumor growth, and can be used for preparing antitumor drugs. In addition, the enrichment effect of the nano composite material with the ultra-small particle size enables the nano composite material to show good in-vitro CT/Photoacoustic (PAI) bimodal imaging effect; and the nano composite material also has good photo-thermal effect, and the noble metal (gold) and bismuth have excellent radiotherapy sensitization effect, so that a radiotherapy/photo-thermal therapy/immunotherapy integrated anti-tumor treatment system based on improvement of a tumor microenvironment is formed.
Drawings
The invention is further described with reference to the following figures and examples, in which:
FIG. 1 shows Au @ Bi obtained in example 1 of the present invention 2 Te 3 XRD pattern of (a);
FIG. 2 shows Au @ Bi obtained in example 1 of the present invention 2 Te 3 EDS elemental analysis of (a);
FIG. 3 shows Au @ Bi obtained in example 1 of the present invention 2 Te 3 Electron micrographs of (A);
FIG. 4 shows Au @ Bi obtained in example 2 of the present invention 2 Te 3 Electron micrographs of (A);
FIG. 5 shows Au @ Bi obtained in example 3 of the present invention 2 Te 3 Electron microscope images of (a);
FIG. 6 shows Au @ Bi obtained in example 1 2 Te 3 In vitro CT imaging mapAnd a CT value-material concentration relation graph;
FIG. 7 shows Au @ Bi obtained in example 1 2 Te 3 The in-vitro photoacoustic imaging graph and the photoacoustic value-material concentration relation graph are obtained;
FIG. 8 shows Au @ Bi obtained in example 1 2 Te 3 Generating an oxygen content map in vitro;
FIG. 9 is the Au @ Bi obtained in example 1 2 Te 3 And Au @ Bi obtained in comparative example 1 2 Se 3 Generating an oxygen content map in vitro;
FIG. 10 shows Au @ Bi obtained in example 1 2 Te 3 The in vitro glucose oxidase activity verification diagram.
Detailed Description
The concept and technical effects of the present invention will be clearly and completely described below in conjunction with the embodiments to fully understand the objects, features and effects of the present invention. It is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all embodiments, and other embodiments obtained by those skilled in the art without inventive efforts are within the protection scope of the present invention based on the embodiments of the present invention.
Example 1
This example prepares an Au @ Bi 2 Te 3 The powder (nano composite material) comprises the following specific processes:
1) Mixing 243mg (0.62 mmol) of bismuth nitrate and 100mL of ethylene glycol, adding the mixture into a three-neck flask, and shaking up to obtain a solution I;
2) Weighing 95.7mg (0.75 mmol) of tellurium powder and 37mg (0.98 mmol) of sodium borohydride, mixing the tellurium powder and 5mL of deionized water into another three-neck flask, and heating the mixture to 60 ℃ until the color of the solution becomes purple to obtain a solution II;
3) Quickly extracting the solution II, injecting the solution I, continuously stirring at room temperature for 5min to obtain a solution III, and carrying out solid-liquid separation to obtain bismuth telluride nanoparticles;
4) Dissolving 50mg of the bismuth telluride nano-particles in 50mL of deionized water, adding 120 mu L of 48.54mM chloroauric acid aqueous solution, and stirring to obtain a solution IV;
5) Preparing 1200 mu L of 0.1M sodium borohydride aqueous solution, adding the solution IV, stirring to obtain a solution V, reacting at room temperature for 12h, standing and cooling at room temperature, centrifugally washing with absolute ethyl alcohol at 12000rpm, collecting precipitate, and drying in vacuum to obtain the black gold @ bismuth telluride (Au @ Bi) 2 Te 3 ) And (3) powder.
Example 2
This example prepares an Au @ Bi 2 Te 3 The powder (nano composite material) comprises the following specific processes:
1) Mixing 243mg (0.77 mmol) of bismuth chloride and 100mL of ethylene glycol, adding the mixture into a three-neck flask, and shaking up to obtain a solution I;
2) Weighing 95.7mg (0.75 mmol) of tellurium powder and 74mg (1.96 mmol) of sodium borohydride, mixing the tellurium powder and the sodium borohydride with 5mL of deionized water, and heating the mixture to 80 ℃ until the color of the solution becomes purple to obtain a solution II;
3) Quickly extracting the solution II, injecting the solution I, continuously stirring the solution I for 30min at 40 ℃ to obtain a solution III, and carrying out solid-liquid separation to obtain bismuth telluride nano particles;
4) Dissolving 30mg of the bismuth telluride nano-particles in 30mL of deionized water, adding 120 mu L of 48.54mM chloroauric acid aqueous solution, and stirring to obtain a solution IV;
5) Preparing 1200 mu L of 0.2M sodium borohydride aqueous solution, adding the solution IV, stirring to obtain a solution V, reacting at room temperature for 6h, standing and cooling at room temperature, centrifugally washing with absolute ethyl alcohol at 12000rpm, collecting precipitate, and drying in vacuum to obtain the black gold @ bismuth telluride (Au @ Bi) 2 Te 3 ) And (3) powder.
Example 3
This example prepares an Au @ Bi 2 Te 3 The powder (nano composite material) comprises the following specific processes:
1) Mixing 485mg of bismuth chloride (1.53 mmol) and 100mL of glycol, adding the mixture into a three-neck flask, and shaking up to obtain a solution I;
2) Weighing 191.4mg (1.5 mmol) of tellurium powder and 74mg (1.96 mmol) of sodium borohydride, mixing the tellurium powder and 5mL of deionized water into another three-neck flask, and heating the mixture to 90 ℃ until the color of the solution is purple to obtain a solution II;
3) Quickly extracting the solution II, injecting the solution I, continuously stirring the solution II for 5min at 90 ℃ to obtain a solution III, obtaining a solution III, and carrying out solid-liquid separation to obtain bismuth telluride nano particles;
4) Dissolving 100mg of the bismuth telluride nano-particles in 100mL of deionized water, adding 1200 mu L of 48.54mM chloroauric acid aqueous solution, and stirring to obtain a solution IV;
5) Preparing 1200 mu L of 0.2M sodium borohydride aqueous solution, adding the solution IV, stirring to obtain a solution V, reacting at room temperature for 12h, standing and cooling at room temperature, centrifugally washing with absolute ethyl alcohol at 12000rpm, collecting precipitate, and drying in vacuum to obtain the black gold @ bismuth telluride (Au @ Bi) 2 Te 3 ) And (3) powder.
Comparative example 1
This comparative example prepared an Au @ Bi 2 Se 3 The powder comprises the following specific processes:
1) Mixing 243mg (0.62 mmol) of bismuth nitrate and 100mL of ethylene glycol, adding the mixture into a three-neck flask, and shaking up to obtain a solution I;
2) Weighing 59mg (0.75 mmol) of selenium powder and 37mg (0.98 mmol) of sodium borohydride, mixing the selenium powder and 5mL of deionized water into another three-neck flask, and heating the mixture to 60 ℃ until the color of the solution becomes purple to obtain a solution II;
3) Rapidly extracting the solution II, injecting the solution I, continuously stirring at room temperature for 5min to obtain a solution III, and carrying out solid-liquid separation to obtain bismuth selenide nano-particles;
4) Dissolving 50mg of the bismuth selenide nano-particles in 50mL of deionized water, adding 120 mu L of 48.54mM chloroauric acid aqueous solution, and stirring to obtain a solution IV;
5) Preparing 1200 mu L of 0.1M sodium borohydride aqueous solution, adding the solution IV, stirring to obtain a solution V, reacting at room temperature for 12h, standing and cooling at room temperature, centrifugally washing with absolute ethyl alcohol at 12000rpm, collecting precipitate, and drying in vacuum to obtain the black gold @ bismuth selenide (Au @ Bi) 2 Se 3 ) And (3) powder.
Comparative example 2
This example prepares an Au @ Bi 2 S 3 The powder comprises the following specific processes:
1) Mixing 243mg (0.62 mmol) of bismuth nitrate and 100mL of ethylene glycol, adding the mixture into a three-neck flask, and shaking up to obtain a solution I;
2) Weighing 32mg (1 mmol) of sulfur powder and 37mg (0.98 mmol) of sodium borohydride, mixing the sulfur powder and 5mL of deionized water into another three-neck flask, and heating the mixture to 60 ℃ until the color of the solution becomes purple to obtain a solution II;
3) Quickly extracting the solution II, injecting the solution I, continuously stirring at room temperature for 5min to obtain a solution III, and carrying out solid-liquid separation to obtain bismuth sulfide nanoparticles;
4) Dissolving 50mg of the bismuth sulfide nano-particles in 50mL of deionized water, adding 120 mu L of 48.54mM chloroauric acid aqueous solution, and stirring to obtain a solution IV;
5) Preparing 1200 mu L of 0.1M sodium borohydride aqueous solution, adding the solution IV, stirring to obtain a solution V, reacting at room temperature for 12h, standing and cooling at room temperature, centrifugally washing with absolute ethyl alcohol at 12000rpm, collecting precipitate, and drying in vacuum to obtain the black gold @ bismuth sulfide (Au @ Bi) 2 S 3 ) And (3) powder.
Test examples
This test example tested the structure and properties of the nanocomposites prepared in the examples and comparative examples. Wherein:
the method for testing the catalase-like activity comprises the following steps: respectively using deionized water to prepare 200 mu g/mL Au @ Bi 2 Te 3 Solution, 200. Mu.g/mL nanogold solution and Bi 2 Te 3 Solution mixture, 200. Mu.g/mL nano-gold solution, 200. Mu.g/mLBi 2 Te 3 The solution is prepared, and 1mM H is added into the solution respectively 2 O 2 Adding H into the four solutions respectively 2 O 2 After the solution, the oxygen content in the solution is respectively measured by using a probe of an oxygen dissolving instrument.
The method for testing the activity of the glucose oxidase comprises the following steps: the experimental group is 4mg Au @ Bi 2 Te 3 Dissolving in 20mL deionized water, adding 5mL 1mM glucose solution, reacting at room temperature for 30 minutes, further measuring the gluconic acid in the solution, and detecting the solution at 495 ℃by using an ultraviolet spectrophotometerAn absorption peak at 500 nm; adding a contrast group of 5mL of 1mM glucose solution into 20mL of deionized water, reacting at room temperature for 30 minutes, and detecting the absorption peak of the solution at 495-500 nm by using an ultraviolet spectrophotometer.
As is clear from the XRD pattern of FIG. 1 and the elemental analysis pattern of FIG. 2, au @ Bi was successfully prepared in the present invention 2 Te 3 Nano-composite material, and as can be seen from FIGS. 3 to 5, au @ Bi prepared in examples 1 to 3 of the present invention 2 Te 3 The bismuth telluride particles are embedded into the gold nanoparticles, so that the nano composite material has an ultra-small particle size, and the particle sizes of the particles are smaller than 10nm.
As can be seen from FIG. 6, au @ Bi prepared in example 1 of the present invention 2 Te 3 Has better CT imaging function, can effectively increase the CT signal intensity and is along with Au @ Bi 2 Te 3 With increasing concentration, the CT intensity values also increased. Compared with the current clinical CT contrast agent iohexol, au @ Bi 2 Te 3 The CT values of the samples are all higher than that of the iohexol solution with the same concentration, au @ Bi prepared in the embodiment 1 of the invention 2 Te 3 Has better CT imaging function.
As can be seen from FIG. 7, au @ Bi prepared in example 1 of the present invention 2 Te 3 Can obviously enhance the signal intensity of photoacoustic imaging, and Au @ Bi 2 Te 3 The linear correlation between the concentration and the photoacoustic signal intensity is strong, and Au @ Bi can be adjusted 2 Te 3 And the concentration accurately adjusts the required photoacoustic signal intensity.
As can be seen from FIG. 8, au @ Bi prepared in example 1 of the present invention 2 Te 3 The nanocomposites exhibited very good oxygen generation performance, while none of the other groups showed significant oxygen generation. Au @ Bi 2 Te 3 The nano material can consume hydrogen peroxide and generate oxygen, and has good catalase-like activity. As can be seen from FIG. 9, in comparison with example 1, au @ Bi prepared in comparative example 1 2 Se 3 No obvious oxygen generation, no catalase-like activity, au @ Bi prepared in comparative example 2 2 S 3 Similar to the effect of comparative example 1, no obvious oxygen generation, no catalase-like enzymeAnd (4) activity.
Glucose oxidase can react with glucose to generate gluconic acid, and the gluconic acid has a unique absorption peak at 500nm of an ultraviolet spectrum, and the result of fig. 10 shows that: when glucose was compared with Au @ Bi prepared in example 1 2 Te 3 When the nano materials coexist, an obvious absorption peak can be seen at 500nm, which indicates that gluconic acid is generated by the reaction, and a glucose absorption peak is not seen in a simple glucose group curve. Au @ Bi 2 Te 3 The nano material can catalyze glucose to be gluconic acid, and has good glucose oxidase-like performance.
Au @ Bi prepared in examples 2 to 3 2 Te 3 The technical effect of the nanocomposite is similar to that of example 1, and is not described herein.
Au @ Bi prepared by the invention 2 Te 3 The nano composite material has ultra-small particle size (less than 10 nm), can better escape from phagocytosis of a reticulum system in the liver, and can be accumulated in tumors through blood circulation. Au @ Bi 2 Te 3 The nano composite material has dual nano enzyme activities of catalase-like enzyme and glucose oxidase-like enzyme, the catalase-like activity can obviously improve the anaerobic state of a tumor area, and the glucose oxidase-like activity can consume glucose in the tumor area and reduce the energy supply of tumor cells; but also has the dual imaging functions of CT and photoacoustic imaging, and realizes the integration of imaging and treatment. The gold @ bismuth telluride nanoparticle also has a good photo-thermal effect, and the noble metal (gold) and bismuth have excellent radiotherapy sensitization effects, so that a radiotherapy/photo-thermal therapy/immunotherapy integrated anti-tumor therapy system based on improvement of a tumor microenvironment is formed.
The embodiments of the present invention have been described in detail with reference to the accompanying drawings, but the present invention is not limited to the above embodiments, and various changes can be made within the knowledge of those skilled in the art without departing from the gist of the present invention. Furthermore, the embodiments of the present invention and the features of the embodiments may be combined with each other without conflict.
Claims (10)
1. A nanocomposite characterized by: the nano composite material comprises noble metal nano particles and bismuth telluride particles embedded in the noble metal nano particles, wherein the particle size of the nano composite material is less than 50nm.
2. The nanocomposite as claimed in claim 1, wherein: the noble metal nanoparticles comprise at least one of gold, palladium and platinum nanoparticles.
3. The nanocomposite as claimed in claim 1, wherein: the molar ratio of the noble metal nano particles to the bismuth telluride is 1-4: 1.
4. a process for the preparation of a nanocomposite as claimed in any of claims 1 to 3, characterized by comprising the following steps:
and mixing the bismuth telluride particles, noble metal salt and a reducing agent, and reacting to obtain the nano composite material.
5. The method for preparing a nanocomposite material according to claim 4, wherein: the molar ratio of the bismuth telluride to the noble metal salt is 1:0.05 to 2.
6. The method for preparing a nanocomposite material according to claim 4, wherein: the molar ratio of the noble metal salt to the reducing agent is 1:5 to 50.
7. The method for preparing a nanocomposite material according to claim 4, wherein: the reducing agent comprises at least one of sodium borohydride and sodium citrate.
8. The method for preparing a nanocomposite material according to claim 4, wherein: the reaction temperature is 30-90 ℃; the reaction time is 6-12 h.
9. Use of the nanocomposite material of any one of claims 1 to 3 for the preparation of an antitumor medicament.
10. Use of the nanocomposite material of any one of claims 1 to 3 in CT imaging and/or photoacoustic imaging.
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