A prussian blue nanocomposite with light-responsive release of carbon monoxide and a preparation method and application thereof

Abstract

The present application relates to a kind of prussian blue nanocomposite with photoresponsive release carbon monoxide and its preparation method and application, belong to medical preparation technical field.The present application has prussian blue nanocomposite with photoresponsive release carbon monoxide, including prussian blue nanoparticles and group a grafted on the surface of prussian blue nanoparticle: And group b:This prussian blue nanocomposite not only has good biocompatibility, also has excellent thermal conversion efficiency, simultaneously can also utilize light to control CO release amount, so that photothermal therapy and gas therapy synergistic effect, and then significantly improve the cure rate of tumor.

Description

Technical Field

[0001] The present invention relates to the technical field of medical preparations, in particular to a Prussian blue nanocomposite material capable of releasing carbon monoxide in response to light, and a preparation method and application thereof. Background Art

[0002] Cancer poses a significant threat to human life and is one of the world's leading killers. Currently, in addition to surgery and radiotherapy, chemotherapy is primarily administered through oral or intravenous injections of anticancer drugs. However, most anticancer drugs are not targeted and reach low concentrations at the tumor site, resulting in poor treatment efficacy and severe side effects.

[0003] Compared to the aforementioned treatments, phototherapy offers significant advantages in increasing tumor treatment efficacy and reducing side effects, and has gradually become a primary method of tumor treatment in recent years. Phototherapy primarily includes photodynamic therapy (PDT) and photothermal therapy (PTT). PDT utilizes the large amounts of reactive oxygen species (ROS) produced by photosensitizers under specific light irradiation to kill tumor cells, while PTT utilizes light of a specific wavelength to heat up the photothermal agent, killing tumor cells.

[0004] For photothermal therapy, photothermal conversion materials (photothermal therapeutic agents) are key factors affecting the photothermal treatment effect of tumor cells. At present, inorganic nanoparticles represented by gold nanoparticles, metal sulfides, etc., although they can efficiently absorb near-infrared light and show good photothermal treatment effects, have the disadvantages of harsh synthesis conditions, expensive raw materials, and low biocompatibility in clinical applications. Compared with the above-mentioned inorganic nanoparticles, Prussian blue nanoparticles have excellent biocompatibility and biosafety, and show a very high molar extinction coefficient in the near-infrared region, making them one of the most promising photothermal conversion materials.

[0005] However, in actual application, it was found that even though photothermal conversion materials can convert light energy into heat energy to achieve the effect of ablating cancer cells, single photothermal therapy still has limitations in terms of heat resistance or adverse reactions. At the same time, high temperature treatment will also promote the synthesis of heat shock proteins, thereby inhibiting the effect of photothermal therapy, making it difficult to achieve better therapeutic effects.

[0006] In order to improve the effect of photothermal therapy, people begin to combine it with gas therapy, which mainly uses small gas signal molecules such as nitric oxide (NO), hydrogen sulfide (H2S), carbon monoxide (CO) and the like to make tumor cells die. Among the many small gas signal molecules, CO can target mitochondria, promote the generation of active oxygen in situ, thereby disrupting mitochondria to make tumor cells die, and is more suitable for gas therapy; but low concentration of CO is difficult to effectively improve the effect of photothermal therapy, and high concentration of CO will cause poisoning and adverse reactions, so it is urgent to solve the controllable release of CO to improve the effect of photothermal therapy. SUMMARY

[0007] The purpose of the present application is to overcome the shortcomings of the prior art and provide a Prussian blue nanocomposite with light-responsive release of carbon monoxide and a preparation method and application thereof.

[0008] To achieve the above-mentioned purpose, the technical solution adopted by the present application is:

[0009] In the first aspect, the present application provides a Prussian blue nanocomposite with light-responsive release of carbon monoxide, which comprises Prussian blue nanoparticles and groups a and b grafted on the surface of the Prussian blue nanoparticles.

[0010] The chemical structural formula of the group a is shown as formula (I), wherein PEG is polyethylene glycol.

[0011]

[0012] The chemical structural formula of the group b is shown as formula (II):

[0013]

[0014] Optionally, the molecular weight of the PEG is in the range of 300-400 Da, and the PEG with the molecular weight in the range is more conducive to improving the biocompatibility of the Prussian blue nanocomposite; specifically, the molecular weight of the PEG can be 320 Da, 340 Da, 360 Da or 380 Da.

[0015] As a preferred embodiment of the Prussian blue nanocomposite of the present application, the mass ratio of the Prussian blue nanoparticles to the group a is 1:(20-50). Optionally, the mass ratio of the Prussian blue nanoparticles to the group a can be 1:23, 1:25, 1:27, 1:30, 1:33, 1:35, 1:37, 1:40, 1:43, 1:45 or 1:48.

[0016] As a preferred embodiment of the Prussian blue nanocomposite of the present application, the mass ratio of the Prussian blue nanoparticles to the group b is 1:(20-50). Alternatively, the mass ratio of the Prussian blue nanoparticles to the group b can be specifically 1:23, 1:25, 1:27, 1:30, 1:33, 1:35, 1:37, 1:40, 1:43, 1:45, 1:48.

[0017] As a preferred embodiment of the Prussian blue nanocomposite of the present application, the average particle size of the Prussian blue nanoparticles is 100-200 nm, and can be specifically 110 nm, 130 nm, 150 nm, 170 nm, or 190 nm. It has been found that the Prussian blue nanocomposite prepared by using Prussian blue nanoparticles with the above average particle size range is more easily taken up by cells.

[0018] In a second aspect, the present application provides a preparation method of the above-mentioned Prussian blue nanocomposite with light-responsive release of carbon monoxide, which comprises the following steps:

[0019] S1, reacting compound A, trichloroacetic acid and Prussian blue nanoparticles in an organic solvent to obtain bipyridine-modified Prussian blue nanoparticles;

[0020] S2, reacting the bipyridine-modified Prussian blue nanoparticles in S1 with manganese pentacarbonylbromide and double-end amino polyethylene glycol to obtain the Prussian blue nanocomposite with light-responsive release of carbon monoxide;

[0021] The chemical structural formula of the compound A in S1 is shown in formula (III):

[0022]

[0023] Alternatively, the Prussian blue nanoparticles in the above preparation method can be obtained by purchase or prepared by a conventional preparation method of Prussian blue nanoparticles, for example, the method in the literature (Li W P, et al. ACS Nano, 2016, 10, 11027-11036) can be used for preparation, which specifically comprises the following steps:

[0024] Dissolve potassium ferricyanide in a hydrochloric acid solution, then add polyvinylpyrrolidone, stir and mix uniformly at room temperature, seal and react at 80-85℃ for 20-22h, then centrifuge, wash with water and freeze-dry the reaction solution after the reaction is completed to obtain Prussian blue nanoparticles.

[0025] As a preferred embodiment of the preparation method of the Prussian blue nanocomposite, the step S1 is specifically: first, reacting the compound A with trifluoroacetic acid in an organic solvent to obtain compound B; and then, reacting the compound B with Prussian blue nanoparticles in an organic solvent under the conditions of room temperature, closed, and avoiding light for ≥24h to obtain the bipyridine-modified Prussian blue nanoparticles.

[0026] The mass ratio of the compound A to the trifluoroacetic acid is 1:(20-25), and specifically can be 1:21, 1:22, 1:23, 1:24, and preferably 1:25; and the mass ratio of the Prussian blue nanoparticles to the compound B is 1:(25-75), and specifically can be 1:30, 1:35, 1:40, 1:45, 1:50, 1:55, 1:60, 1:65, 1:70, preferably 1:(45-55), and more preferably 1:50. It is found that when the mass ratio of the Prussian blue nanoparticles to the compound B is within the above range, the Prussian blue nanoparticles can better carry an appropriate amount of carbon monoxide, thereby effectively killing tumor cells.

[0027] As a preferred embodiment of the preparation method of the Prussian blue nanocomposite, the mass ratio of the bipyridine-modified Prussian blue nanoparticles to the manganese pentacarbonyl bromide in the step S2 is 1:(1-2).

[0028] As a preferred embodiment of the preparation method of the Prussian blue nanocomposite, the mass ratio of the bipyridine-modified Prussian blue nanoparticles to the double-end amino polyethylene glycol in the step S2 is 1:(1-3).

[0029] As a preferred embodiment of the preparation method of the Prussian blue nanocomposite, the compound A in the step S1 is prepared by the following preparation method: uniformly mixing 2,2'-bipyridine-4,4'-dicarboxylic acid (CAS No. 6813-38-3), 1-ethyl-(3-dimethylaminopropyl) carbodiimide (EDC, CAS No. 1892-57-5), N-Boc-1,6-hexanediamine (CAS No. 51857-17-1), N-hydroxysuccinimide (CAS No. 6066-82-6), and an organic solvent (DMSO), and reacting at room temperature for 24-48h, and then purifying and drying to obtain the compound A.

[0030] Optionally, in the above preparation method, the molar ratio of 2,2'-bipyridine-4,4'-dicarboxylic acid to N-Boc-1,6-hexanediamine is 1:(1-3), which can be specifically 1:1.5, 1:2, 1:2.5, and preferably 1:3; the molar ratio of 2,2'-bipyridine-4,4'-dicarboxylic acid to 1-ethyl-(3-dimethylaminopropyl) carbonyldiimidazole is 1:(4-8), which can be specifically 1:5, 1:6, 1:7, and preferably 1:8; and the molar ratio of 2,2'-bipyridine-4,4'-dicarboxylic acid to N-hydroxysuccinimide is 1:(4-8), which can be specifically 1:5, 1:6, 1:7, and preferably 1:8.

[0031] In a third aspect, the application provides a use of the above-mentioned Prussian blue nanocomposite with light-responsive release of carbon monoxide in the preparation of a photothermal conversion agent. The photothermal conversion agent (PTA) refers to a photothermal conversion material used in photothermal tumor therapy (PTT).

[0032] Compared with the prior art, the application has the following beneficial effects:

[0033] The Prussian blue nanocomposite with light-responsive release of carbon monoxide has not only good biocompatibility and can be recognized and delivered by cells, but also excellent heat conversion efficiency, which can convert light energy into heat energy to heat ablate tumor cells under light conditions; at the same time, the release amount of CO can be regulated by light, so that the photothermal therapy and gas therapy synergize, thereby significantly improving the cure rate of tumors. BRIEF DESCRIPTION OF DRAWINGS

[0034] Figure 1 UV-visible light absorption spectrum of Prussian blue nanoparticles (PB) in Example 1;

[0035] Figure 2 NMR spectrum of compound A in Example 2;

[0036] Figure 3 Mass spectrum of compound A in Example 2;

[0037] Figure 4 Transmission electron microscopy of Prussian blue nanoparticles (PB) in Example 1;

[0038] Figure 5 Transmission electron microscopy of PB-Mn-CO / PEG in Example 3;

[0039] Figure 6 Fourier infrared spectrum of PB in Example 1, PB-BPY in Example 3, PB-Mn-CO and PB-Mn-CO / PEG;

[0040] Figure 7CO in vitro release profile of PB-Mn-CO / PEG in Example 3;

[0041] Figure 8 Cytotoxicity profile of PB-Mn-CO / PEG in Example 3;

[0042] Figure 9 Cell survival profile of PB-Mn-CO / PEG in Example 3 after light exposure;

[0043] Figure 10 Comparison of cell death of PB-Mn-CO / PEG in Example 3 before and after light exposure;

[0044] Figure 11 CO release behavior of PB-Mn-CO / PEG in Example 3 in vivo. DETAILED DESCRIPTION

[0045] In order to better illustrate the purposes, technical solutions and advantages of the present application, the present application will be further described below in combination with specific examples.

[0046] Other materials, reagents, etc. used in the examples can be obtained from commercial channels unless otherwise specified.

[0047] Example 1

[0048] Prussian blue nanoparticles can be prepared by the following preparation method:

[0049] Weigh 132 mg of potassium ferricyanide into a 100 mL flask, and add 40 mL of hydrochloric acid solution (0.1 M) and stir until completely dissolved. Then add 3 g of polyvinylpyrrolidone and stir at room temperature for 30 min. Place in an 80°C drying oven for 20 h. After the reaction is completed, centrifuge and wash with water four times, and freeze-dry to obtain a blue product, which is the Prussian blue nanoparticles (denoted as PB).

[0050] Example 2

[0051] Compound A can be prepared by the following preparation method:

[0052] Dissolve 1 g of 2,2'-dipyridyl-4,4'-dicarboxylic acid in 50 mL of DMSO, and then add 3.138 g of 1-ethyl-(3-dimethylaminopropyl) carbodiimide (EDC) to activate the carboxyl group for 2 h. Then add 3 mL of N-Boc-1,6-hexanediamine and 1.9 g of N-hydroxysuccinimide (NHS) and react at room temperature (25°C) for 24-48 h. After the reaction is completed, the reaction solution is precipitated with water, filtered, and vacuum dried. Then hot melt with ethyl acetate, filtered, cooled and crystallized, suction filtered, and dried to obtain Compound A.

[0053] Example 3

[0054] An embodiment of the present application has a Prussian blue nanocomposite capable of releasing carbon monoxide in response to light, and a preparation method of the Prussian blue nanocomposite includes the following steps:

[0055] S1, 500 mg of compound A was added to a solution of 20 mL trifluoroacetic acid in dichloromethane (25% by mass) and reacted at room temperature (25°C) for 2 h. After the reaction was completed, rotary evaporation was performed to obtain compound B in the form of an oil. 5 mg of Prussian blue nanoparticles was placed in 30 mL of methanol and ultrasonically dispersed for 0.5 h. Then, 250 mg of compound B was added, and the reaction was carried out at room temperature (25°C) for 24 h in a sealed and light-protected manner to obtain bipyridine-modified Prussian blue nanoparticles (denoted as PB-BPY);

[0056] S2, the bipyridine-modified Prussian blue nanoparticles (5 mg) in S1 were placed in 50 mL of DMSO and ultrasonically dispersed for 0.5 h. Then, 5 mg of manganese pentacarbonyl bromide was added, and the reaction was carried out at room temperature (25°C) for 24 h in a sealed and light-protected manner. After the reaction was completed, the reaction solution was centrifuged, washed with a methanol solution, centrifuged with an aqueous solution, and freeze-dried to obtain PB-Mn-CO;

[0057] S3, PB-Mn-CO in S2 was reacted with double-end amino polyethylene glycol at room temperature for 20 h. After the reaction was completed, the reaction solution was centrifuged, washed with a methanol solution, centrifuged with an aqueous solution, and freeze-dried to obtain a Prussian blue nanocomposite capable of releasing carbon monoxide in response to light (denoted as PB-Mn-CO / PEG).

[0058] Performance test

[0059] 1. Ultraviolet-visible light absorption, nuclear magnetic resonance, and mass spectrometry tests

[0060] Figure 1 For the ultraviolet-visible light absorption spectrum of PB in Example 1, the following was obtained: Figure 1 It can be seen that the Prussian blue nanoparticles have good absorption in the near-infrared region. Figure 2 and Figure 3 The nuclear magnetic resonance spectrum and the mass spectrum of compound A in Example 2 are shown in the following figures, respectively: Figure 2 It can be seen that the characteristic peaks of hydrogen on the pyridine ring of compound A are 7.81 ppm, 5.91 ppm, and 5.73 ppm, respectively. Figure 3 It can be seen from the following figure that the relative molecular mass of compound A is 530.39, indicating that compound A is successfully synthesized and its chemical structure is shown below:

[0061]

[0062] 2. Transmission electron microscopy test

[0063] Figure 4 andFigure 5 They are transmission electron micrographs of PB in Example 1 and PB-Mn-CO / PEG in Example 3, respectively. Figure 4 It can be seen that the Prussian blue nanoparticles are cubic in shape with an average particle size of 200nm. Figure 5 It can be found that the average particle size of PB-Mn-CO / PEG is also around 200 nm, and the size of the modified Prussian blue nanoparticles has not changed significantly.

[0064] 3. Fourier transform infrared spectroscopy test

[0065] Figure 6 The Fourier transform infrared spectra of PB in Example 1, PB-BPY, PB-Mn-CO and PB-Mn-CO / PEG in Example 3 are shown; Figure 6 It can be seen that the wavelength of PB's infrared spectrum is 2081cm -1 It is the Fe-CN-Fe stretching vibration absorption peak. After bipyridine-modified PB, the wavelength corresponding to the Fe-CN-Fe stretching vibration absorption peak shifts by 2919 cm -1 , while producing CH(2089cm -1 )、C=N(1421cm -1 ) bond. When pentacarbonyl manganese bromide reacts with PB-BPY, the infrared spectrum of PB-MN-CO shows the CO stretching vibration absorption peak (2138.4 cm-1), and the stretching vibration absorption peak of Fe-CN-Fe shifts (2841.3 cm-1). -1 ), 2904cm -1 is the CH stretching vibration absorption peak, 1454.4 cm -1 and 1374cm -1 is the stretching vibration absorption peak of PEG, indicating that PB-Mn-CO / PEG was successfully synthesized.

[0066] 4. In vitro light response carbon dioxide release test

[0067] An appropriate amount of the PB-Mn-CO / PEG from Example 3 was uniformly dispersed in ultrapure water to form a PB-Mn-CO / PEG dispersion, which was then diluted to 40 ppm with ultrapure water. One mL of the diluted PB-Mn-CO / PEG dispersion was sealed in a cuvette and irradiated with an 808 nm laser for 5 minutes. The absorbance at 410 nm and 430 nm was then measured using a UV spectrophotometer. After the measurement, the laser was turned off and the mixture was allowed to stand for 5 minutes. The absorbance at 410 nm and 430 nm was then measured using a UV spectrophotometer.

[0068] One cycle is 5 minutes of illumination + 5 minutes of rest. Three cycles are tested in total. The test results are as follows:Figure 7 As shown in Figure 7 It can be seen that the release absorption rate increased from 0.26 μM to 0.5 μM at 0-5 min, remained at 0.5 μM at 5-10 min, increased from 0.5 μM to 0.65 μM at 10-15 min, remained at 0.65 μM at 15-20 min, increased from 0.65 μM to 1 μM at 20-25 min, and remained at 1 μM at 25-30 min, which fully demonstrated that the release of carbon monoxide from PB-Mn-CO / PEG could be regulated by adjusting the light conditions, and then the carbon monoxide could be adjusted to a suitable concentration to achieve excellent gas treatment effect.

[0069] 5. Cytotoxicity test

[0070] 1) Cytotoxicity of the nanoparticle dispersion liquid for releasing carbon monoxide in response to light under different drug concentrations was investigated by CCK8 method. Osteosarcoma cells were inoculated into a 96-well plate at a seeding density of 1 x 10 4 4 / well. PBS buffer was used as a blank control group, and PB-Mn-CO / PEG solutions (solvent: PBS) with concentrations of 20 μg / mL, 40 μg / mL, 60 μg / mL, 80 μg / mL and 100 μg / mL were set up respectively, and 3 replicate wells were set up for each concentration. After incubation at 37°C in a 5% CO2 environment for 24 h, the cytotoxicity of each group was detected by CCK8 method, and the corresponding half inhibition rate (IC 50 ) was calculated. The test results are shown in Figure 8 .

[0071] According to Figure 8 , the cell survival rates corresponding to the PB-Mn-CO / PEG solutions with concentrations of 20 μg / mL, 40 μg / mL, 60 μg / mL, 80 μg / mL and 100 μg / mL were 100%, 108%, 98%, 96%, 93% and 88% respectively. It can be seen that the survival rates of osteosarcoma cells all reached more than 80%, which indicated that PB-Mn-CO / PEG had good biocompatibility with osteosarcoma cells.

[0072] 2) Cytotoxicity of the nanoparticle dispersion liquid for releasing carbon monoxide in response to light under different drug concentrations was investigated by CCK8 method. Osteosarcoma cells were inoculated into a 96-well plate at a seeding density of 5 x 10 3 / well. DEME (high-sugar medium) was used as a blank control group, and PB-Mn-CO / PEG solutions (solvent: high-sugar medium) with concentrations of 20 μg / mL, 40 μg / mL, 60 μg / mL, 80 μg / mL, and 100 μg / mL were set up, with three replicate wells for each concentration. A laser with a power of 0.8 w and a wavelength of 808 nm was used for irradiation for 5 min, and then the cells were incubated at 37°C in a 5% CO2 environment for 24 h. The cytotoxicity of each group was detected by the CCK8 method, and the corresponding half-inhibition rate (IC 50 ) was calculated. The test results are shown in Figure 9 .

[0073] According to Figure 9 , the cell survival rates corresponding to the PB-Mn-CO / PEG solutions with concentrations of 20 μg / mL, 40 μg / mL, 60 μg / mL, 80 μg / mL, and 100 μg / mL were 91%, 70%, 62%, 47%, and 18%, respectively. It can be seen that the survival rate of the sarcoma cells gradually decreased with the increase of the concentration of the PB-Mn-CO / PEG solution, indicating that the PB-Mn-CO / PEG can release CO to reduce the survival rate of the osteosarcoma cells after being irradiated.

[0074] 3) The osteosarcoma cells were inoculated into a 96-well plate at a density of 5×10 3 / well. DEME was used as a blank control group, and a PB-Mn-CO / PEG solution (solvent: high-sugar medium) with a concentration of 100 μg / mL was set up. A laser with a power of 0.8 w and a wavelength of 808 nm was used for irradiation for 5 min, and then the cells were incubated at 37°C in a 5% CO2 environment for 24 h. The death images of the osteosarcoma cells were observed by calcein / propidium iodide staining, and the test results are shown in Figure 10 . According to Figure 10 , the cell survival rate decreased with the increase of the concentration of the PB-Mn-CO / PEG, indicating that the PB-Mn-CO / PEG has an effect of inhibiting the growth of tumor cells.

[0075] 6) Test of release of CO in cells

[0076] The release of CO in cells was observed by using a nuclear stain (Hoechst 33342), a carbon monoxide probe (COP-1), and a mitochondrial stain (MitoRed). The osteosarcoma cells were inoculated into a confocal special dish at a density of 1×10 6μg / mL of PB-Mn-CO / PEG solution (solvent is PBS) were set as three groups, and then the groups were irradiated by a laser with a power of 0.8 w and a wavelength of 808 nm for 5 min. Then, Hoechst33342, COP-1 and MitoRed staining agents were added respectively, and the samples were incubated in a 37°C, 5% CO2 environment for 0.5 h. Finally, the CO release behavior images of PB-Mn-CO / PEG in vivo were obtained by laser confocal shooting, and the test results are shown in FIG. 8. Figure 11 As shown in FIG. 8, the results show that PB-Mn-CO can release carbon monoxide under laser irradiation.

[0077] Finally, it should be noted that the above examples are only used to illustrate the technical solutions of the present application and not to limit the protection scope of the present application. Although the present application has been described in detail with reference to the preferred embodiments, those skilled in the art should understand that the technical solutions of the present application can be modified or replaced by equivalents without departing from the essence and scope of the technical solutions of the present application.

Claims

1. A Prussian blue nanocomposite material capable of releasing carbon monoxide in response to light, characterized in that: The invention comprises Prussian blue nanoparticles and a group a and a group b grafted onto the surface of the Prussian blue nanoparticles; The chemical structural formula of the group a is shown in formula (I), wherein PEG is polyethylene glycol; The chemical structural formula of the group b is shown in formula (II):

2. The Prussian blue nanocomposite material according to claim 1, wherein The mass ratio of the Prussian blue nanoparticles to the group a is 1:(20-50).

3. The Prussian blue nanocomposite material according to claim 1, wherein The mass ratio of the Prussian blue nanoparticles to the group b is 1:(20-50).

4. The Prussian blue nanocomposite material according to any one of claims 1 to 3, characterized in that The average particle size of the Prussian blue nanoparticles is 100-200 nm.

5. The method for preparing the Prussian blue nanocomposite material capable of releasing carbon monoxide in response to light according to any one of claims 1 to 4, characterized in that: The following steps are involved: S1, reacting compound A with trichloroacetic acid and Prussian blue nanoparticles in an organic solvent to obtain bipyridine-modified Prussian blue nanoparticles; S2, reacting the bipyridine-modified Prussian blue nanoparticles in S1 with pentacarbonyl manganese bromide and double-terminated amino polyethylene glycol to obtain a Prussian blue nanocomposite material capable of light-responsively releasing carbon monoxide; The chemical structural formula of compound A in S1 is shown in formula (III):

6. The method for preparing the Prussian blue nanocomposite material according to claim 5, wherein: Step S1 is specifically as follows: First, compound A is reacted with trichloroacetic acid in an organic solvent to obtain compound B, and then compound B is reacted with Prussian blue nanoparticles in an organic solvent at room temperature, in a sealed manner, and in the dark for ≥24 hours to obtain bipyridine-modified Prussian blue nanoparticles; the mass ratio of the Prussian blue nanoparticles to compound B is 1:(25-75).

7. The method for preparing the Prussian blue nanocomposite material according to claim 5, wherein: The mass ratio of the bipyridine-modified Prussian blue nanoparticles to manganese bromide pentacarbonyl in step S2 is 1:(1-2).

8. The method for preparing the Prussian blue nanocomposite material according to claim 5, wherein: The mass ratio of the bipyridine-modified Prussian blue nanoparticles to the double-terminated amino polyethylene glycol in step S2 is 1:(1-3).

9. The method for preparing the Prussian blue nanocomposite material according to claim 5, wherein: The compound A in step S1 is prepared by the following preparation method: 2,2'-bipyridine-4,4'-dicarboxylic acid, 1-ethyl-(3-dimethylaminopropyl)carbodiimide, N-Boc-1,6-hexanediamine, N-hydroxysuccinimide and an organic solvent are uniformly mixed, reacted at room temperature for 24 to 48 hours, purified and dried to obtain compound A.

10. Use of the Prussian blue nanocomposite material capable of releasing carbon monoxide in response to light according to any one of claims 1 to 4 in the preparation of a photothermal conversion agent.

Images