A kind of rhenium-based polypyrrole nanoparticles and preparation method and application thereof

Abstract

The invention discloses a rhenium-based polypyrrole nanoparticle and a preparation method and application thereof. The preparation method comprises the following steps: dissolving a stabilizer in deionized water to obtain a stabilizer solution; under heating and stirring conditions, sequentially dropping an oxidant and pyrrole into the stabilizer solution to react; after the reaction is completed and cooled, adding a reducing agent to the reaction solution to continue the reaction and centrifuge to obtain the rhenium-based polypyrrole nanoparticle; the rhenium-based polypyrrole nanoparticle has controllable degradability and good optical absorption, can exert a strong photothermal effect under the stimulation of near-infrared I or II laser, thereby burning the tumor; the rhenium-based polypyrrole nanoparticle can further modify glucose oxidase to consume glucose nutrients in the tumor site to starve the tumor, while increasing hydrogen peroxide in the tumor site to promote the biodegradation behavior of the rhenium-based polypyrrole, thereby realizing a safe and effective photothermal synergistic starvation therapy for anti-cancer.

Description

Technical Field

[0001] The invention relates to the technical field of biomedical materials, and in particular to rhenium-based polypyrrole nanoparticles and a preparation method and application thereof. Background Art

[0002] Malignant tumors seriously endanger human health, and their morbidity and mortality are increasing worldwide. At present, the traditional treatment methods for tumors in clinical practice are mainly radiotherapy, chemotherapy and surgical resection, but there are problems such as high invasiveness to patients, large toxic side effects, and potential long-term toxicity. Therefore, developing safer and more effective treatment methods has great social significance for cancer treatment.

[0003] Photothermal therapy is a new type of therapy with low invasiveness, high efficacy and few side effects. It has been clinically used to treat skin diseases such as cervical erosion, and the therapeutic effect is very significant. In recent decades, researchers have also found that photothermal therapy can specifically kill tumors and can become a new type of anti-cancer therapy. However, most photothermal nanomaterials are based on near-infrared I zone laser excitation, and the tissue penetration depth is very limited, so the treatment effect on deep tumors is not good. In addition, the in vivo degradability and metabolic pathways of nanomaterials are unclear, and there is a potential risk of long-term toxicity. Therefore, the development of a nanophotothermal agent that can be safely degraded and cleared from the body after exerting its photothermal anti-tumor effect is a new breakthrough in tumor photothermal therapy.

[0004] Polypyrrole (PPy) is a common heterocyclic conjugated conductive polymer with excellent biocompatibility and good photothermal conversion performance. It has been applied to fields such as nerve regeneration, drug delivery, tissue repair, and photothermal therapy. For example, Chinese patent application CN104117074A discloses a therapeutic diagnostic preparation based on a polypyrrole complex and its preparation method. The polypyrrole is induced to polymerize by ammonium persulfate as an oxidant, which can efficiently convert light energy into heat energy and effectively kill tumor cells. However, the oxidant doped in the nanoskeleton does not play a pharmacological role itself, and its in vivo degradability is unclear. In addition, the effect of single photothermal therapy is limited, and it is difficult to achieve clinical expectations such as complete removal of tumors and recurrence and metastasis. Therefore, photothermal therapy is often combined with other therapies to achieve synergistic treatment of tumors. Summary of the invention

[0005] The purpose of the present invention is to provide a rhenium-based polypyrrole nanoparticle and a preparation method and application thereof. The rhenium-based polypyrrole nanoparticle of the present invention can exert a strong photothermal effect under near-infrared I or II zone laser stimulation, and at the same time, can cooperate with glucose oxidase to achieve safe and effective photothermal synergistic starvation therapy for cancer.

[0006] In order to achieve the above-mentioned purpose of the present invention, the following technical solutions are particularly adopted:

[0007] The first aspect of the present invention provides a method for preparing rhenium-based polypyrrole nanoparticles, the preparation method comprising the following steps:

[0008] (a) dissolving a stabilizer in deionized water to obtain a stabilizer solution;

[0009] (b) under heating and stirring conditions, sequentially adding an oxidant and pyrrole dropwise to the stabilizer solution for reaction, wherein the oxidant is selected from at least one of rhenium oxide, perrhenic acid, rhenium element and rhenium chloride;

[0010] (c) After the reaction is completed and cooled, a reducing agent is added to the reaction solution to continue the reaction and centrifuge to obtain the rhenium-based polypyrrole nanoparticles.

[0011] Preferably, in step (a), the concentration of the stabilizer solution is 2 to 3 mg / ml;

[0012] The stabilizer is selected from at least one of polyvinyl alcohol, polyvinyl pyrrolidone, ethylene glycol, sodium lauryl sulfate, albumin and chitosan.

[0013] Preferably, in step (b), the mass ratio of the added amount of the oxidant and pyrrole to the stabilizer is (10-100):(10-500):(10-100);

[0014] The pyrrole is a pyrrole monomer, or a mixture of a pyrrole monomer and a tri-carboxypyrrole monomer.

[0015] Preferably, in step (b), the oxidant and pyrrole are sequentially added dropwise to the stabilizer solution for reaction, which specifically comprises:

[0016] The oxidant is added dropwise to the stabilizer solution to react for 20 to 40 minutes, and then pyrrole is added dropwise to react for 20 to 25 hours.

[0017] Preferably, during the oxidant addition process, the oxidant is first prepared into an oxidant ethanol solution, wherein the concentration of the oxidant ethanol solution is 80-120 mg / ml.

[0018] Preferably, when the pyrrole is a mixture of a pyrrole monomer and a tri-carboxypyrrole monomer, during the dropwise addition of the tri-carboxypyrrole monomer, the tri-carboxypyrrole monomer is first prepared into a 60-100 mg / ml aqueous solution.

[0019] Preferably, in step (b), the temperature is heated to 80-100° C. and the stirring speed is 600-1500 r / min.

[0020] Preferably, in step (c), the mass ratio of the amount of the reducing agent added to the reducing agent is (1-30): (10-100);

[0021] The reducing agent is selected from at least one of sodium borohydride, ascorbic acid, potassium borohydride, oxalic acid and stannous chloride;

[0022] The reaction time is 2 to 5 hours.

[0023] Preferably, in step (c), the centrifugal speed is 15000-20000 r / min, and the centrifugal time is 8-12 min.

[0024] The second aspect of the present invention provides rhenium-based polypyrrole nanoparticles prepared by the above preparation method.

[0025] The third aspect of the present invention provides a method for preparing glucose oxidase-modified rhenium-based polypyrrole nanoparticles, the preparation method comprising the following steps:

[0026] (a) preparing a dispersion of the rhenium-based polypyrrole nanoparticles prepared by the above preparation method, wherein the pyrrole in the preparation method is a mixture of a pyrrole monomer and a tri-carboxypyrrole monomer;

[0027] (b) adding EDC / NHS solution to the dispersion to carry out stirring reaction;

[0028] (c) After the reaction is completed, a glucose oxidase aqueous solution is added dropwise to the reaction solution, and the mixture is stirred overnight and dialyzed to obtain the glucose oxidase-modified rhenium-based polypyrrole nanoparticles.

[0029] Preferably, the mass ratio of the rhenium-based polypyrrole, EDC / NHS, and glucose oxidase is (1-30):(1-50):(1-10);

[0030] The stirring reaction has a rotation speed of 600 to 1500 r / min and a time of 0.5 to 2 h.

[0031] Preferably, the concentration of the dispersion is 1-2 mg / ml; the concentration of EDC in the EDC / NHS solution is 4-6 mg / ml, and the concentration of NHS is 3-4 mg / ml.

[0032] The fourth aspect of the present invention provides glucose oxidase-modified rhenium-based polypyrrole nanoparticles prepared by the above preparation method.

[0033] A fifth aspect of the present invention provides a use of rhenium-based polypyrrole nanoparticles or glucose oxidase-modified rhenium-based polypyrrole nanoparticles prepared by the above-mentioned preparation method in the preparation of tumor photothermal therapy and / or starvation therapy products.

[0034] Compared with the prior art, the beneficial effects of the present invention include at least:

[0035] The rhenium-based polypyrrole nanoparticles prepared by the present invention have controllable degradability and good optical absorption, and can exert a strong photothermal effect under the stimulation of near-infrared I or II laser, thereby burning the tumor; in addition, the rhenium-based polypyrrole nanoparticles can be further modified with glucose oxidase to consume glucose nutrients in the tumor site to starve the tumor, while increasing the hydrogen peroxide in the tumor site to promote the biodegradation behavior of the rhenium-based polypyrrole, thereby achieving safe and effective photothermal synergistic starvation therapy for anti-cancer.

[0036] The preparation method of the present invention does not require the use of complex equipment and has the characteristics of simple process, easy product acquisition and controllable reaction; and the prepared rhenium-based polypyrrole nanomaterial has a small particle size, uniform particle size distribution, good biocompatibility, biodegradability and photothermal conversion performance in the near-infrared II region. BRIEF DESCRIPTION OF THE DRAWINGS

[0037] In order to more clearly illustrate the specific embodiments of the present invention or the technical solutions in the prior art, the following is a brief introduction to the drawings required for the specific embodiments or the description of the prior art. In all the drawings, similar elements or parts are generally identified by similar reference numerals. In the drawings, the elements or parts are not necessarily drawn according to the actual scale.

[0038] Figure 1 It is the electron microscope scanning image of ReP and Re@ReP in the experimental example of the present invention;

[0039] Figure 2 Elemental Energy Dispersion Spectrum (EDS) diagram of Re@ReP in the experimental example of the present invention;

[0040] Figure 3 is the X-ray diffraction pattern of ReP and Re@ReP in the experimental example of the present invention;

[0041] Figure 4 Thermogravimetric analysis of Re@ReP and Re@ReP-GOx in the experimental examples of the present invention;

[0042] Figure 5 This is a study on the changes in hydrogen peroxide levels of Re@ReP-GOx in the presence or absence of glucose in the experimental examples of the present invention;

[0043] Figure 6 The degradation of Re@ReP under different concentrations of hydrogen peroxide in the experimental example of the present invention;

[0044] Figure 7 The optical absorption and photothermal performance of Re@ReP-GOx in the experimental example of the present invention (1064nm laser excitation);

[0045] Figure 8 This is a study on the cytotoxicity of different nanoformulations on different cells in the experimental examples of the present invention. DETAILED DESCRIPTION

[0046] The following embodiments of the technical solution of the present invention are described in detail in conjunction with the embodiments. The following embodiments are only used to more clearly illustrate the technical solution of the present invention, and are therefore only used as examples, and cannot be used to limit the protection scope of the present invention.

[0047] It should be noted that, unless otherwise specified, the technical terms or scientific terms used in this application should have the common meanings understood by those skilled in the art to which the present invention belongs.

[0048] Example 1

[0049] This embodiment is a method for preparing rhenium-based polypyrrole nanoparticles, and the preparation method comprises the following steps:

[0050] (a) Add 19 mL of deionized water to a 100 mL single-necked round-bottom flask, then add 50 mg of polyvinyl alcohol (PVA), and gently stir and condense under reflux at 90° C. for 1 hour to obtain a stable solution;

[0051] (b) under the stirring conditions of 90° C. and 1000 rpm (magnetic stirring), 1 mL of rhenium heptoxide ethanol solution (containing 100 mg of rhenium heptoxide) was added dropwise, and stirring was continued for 30 min; then 100 μL of pyrrole monomer (99%) and 1 mL of tris-carboxypyrrole monomer aqueous solution (containing 80 mg of tris-carboxypyrrole monomer) were added dropwise, and the mixture was stirred at 1000 rpm for 23 hours;

[0052] (c) After the solution was naturally cooled to room temperature, 4 mL of sodium borohydride aqueous solution (4 mg / mL) was added and the reaction was continued for 3 hours. The resulting reaction solution was centrifuged at 18000 rpm / min for 10 min in a low-temperature ultracentrifuge, and the precipitate was collected to obtain rhenium-based polypyrrole nanoparticles (denoted as Re@ReP).

[0053] Example 2

[0054] This embodiment is a method for preparing rhenium-based polypyrrole nanoparticles, and the preparation method comprises the following steps:

[0055] (a) Add 19 mL of deionized water to a 100 mL single-necked round-bottom flask, then add 50 mg of ethylene glycol, and gently stir and condense under reflux at 90° C. for 1 hour to obtain a stable solution;

[0056] (b) under the stirring conditions of 90° C. and 1000 rpm (magnetic stirring), 1 mL of rhenium heptoxide ethanol solution (containing 100 mg of rhenium heptoxide) was added dropwise, and stirring was continued for 30 min; then 200 μL of pyrrole monomer (99%) was added dropwise, and the reaction was stirred at 1000 rpm for 23 hours;

[0057] (c) After the solution was naturally cooled to room temperature, 4 mL of sodium borohydride aqueous solution (4 mg / mL) was added and the reaction was continued for 3 hours. The resulting reaction solution was centrifuged at 18000 rpm / min for 10 min in a low-temperature ultracentrifuge, and the precipitate was collected to obtain rhenium-based polypyrrole nanoparticles (denoted as Re@ReP).

[0058] Example 3

[0059] This embodiment is a method for preparing glucose oxidase-modified rhenium-based polypyrrole nanoparticles, which comprises the following steps:

[0060] (a) The Re@ReP nanoparticles (10 mg) prepared in Example 1 were dispersed in 8 mL of deionized water, and then 2 mL of a mixed aqueous solution of EDC / NHS (EDC: 10 mg, NHS: 6.5 mg) was added, and the mixture was magnetically stirred at 600-1500 rpm for 1 hour; 1 mL of an aqueous solution of glucose oxidase (GOx) (5 mg / mL) was added dropwise, and the mixture was stirred overnight at 600-1500 rpm; the resulting reaction solution was dialyzed in a 300KD dialysis bag for 48 hours to obtain glucose oxidase-modified rhenium-based polypyrrole nanoparticles (denoted as Re@ReP-GOx) with controllable degradability.

[0061] Comparative Example 1

[0062] This comparative example is a method for preparing rhenium-based polypyrrole nanoparticles, which comprises the following steps:

[0063] (a) Add 19 mL of deionized water to a 100 mL single-necked round-bottom flask, then add 50 mg of polyvinyl alcohol (PVA), and gently stir and condense under reflux at 90° C. for 1 hour to obtain a stable solution;

[0064] (b) under the stirring conditions of 90° C. and 1000 rpm (magnetic stirring), 1 mL of rhenium heptoxide ethanol solution (containing 100 mg of rhenium heptoxide) was added dropwise, and stirring was continued for 30 min; then 100 μL of pyrrole monomer (99%) and 1 mL of tris-carboxypyrrole monomer aqueous solution (containing 80 mg of tris-carboxypyrrole monomer) were added dropwise, and the mixture was stirred at 1000 rpm for 23 hours;

[0065] (c) After the solution was cooled to room temperature naturally, the reaction solution was centrifuged at 18000 rpm / min for 10 min using a low-temperature ultracentrifuge, and the precipitate was collected to obtain rhenium-based polypyrrole nanoparticles (denoted as ReP).

[0066] Experimental Example 1

[0067] This experimental example is to analyze the structural characteristics and performance of the intermediates and products in the preparation process of the examples.

[0068] The morphology and size of ReP and Re@ReP were analyzed by electron microscopy. Figure 1 As shown, Figure 1 In the figure, A is the electron microscope scanning image of ReP; B is the electron microscope scanning image of Re@ReP.

[0069] Depend on Figure 1 It can be seen that both ReP and Re@ReP exhibit good dispersibility and uniform particle size. Under the electron microscope, the particle sizes of ReP and Re@ReP are between 60 and 100 nm.

[0070] The element energy dispersion spectrum analysis of Re@ReP nanoparticles is shown in the following results: Figure 2 shown.

[0071] Depend on Figure 2 It can be seen that the Re@ReP nanoparticles contain Re, C, N, and O elements, indicating that the Re@ReP nanoparticles of the present invention are successfully prepared.

[0072] X-ray diffraction analysis of ReP and Re@ReP nanoparticles showed Figure 3 shown.

[0073] Depend on Figure 3 It can be seen that both ReP and Re@ReP nanoparticles have the characteristic broad absorption peak of polypyrrole (15-30°); compared with ReP, Re@ReP nanoparticles have a new characteristic absorption peak of Re element, indicating that the Re@ReP nanoparticles of the present invention successfully reduce rhenic acid to rhenium element and exist in the nanoskeleton.

[0074] Thermogravimetric analysis of Re@ReP and Re@ReP-GOx nanoparticles showed Figure 4 shown.

[0075] Depend on Figure 4 It can be seen that the content of GOx is 4.45%.

[0076] Experimental Example 2

[0077] In this experimental example, the physicochemical properties of rhenium-based polypyrrole nanoparticles modified with glucose oxidase with controllable degradation were analyzed.

[0078] The enzyme activity of Re@ReP-GOx nanoparticles was analyzed by the following method:

[0079] A 1mM glucose aqueous solution was added to a test tube and incubated with 225μg / mL Re@RePy-GOx (where GOx was 10μg / mL) at room temperature. At different time points, 50μL of the reaction solution was added to a 96-well plate, followed by 100μL of hydrogen peroxide detection reagent, oscillated and mixed, and placed at room temperature for 30 minutes. The absorbance at 560nm was measured using an ELISA reader. The hydrogen peroxide standard curve was used to obtain the concentration of hydrogen peroxide at different time points; the analysis results are shown in Figure 2. Figure 5 shown.

[0080] Depend on Figure 5 It can be seen that Re@ReP-GOx nanoparticles can produce a large amount of hydrogen peroxide in the presence of glucose, and have the ability to increase the concentration of hydrogen peroxide in the tumor microenvironment; at the same time, it once again confirms the successful modification of GOx.

[0081] The degradability and controllable performance of Re@ReP nanoparticles were analyzed as follows:

[0082] Re@ReP nanoparticles were added to hydrogen peroxide solutions with hydrogen peroxide concentrations of 0, 200, 400, and 800 mM, respectively, where the concentration of Re@ReP nanoparticles was 100 μg / mL. After stirring for 24 hours, the state of the nanoparticle solution was observed. The analysis results are shown in Figure 6 shown.

[0083] Depend on Figure 6 It can be seen that Re@ReP nanoparticles can undergo different degrees of degradation under different hydrogen peroxide concentrations (0, 200, 400, 800 mM from left to right), and the degradation rate accelerates with the increase of hydrogen peroxide concentration.

[0084] The optical absorption and photothermal properties of Re@ReP-GOx nanoparticles were evaluated as follows:

[0085] Aqueous solutions of Re@ReP-GOx nanoparticles with concentrations of 12.5, 25, 50, 100, and 200 μg / mL were prepared, and their absorption spectra at 200-1100 nm were measured by UV spectrophotometer. In order to further verify the photothermal performance of Re@ReP-GOx nanoparticles, Re@ReP-GOx nanoparticles with different concentrations (0, 25, 50, 100, and 200 μg / mL) were exposed to different power densities (0.5, 1.0, 1.5, and 2.0 W / cm 2 ) with a 1064 nm laser and the irradiation time was 5 min. Figure 7 As shown, Figure 7In the figure, A is the UV absorption of Re@ReP-GOx nanoparticles aqueous solution with different concentrations at a wavelength of 200-1100 nm; B is the UV absorption of Re@ReP-GOx nanoparticles aqueous solution with different concentrations at a power of 1 W / cm 2 Figure 1 shows the temperature rise curve of 100 μg / mL Re@ReP-GOx nanoparticles aqueous solution during 5 min of 1064 nm laser irradiation; C shows the temperature rise curve of 100 μg / mL Re@ReP-GOx nanoparticles aqueous solution during 5 min of 1064 nm laser irradiation at different powers; D shows the temperature rise curve of 100 μg / mL Re@ReP-GOx nanoparticles aqueous solution during 5 min of 1064 nm laser irradiation at different powers; 2 Temperature variation curve of 100 μg / mL Re@ReP-GOx nanoparticle aqueous solution during 5 laser switching cycles under 1064 nm laser irradiation.

[0086] Depend on Figure 7 As shown in Figure A, Re@ReP-GOx nanoparticles have strong optical absorption in the near-infrared I and II regions and are concentration-dependent.

[0087] Depend on Figure 7 As can be seen from B to D, Re@ReP-GOx nanoparticles have a high temperature rise under 1064nm laser excitation, showing good photothermal conversion ability.

[0088] In summary, Re@ReP-GOx nanoparticles have the required temperature for photothermal therapy to burn tumors, and their near-infrared II laser response capability can greatly increase the cure rate of deep-seated tumors.

[0089] Experimental Example 3

[0090] This experimental example conducted a cell-level safety assessment on the intermediates and products in the preparation process of the example. The assessment results are as follows: Figure 8 As shown; the evaluation method is as follows:

[0091] Human breast cancer cells MCF-7 and mouse fibroblasts 3T3 were respectively cultured at 5×10 3 Cells were seeded at a density of 100 cells / mL in a 96-well plate and cultured for 12 h. After washing once with PBS, the cells were incubated with gradient concentrations of Re@ReP (0, 6.25, 12.5, 25, 50, 100, 200, 400 μg / mL) for 24 h and 48 h. After washing with PBS, the cells were incubated for 2 h using Cell Counting Kit-8 (CCK-8), and the absorbance was measured at a wavelength of 450 nm. Standard cell viability assay was performed to determine relative cell viability. The results are shown in Figure 8 Middle A.

[0092] Mouse breast cancer MCF-7 cells were cultured at 5 × 10 3The cells were seeded in a 96-well plate at a density of 10 cells / mL and cultured for 12 hours. After washing once with PBS, the cells were incubated with gradient concentrations of Re@ReP-GOx (0, 12.5, 25, 50, 75, 100, 125, 150 g / mL) for 24 hours. After washing with PBS, the cells were incubated for 2 hours using Cell Counting Kit-8 (CCK-8), and the absorbance was measured at a wavelength of 450 nm. A standard cell viability assay was performed to determine the relative cell viability. The results are shown in Figure 8 Middle B.

[0093] The experiment was divided into the following six treatment groups: 1) Control, 2) 1064nm, 3) Re@RePy (abbreviated as RRP), 4) Re@RePy+1064nm, 5) Re@RePy-GOx (abbreviated as RRPG), 6) Re@RePy-GOx+1064nm. The drug concentration was 75g / mL and the 1064nm laser was 1W / cm 2 Mouse breast cancer MCF-7 cells were irradiated at 5×10 3 After 12 hours of inoculation, the cells were grouped as above and cultured for another 24 hours. After washing with PBS, the cells were incubated for 2 hours using Cell Counting Kit-8 (CCK-8), and the absorbance was measured at 450 nm. Standard cell viability assay was performed to determine relative cell viability. The results are shown in Figure 8 Middle C;

[0094] Depend on Figure 8 It can be seen that under conditions without laser irradiation, Re@ReP nanoparticles of different concentrations have almost no toxicity to normal cells and tumor cells; while Re@ReP-GOx is toxic to tumor cells and shows concentration dependence; under conditions of 1064nm laser irradiation, Re@ReP-GOx nanoparticles have the strongest toxicity to tumor cells.

[0095] Finally, it should be noted that the above embodiments are only used to illustrate the technical solutions of the present invention, rather than to limit it. Although the present invention has been described in detail with reference to the aforementioned embodiments, those skilled in the art should understand that they can still modify the technical solutions described in the aforementioned embodiments, or replace some or all of the technical features therein by equivalents. These modifications or replacements do not make the essence of the corresponding technical solutions deviate from the scope of the technical solutions of the embodiments of the present invention, and they should all be included in the scope of the claims and specification of the present invention.

Claims

1. A method for preparing glucose oxidase-modified rhenium-based polypyrrole nanoparticles, characterized in that: The steps include: (1) preparing a dispersion of rhenium-based polypyrrole nanoparticles; (2) adding EDC / NHS solution to the dispersion to carry out stirring reaction; (3) After the reaction is completed, a glucose oxidase aqueous solution is added dropwise to the reaction solution, and the mixture is stirred overnight and dialyzed to obtain the glucose oxidase-modified rhenium-based polypyrrole nanoparticles; The preparation method of the rhenium-based polypyrrole nanoparticles comprises the following steps: (a) dissolving a stabilizer in deionized water to obtain a stabilizer solution; (b) under heating and stirring conditions, sequentially adding an oxidant and pyrrole dropwise to a stabilizer solution for reaction, wherein the oxidant is at least one selected from rhenium oxide, perrhenic acid, rhenium element and rhenium chloride; and the pyrrole is a mixture of a pyrrole monomer and a tri-carboxypyrrole monomer; (c) After the reaction is completed and cooled, a reducing agent is added to the reaction solution to continue the reaction and centrifuge to obtain the rhenium-based polypyrrole nanoparticles.

2. The preparation method according to claim 1, characterized in that: In the step (a), the concentration of the stabilizer solution is 2 to 3 mg / ml; The stabilizer is selected from at least one of polyvinyl alcohol, polyvinyl pyrrolidone, ethylene glycol, sodium lauryl sulfate, albumin and chitosan.

3. The preparation method according to claim 1, characterized in that: In the step (b), the mass ratio of the added amount of the oxidant and pyrrole to the stabilizer is (10-100): (10-500): (10-100); The pyrrole is a pyrrole monomer, or a mixture of a pyrrole monomer and a tri-carboxypyrrole monomer.

4. The preparation method according to claim 1, characterized in that: In the step (b), the oxidant and pyrrole are sequentially added dropwise to the stabilizer solution for reaction, specifically comprising: The oxidant is added dropwise to the stabilizer solution to react for 20 to 40 minutes, and then pyrrole is added dropwise to react for 20 to 25 hours.

5. The preparation method according to claim 1, characterized in that: In the step (c), the mass ratio of the amount of the reducing agent added to the reducing agent is (1-30): (10-100); The reducing agent is selected from at least one of sodium borohydride, ascorbic acid, potassium borohydride, oxalic acid and stannous chloride; The reaction time is 2 to 5 hours.

6. The preparation method according to claim 1, characterized in that: The mass ratio of the rhenium-based polypyrrole nanoparticles, EDC / NHS, and glucose oxidase is (1-30): (1-50): (1-10); The stirring reaction has a rotation speed of 600 to 1500 r / min and a time of 0.5 to 2 h.

7. Glucose oxidase-modified rhenium-based polypyrrole nanoparticles prepared by the preparation method according to any one of claims 1 to 6.

8. Use of glucose oxidase-modified rhenium-based polypyrrole nanoparticles prepared by the preparation method according to any one of claims 1 to 6 in the preparation of tumor photothermal therapy and / or starvation therapy products.

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