CN113730578A - Composite photo-thermal material and preparation method and application thereof - Google Patents
Composite photo-thermal material and preparation method and application thereof Download PDFInfo
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K41/00—Medicinal preparations obtained by treating materials with wave energy or particle radiation ; Therapies using these preparations
- A61K41/0052—Thermotherapy; Hyperthermia; Magnetic induction; Induction heating therapy
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K31/00—Medicinal preparations containing organic active ingredients
- A61K31/33—Heterocyclic compounds
- A61K31/335—Heterocyclic compounds having oxygen as the only ring hetero atom, e.g. fungichromin
- A61K31/337—Heterocyclic compounds having oxygen as the only ring hetero atom, e.g. fungichromin having four-membered rings, e.g. taxol
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K41/00—Medicinal preparations obtained by treating materials with wave energy or particle radiation ; Therapies using these preparations
- A61K41/0057—Photodynamic therapy with a photosensitizer, i.e. agent able to produce reactive oxygen species upon exposure to light or radiation, e.g. UV or visible light; photocleavage of nucleic acids with an agent
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K47/00—Medicinal preparations characterised by the non-active ingredients used, e.g. carriers or inert additives; Targeting or modifying agents chemically bound to the active ingredient
- A61K47/50—Medicinal preparations characterised by the non-active ingredients used, e.g. carriers or inert additives; Targeting or modifying agents chemically bound to the active ingredient the non-active ingredient being chemically bound to the active ingredient, e.g. polymer-drug conjugates
- A61K47/51—Medicinal preparations characterised by the non-active ingredients used, e.g. carriers or inert additives; Targeting or modifying agents chemically bound to the active ingredient the non-active ingredient being chemically bound to the active ingredient, e.g. polymer-drug conjugates the non-active ingredient being a modifying agent
- A61K47/62—Medicinal preparations characterised by the non-active ingredients used, e.g. carriers or inert additives; Targeting or modifying agents chemically bound to the active ingredient the non-active ingredient being chemically bound to the active ingredient, e.g. polymer-drug conjugates the non-active ingredient being a modifying agent the modifying agent being a protein, peptide or polyamino acid
- A61K47/64—Drug-peptide, drug-protein or drug-polyamino acid conjugates, i.e. the modifying agent being a peptide, protein or polyamino acid which is covalently bonded or complexed to a therapeutically active agent
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61P—SPECIFIC THERAPEUTIC ACTIVITY OF CHEMICAL COMPOUNDS OR MEDICINAL PREPARATIONS
- A61P35/00—Antineoplastic agents
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/26—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24
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- B22—CASTING; POWDER METALLURGY
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- B22F9/00—Making metallic powder or suspensions thereof
- B22F9/16—Making metallic powder or suspensions thereof using chemical processes
- B22F9/18—Making metallic powder or suspensions thereof using chemical processes with reduction of metal compounds
- B22F9/24—Making metallic powder or suspensions thereof using chemical processes with reduction of metal compounds starting from liquid metal compounds, e.g. solutions
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
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Abstract
The application discloses a composite photo-thermal material and a preparation method and application thereof. The composite photo-thermal material comprises a two-dimensional photo-thermal material matrix, wherein the two-dimensional photo-thermal material matrix is two-dimensional stibene, and nano silver particles are loaded on the two-dimensional stibene. The preparation method comprises the following steps: providing a two-dimensional stibene; and forming nano silver particles on the two-dimensional stibene, so that the nano silver particles are loaded on the two-dimensional stibene to obtain the composite photo-thermal material. The composite photo-thermal material takes two-dimensional stibene as a matrix of a difunctional response platform, and realizes the photo-thermal/photodynamic synergistic treatment effect together with nano silver particles, so that the effect of remarkably treating cancers is achieved. The preparation method can ensure that the prepared composite photo-thermal material has stable performance of photo-thermal/photodynamic cooperative treatment, and the preparation method has high efficiency and reduces economic cost.
Description
Technical Field
The application belongs to the technical field of photo-thermal materials, and particularly relates to a composite photo-thermal material and a preparation method and application thereof.
Background
Cancer, also known as malignant tumor, has been a serious impact on human life and health. According to statistics, the number of new cancer cases rises from 1400 million per year to 2200 million per year by 2030, at present, 6 people are diagnosed as cancer every minute in China, 1 person in every 7-8 people die of cancer, and the cancer is becoming one of the most serious and harsh killers of human life and health. According to the latest tumor monitoring data published by the Shenzhen city chronic disease prevention and treatment center, 25587 new tumor cases of the resident population are reported in the Shenzhen city in 2018, wherein 11399 cases of men and 14188 cases of women have more number of women than men. Lung cancer remains localized to the whole and the first malignant tumor in men, and breast cancer remains localized to the first malignant tumor in women.
Currently, the methods for treating cancer are usually based on surgical treatment and chemotherapy. However, the conventional surgical treatment is difficult to completely remove the cancer tissues and cannot overcome the recurrence caused by the high metastasis of the malignant tumor. Although the chemotherapy can realize the whole body treatment, the administration efficiency of the current chemotherapy drugs is low, the toxic and side effects are large, and a large amount of normal body cells are killed while cancer cells are killed. In addition, the existing chemotherapy means is difficult to effectively track drug molecules and cannot judge the drug effect in real time, so that the accurate drug administration treatment of cancer cannot be realized. Therefore, the development of highly effective anticancer drugs with light-controlled release and precise administration has become a popular topic in the medical research field today.
Currently, photothermal therapy is receiving more and more attention as a novel tumor treatment method, and on one hand, the treatment characteristics of photothermal therapy enable a tumor region to form a high-temperature environment through near infrared light irradiation, so as to promote apoptosis of tumor cells; on the other hand, the controllable release of the drug at the tumor part can be promoted through high temperature, and the effects of precise drug delivery and synergistic promotion of killing of tumor cells are achieved. Wherein the two-dimensional materialThe material is widely used for the photothermal therapy of tumors due to good biocompatibility and higher photothermal conversion efficiency. For example, Huang Xiaohua at California university, san Francisco, regulates Ag in the growth liquid+A series of gold nanorods (AuNRs) with different sizes are synthesized in concentration, and the AuNRs with the best photothermal conversion efficiency are screened and used for photothermal therapy of metastatic cancer cells. The physical and chemical institute of the Chinese academy of sciences Geng Jianxin reports that the Graphene (GO) with functionalized surface is used as a photo-thermal agent to show enhanced photo-thermal effect in tumor treatment, and the enhancement mechanism is mainly that photo-generated energy is transferred from surface polymer molecules to the surface of the graphene so that the photo-thermal conversion efficiency reaches about 25%. The two-dimensional Black Phosphorus Quantum Dots (BPQDs) prepared by Zhang Han of Shenzhen university are used as photothermal agents for photothermal treatment of tumors, the photothermal conversion efficiency of the two-dimensional black phosphorus quantum dots reaches 28.4%, and the two-dimensional black phosphorus quantum dots show good biocompatibility. However, current two-dimensional materials such as gold nanorods and graphene still face the disadvantages of low photothermal conversion efficiency and poor stability as a photothermal agent. The search for a novel two-dimensional material photothermal agent with high photothermal conversion efficiency and high stability is still the key of the research on tumor photothermal therapy.
In addition, with the increasing improvement of pharmacology, pathology and diagnosis and treatment means, anticancer drugs with single function or treatment methods have not been able to meet the requirements of scientific research and application. Combination therapy is becoming a new strategy for current cancer treatment. Two or more anticancer drugs with different action mechanisms or treatment methods are effectively combined to play a synergistic effect so as to achieve the aim of better inhibiting the growth of tumors. Particularly, accurate administration of the nano composite medicine and efficient combined treatment of tumors through regulation and control of near infrared light have important research value and application prospect. Although the progress of combined treatment is reported in a public way at present, for example, the effect of doxorubicin (Dox) loaded on the carrier by the mesoporous silica-coated graphene oxide disclosed at present is better than that of a single-function anticancer drug on cytotoxicity, the current combined treatment drug has certain defects. The specific conditions include low photothermal conversion efficiency, and commonly used photothermal agents such as gold nanoshell (13%), gold nanorod (21%), graphene oxide (25%), and Cu2-xSe nanoparticles (22%), MoS2PEG nanosheets (27.6%), BPQD (28.4%), Bi2S3Nanorod (28.1%) or Bi2S3Nano spherical sponge (31.1%) and the like have low photothermal efficiency, so that the photothermal treatment effect is not ideal.
Disclosure of Invention
The application aims to overcome the defects in the prior art, and provides a composite photothermal material, and a preparation method and application thereof, so as to solve the technical problems of low photothermal conversion efficiency and unsatisfactory stability of the conventional photothermal agent and the unsatisfactory curative effect of the combined treatment medicament.
To achieve the above object, in a first aspect of the present application, a composite photo-thermal material is provided. The composite photo-thermal material comprises a two-dimensional photo-thermal material matrix, wherein the two-dimensional photo-thermal material matrix is two-dimensional stibene, and nano silver particles are loaded on the two-dimensional stibene.
Further, the thickness of the two-dimensional stibene is 0.5 nm-1 μm.
Further, the planar area of the two-dimensional stibene is 50nm2～3000nm2。
Further, the nano silver particles are grown in situ on the two-dimensional stibene.
Further, the nano silver particles are sub-nano silver clusters.
Furthermore, the particle size of the nano silver particles is 0.5 nm-100 nm.
Further, the molar ratio of the two-dimensional stibene to the nano silver particles is 1: 0.05-1: 0.5.
Further, the anti-cancer drug also comprises a targeting agent, wherein the targeting agent is combined on the two-dimensional stibene and/or the nano silver particles.
Still further, the targeting agent includes at least one of a targeting polypeptide, a growth factor, a targeting agent.
Furthermore, the molar ratio of the two-dimensional stibene to the targeting agent is 1: 0.05-1: 0.2.
Specifically, the targeting polypeptide comprises at least one of RGD-PEG-PLA targeting polypeptide, DSPE-PEG-OTC growth inhibitory receptor targeting polypeptide, temperature-responsive elastin-like polypeptide, arginine-rich polypeptide, DSPE-PEG5000-RGD | phospholipid-PEG-targeting peptide and paclitaxel CSNRDARRC-PCL-PGA/TPGS polypeptide.
In particular, growth factors include specific targeting of VEGFR 2.
Specifically, the targeting agent comprises at least one of an Evimos targeting agent and a T-DM1 breast cancer targeting agent.
Further, the coating also comprises a surfactant, and the surfactant is modified and combined on the two-dimensional stibene.
Further, the surfactant comprises at least one of polyethylene glycol, polyvinylpyrrolidone and Tween; and/or
Furthermore, the molar ratio of the two-dimensional stibene to the surfactant is 1: 0.2-1: 2.
In a second aspect of the application, a preparation method of the composite photo-thermal material is provided. The preparation method of the composite photo-thermal material comprises the following steps:
providing a two-dimensional stibene;
and forming nano silver particles on the two-dimensional stibene, so that the nano silver particles are loaded on the two-dimensional stibene to obtain the composite photo-thermal material.
Further, the method for forming nano silver particles on two-dimensional antimonene comprises the following steps:
preparing two-dimensional antimonene modified by a surfactant into a two-dimensional antimonene dispersion liquid;
adding silver salt and a reducing agent into the two-dimensional stibene dispersion liquid, carrying out mixing treatment and reduction reaction, and depositing nano silver particles on the two-dimensional stibene in situ.
Further, the method also comprises the following steps:
the composite photo-thermal material is prepared into dispersion liquid, the dispersion liquid and the targeting agent are mixed, and the targeting agent is combined on the two-dimensional stibene and/or the nano silver particles.
Further, the two-dimensional antimonene dispersion and silver salt are in the following order: mixing the silver ions at a molar ratio of 1: 0.05-1: 0.5.
Further, the silver salt is a silver ion complex.
Furthermore, the mixing ratio of the dispersion liquid and the targeting agent ensures that the two-dimensional stibene: the molar ratio of the targeting agent is 1: 0.05-1: 0.2.
In a third aspect of the present application, a method of application of the present application is provided. The application of the composite photo-thermal material in photo-thermal agents, drug carriers, photo-thermal catalysis, photo-thermal therapeutic agents or photo-thermal power generation materials.
Compared with the prior art, the method has the following technical effects:
the composite photo-thermal material provided by the application uses two-dimensional antimonene as a substrate of a difunctional response platform, on one hand, the antimonene is used for photo-thermal treatment guided by a photo-thermal agent, on the other hand, the antimonene photo-thermal conversion effect is used for promoting the loaded nano silver particles to dissociate and guide the photo-dynamic treatment, and then the photo-thermal/photo-dynamic cooperative treatment effect is realized through near-infrared light regulation and control, so that the effect of obviously treating cancers is achieved.
According to the preparation method of the composite photo-thermal material provided by the second aspect of the application, the nano silver particles are formed on the two-dimensional stibene, and the two-dimensional stibene is loaded with the nano silver particles, so that the prepared composite photo-thermal material is endowed with the characteristic that the composite photo-thermal material can realize photo-thermal/photodynamic cooperative treatment effect through near infrared light regulation, the preparation method of the composite photo-thermal material is controllable in process steps and conditions, the prepared composite photo-thermal material has the photo-thermal/photodynamic cooperative treatment effect and is stable in performance, the preparation method is high in efficiency, and the economic cost is reduced.
In the application of the composite photo-thermal material provided by the third aspect of the application, the application has the effect of realizing photo-thermal/photodynamic cooperative therapy through near-infrared light regulation and control, so that the application effect and the field of the composite photo-thermal material are effectively enhanced.
Drawings
In order to more clearly illustrate the detailed description of the present application or the technical solutions in the prior art, the drawings needed to be used in the detailed description of the present application or the prior art description will be briefly introduced below, and it is obvious that the drawings in the following description are some embodiments of the present application, and other drawings can be obtained by those skilled in the art without creative efforts.
FIG. 1 is a schematic structural diagram of a composite photothermal material according to an embodiment of the present application;
FIG. 2 is a schematic structural diagram of the composite photothermal material of the embodiment of the present application shown in FIG. 1 containing a targeting agent;
FIG. 3 is a schematic diagram illustrating the photothermal/photodynamic synergistic cancer treatment effect of the composite photothermal material containing the targeting agent of the embodiment of the present application shown in FIG. 2 at the targeted site;
FIG. 4 is a flow chart of a method for preparing the composite photo-thermal material according to the embodiment of the present application;
FIG. 5 is a schematic flow chart of a method for preparing the composite photo-thermal material according to the embodiment of the present application;
after the composite photo-thermal material reaches the target site through the targeting agent loaded on the composite photo-thermal material, the composite photo-thermal material passes through the cell wall and is irradiated by light such as infrared light,
FIG. 6 is a graph showing the temperature change of the aqueous dispersion of two-dimensional antimonylene in comparative example 1 under light irradiation; wherein, a is a temperature change curve chart of different two-dimensional stibene water dispersions along with near infrared light irradiation time in comparative example 1; b is a graph of the temperature change of the two-dimensional stibene aqueous dispersion with the laser on and off in comparative example 1;
FIG. 7 is a graph showing the change in ROS content of dispersions of example 1, comparative example 1 and blank under 808nm near-infrared laser irradiation.
Detailed Description
In order to make the technical problems, technical solutions and advantageous effects to be solved by the present application more clearly apparent, the present application is further described in detail below with reference to the embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the present application and are not intended to limit the present application.
In this application, the term "and/or" describes an association relationship of associated objects, meaning that there may be three relationships, e.g., a and/or B, which may mean: a is present alone, A and B are present simultaneously, and B is present alone. Wherein A and B can be singular or plural. The character "/" generally indicates that the former and latter associated objects are in an "or" relationship.
In the present application, "at least one" means one or more, "a plurality" means two or more. "at least one of the following" or similar expressions refer to any combination of these items, including any combination of the singular or plural items. For example, "at least one (a), b, or c", or "at least one (a), b, and c", may each represent: a, b, c, a-b (i.e., a and b), a-c, b-c, or a-b-c, wherein a, b, and c may be single or plural, respectively.
It should be understood that, in various embodiments of the present application, the sequence numbers of the above-mentioned processes do not mean the execution sequence, some or all of the steps may be executed in parallel or executed sequentially, and the execution sequence of each process should be determined by its function and inherent logic, and should not constitute any limitation to the implementation process of the embodiments of the present application.
The terminology used in the embodiments of the present application is for the purpose of describing particular embodiments only and is not intended to be limiting of the application. As used in the examples of this application and the appended claims, the singular forms "a", "an", and "the" are intended to include the plural forms as well, unless the context clearly indicates otherwise.
The weight of the related components mentioned in the description of the embodiments of the present application may not only refer to the specific content of each component, but also represent the proportional relationship of the weight among the components, and therefore, the content of the related components is scaled up or down within the scope disclosed in the description of the embodiments of the present application as long as it is scaled up or down according to the description of the embodiments of the present application. Specifically, the mass described in the specification of the embodiments of the present application may be a mass unit known in the chemical industry field such as μ g, mg, g, kg, etc.
In a first aspect, embodiments of the present application provide a composite photothermal material. The composite photo-thermal material comprises a two-dimensional photo-thermal material matrix and nano silver particles. The structure of the two-dimensional photothermal material comprises a two-dimensional photothermal material matrix 1 and nano silver particles 2 loaded on the two-dimensional photothermal material matrix 1, as shown in fig. 1 and 2.
The two-dimensional photo-thermal material matrix 1 contained in the composite photo-thermal material in the embodiment of the application is two-dimensional stibene. Therefore, the composite photo-thermal material in the embodiment of the application takes the two-dimensional stibene as the photo-thermal material, namely the two-dimensional photo-thermal material matrix 1 as the matrix of the dual-function response platform, and can effectively absorb infrared light energy and convert the infrared light energy into heat energy, so that the effect of killing focus viruses or cancer cells is realized, and the photo-thermal treatment effect is realized. Meanwhile, when the composite photo-thermal material is used as a carrier to carry the drug activity, the photo-thermal conversion effect of the two-dimensional stibene can also promote the controllable release of the drugs on the focus such as a tumor part. In addition, the two-dimensional stibene loaded nano silver particles 2 can play a role of a conductive electron assistant, and the electron conduction generated by the two-dimensional stibene in the process of exerting the photothermal conversion effect is transmitted to the nano silver particles 2, so that the nano silver particles 2 and the two-dimensional stibene are promoted to generate active oxygen so as to realize the effect of killing focus viruses or cancer cells, and the composite photothermal material has the photodynamic therapy effect. Therefore, the composite photo-thermal material provided by the embodiment of the application has the photo-thermal/photodynamic synergistic treatment effect simultaneously through the synergistic interaction between the two-dimensional stibene matrix and the nano silver particles 2 loaded on the two-dimensional stibene matrix, so that the effect and the effect of enhancing the treatment of cancer are achieved.
In the embodiment, the molar ratio of the two-dimensional stibene to the nano-silver particles in the composite photo-thermal material provided by the embodiment of the application is 1: 0.05-1: 0.5. By controlling the proportion of the composite photo-thermal material and the composite photo-thermal material, the synergistic effect of the composite photo-thermal material and the composite photo-thermal material is improved, so that the photo-thermal/photodynamic synergistic treatment effect of the composite photo-thermal material is improved, and the cancer treatment effect and effect of the composite photo-thermal material are further enhanced.
In the examples, the thickness of the two-dimensional photothermal material matrix 1, that is, the two-dimensional antimonene contained in the composite photothermal material of the embodiments of the present application is 0.5nm to 1 μm, and further 0.5nm to 10nm, and specifically may be a typical but non-limiting thickness such as 0.5nm, 1nm, 2nm, 3nm, 4nm, 5nm, 6nm, 7nm, 8nm, 9nm, 10nm, 50nm, 100nm, 200nm, 300nm, 400nm, 500nm, 600nm, 700nm, 800nm, 900nm, 1000nm, and the like. Through the control to two-dimensional antimonylene thickness, carry out optimal control to the number of piles of two-dimensional antimonylene indirectly to make two-dimensional antimonylene have more abundant active site in order to have relatively high light and heat effect and improve its photodynamic effect who impels.
In the examples, the planar area of the two-dimensional antimonene is 50nm2～3000nm2And further 50nm2～200nm2Specifically, it may be 50nm2、100nm2、150nm2、200nm2、500nm2、1500nm2、2000nm2、2500nm2、3000nm2Etc. are typical but not limiting areas. Through the selection and the adjustment of the area of the two-dimensional antimonene plane, the size of the composite photo-thermal material can be controlled, so that the application performance of the composite photo-thermal material in the embodiment of the application can be enhanced, and the photo-thermal/photodynamic synergistic treatment effect of the composite photo-thermal material is improved.
The nano silver particles 2 contained in the composite photothermal material in the embodiment of the application are as described above, and can play a role of a conductive electron assistant, so that electrons generated by the two-dimensional antimonene in the process of exerting the photothermal conversion effect are conducted to the nano silver particles 2, and the nano silver particles 2 and the two-dimensional antimonene are promoted to generate active oxygen so as to kill focus viruses or cancer cells, so that the composite photothermal material has a photodynamic therapy effect. In the example, the nano silver particles 2 are grown in situ on two-dimensional antimonene. Like this, not only can strengthen the stability of nano-silver granule 2 load, improve the structural stability of compound light and heat material of this application embodiment, improved the electric conductivity rate between nano-silver granule 2 and the two-dimensional antimonene moreover to can improve the electron that two-dimensional antimonene produced at the light and heat effect in-process and reach nano-silver granule 2, thereby improve nano-silver granule 2 and two-dimensional antimonene and produce the quantity of active oxygen thing and in order to improve and kill the effect to focus virus or cancer cell.
In an embodiment, the nano silver particles 2 are sub-nano silver clusters, and in a further embodiment, the particle size of the nano silver particles is 0.5nm to 100nm, further 0.5nm to 5nm, and specifically may be a typical but non-limiting particle size such as 0.5nm, 1nm, 2nm, 3nm, 4nm, 5nm, 6nm, 7nm, 8nm, 9nm, 10nm, 20nm, 30nm, 40nm, 50nm, 60nm, 70nm, 80nm, 90nm, 1000 nm. In the research, the inventors found that, by controlling the particle size of the nano silver particles 2 to be in the sub-nano silver cluster, further in the range of 0.5nm to 100nm, further in the range of 0.5nm to 5nm, the nano silver particles 2 exert the above-mentioned amount of the nano silver particles 2 and the two-dimensional antimonene generating active oxygen in the photothermal effect to have a more excellent effect of killing the focus virus or the cancer cell.
In a further embodiment, in each of the above embodiments, the composite photothermal material of the present embodiment further includes a targeting agent, specifically, targeting agent 3 shown in fig. 2. The targeting agent 3 is combined on the two-dimensional antimonene 1 and/or the nano silver particles 2. By means of the targeting agent 3, on the basis of the photo-thermal/photo-dynamic cooperative treatment effect of the composite photo-thermal material provided by the embodiment of the application, the composite photo-thermal material is provided with targeting property, so that accurate targeted drug delivery of the composite photo-thermal material provided by the embodiment of the application and the photo-thermal/photo-dynamic cooperative treatment effect can be realized easily, or accurate targeted drug delivery can be further realized, and active drug ingredients are released. Specifically, as shown in fig. 3, after the composite photo-thermal material of the embodiment of the present application reaches a target site through the targeting agent loaded thereon, the composite photo-thermal material passes through a cell wall and is irradiated by light, such as infrared light, so that the composite photo-thermal material plays a role in photo-thermal/photodynamic cooperative therapy, thereby achieving a role and an effect of treating cancer.
In the embodiment, the molar ratio of the two-dimensional antimonene to the targeting agent 3 is 1: 0.05-1: 0.2, specifically may be 1:0.05, 1:0.06, 1:0.07, 1:0.08, 1:0.09, 1:0.1, 1:0.11, 1:0.12, 1:0.13, 1:0.14, 1:0.15, 1:0.16, 1:0.17, 1:0.18, 1:0.19, 1:0.2 and other typical but non-limiting molar ratios, and the content of the targeting agent 3 is loaded on the composite optothermal material of the embodiment of the present application, so that the targeting effect of the targeting agent 3 is improved, and the precise targeted optothermal/drug delivery of the composite optothermal material of the embodiment of the present application is improved.
In embodiments, the targeting agent 3 comprises at least one of a targeting polypeptide, a growth factor, a targeting agent, a photothermal catalyst, a photothermal therapeutic, or a photothermal power generation material. In a specific embodiment, the targeting polypeptide comprises at least one of RGD-PEG-PLA targeting polypeptide, DSPE-PEG-OTC growth inhibitory receptor targeting polypeptide, temperature-responsive elastin-like polypeptide, arginine-rich polypeptide, DSPE-PEG5000-RGD | phospholipid-PEG-targeting peptide, and paclitaxel CSNRDARRC-PCL-PGA/TPGS polypeptide. Growth factors include, but are not limited to, specifically targeting VEGFR 2. The targeting agent comprises at least one of an Evimos targeting agent and a T-DM1 breast cancer targeting drug. The targeting agents 3 of the types endow the composite photo-thermal material with accurate targeting, and can be selected according to requirements to realize different targeted accurate drug delivery or photo-thermal treatment.
In a further embodiment, in each of the above embodiments, the composite photothermal material of the present application further includes a surfactant (not shown in fig. 1 and 2). The surfactant modification is combined on the two-dimensional antimonene, and can be combined on the nano silver particles 2, or grafted on the two-dimensional antimonene and the nano silver particles 2 simultaneously. By grafting the surface active agent on the composite photo-thermal material in the embodiment of the application, the dispersion performance of the composite photo-thermal material in the embodiment of the application is improved, and the photo-thermal/photodynamic synergistic treatment effect of the composite photo-thermal material is improved. In particular embodiments, the surfactant comprises at least one of polyethylene glycol (PEG), polyvinylpyrrolidone (PVP), and tween. The surfactants can effectively enhance the dispersion performance of the composite photo-thermal material in the embodiment of the application, and do not influence the play of the photo-thermal/photodynamic synergistic treatment effect.
In a second aspect, embodiments of the present application provide a method for preparing the above composite photothermal material. The process flow of the preparation method of the composite photo-thermal material in the embodiment of the application is shown in fig. 4 and 5, and the preparation method comprises the following steps:
s01: providing a two-dimensional stibene;
s02: and forming nano silver particles on the two-dimensional stibene, so that the nano silver particles are loaded on the two-dimensional stibene to obtain the composite photo-thermal material.
Thus, the composite photo-thermal material preparation method provided by the embodiment of the application forms the nano silver particles on the two-dimensional stibene, realizes that the two-dimensional stibene loads the nano silver particles, and forms the composite photo-thermal material with a composite structure, so that the prepared composite photo-thermal material has stable performance with photo-thermal/photodynamic synergistic treatment effect. And the preparation method has high efficiency and reduces the economic cost.
The two-dimensional stibene in step S01 is the two-dimensional photothermal material matrix 1 contained in the above composite photothermal material, that is, the two-dimensional stibene. Therefore, the thickness, area, and the like of the two-dimensional antimonene in step S01 are all the same as those of the two-dimensional antimonene contained in the above composite photothermal material. For the sake of brevity, the two-dimensional antimonene in step S01 will not be described in detail herein.
The two-dimensional stibene can be prepared according to the existing method, such as the ultrasonic-assisted liquid phase stripping method.
In an example, the surface modification of the two-dimensional antimonene in step S01 is combined with a surfactant. The surfactant is the surfactant contained in the composite photo-thermal material. Therefore, the type of the surfactant and the amount of the surfactant bonded to the two-dimensional antimonene are the same as those of the surfactant and the modified bonding amount contained in the composite photothermal material. By modifying and combining the surfactant on the surface of the two-dimensional antimonene, the dispersity and the dispersion stability of the two-dimensional antimonene in the prepared dispersion liquid are improved, so that the uniformity of the loading of the nano silver particles in the step S02 can be improved.
In the embodiment, the method of surface modification of two-dimensional antimonene and combination of surfactant can be used for surface modification by mixing two-dimensional antimonene and surfactant in a solvent. Or in the process of preparing the two-dimensional antimonene, for example, in the process of preparing the two-dimensional antimonene by adopting an ultrasonic-assisted liquid phase stripping method, the two-dimensional antimonene is ultrasonically stripped by adopting a solution containing a surfactant, and the two-dimensional antimonene with the surface modified and combined with the surfactant is directly obtained.
In step S02, the silver nanoparticles formed on the two-dimensional stibene are silver nanoparticles 2 contained in the above composite photothermal material. Therefore, the relevant performance parameters, such as morphology and particle size, of the nano silver particles in step S02 are the same as the relevant performance parameters, etc., of the nano silver particles 2 contained in the above composite photo-thermal material. For the sake of brevity, the description of the nano-silver particles in step S02 is omitted.
In an embodiment, a method of forming nano-silver particles on two-dimensional antimonene includes the steps of:
s021: preparing two-dimensional antimonene modified by a surfactant into a two-dimensional antimonene dispersion liquid;
s022: adding silver salt and a reducing agent into the two-dimensional stibene dispersion liquid, carrying out mixing treatment and reduction reaction, and depositing nano silver particles on the two-dimensional stibene in situ;
wherein the surfactant and the two-dimensional antimonene in step S021 are the surfactant and the two-dimensional antimonene described above, respectively. The concentration of the two-dimensional antimonene dispersion liquid can be prepared and adjusted according to actual conditions, and the premise that the two-dimensional antimonene is fully dispersed is guaranteed.
The mixing ratio of the two-dimensional stibene dispersion liquid and the silver salt in the step S022 is to ensure that the grown nano silver particles meet the condition that the molar ratio of the two-dimensional stibene to the silver ions is 1: 0.05-1: 0.5. In embodiments, the silver salt is added as a silver complex, e.g., the complex should be any complex capable of forming a silver complex with a silver salt, such as but not limited to a silver ammine complexing solution. The silver salt is added in the form of silver complex, so that the morphology and size of the nano silver particles formed by deposition can be effectively controlled, for example, the nano silver particles formed by deposition are controlled to be in the sub-nano silver cluster morphology, and the particle size of the sub-nano silver cluster is further controlled to be 0.5 nm-100 nm.
In an embodiment, the reducing agent in step S022 includes at least one of sodium borohydride, hydrazine hydrate, aldehydes, hydrogen gas, and the like. The addition amount of the reducing agent should ensure that all silver ions are reduced to generate a silver simple substance to be precipitated, that is, the reducing agent should be excessive relative to the silver ions, for example, in the embodiment, the silver salt and the reducing agent are added and mixed according to the mass ratio of 100: 1-100: 20.
Further, the preparation method of the composite photo-thermal material according to the above embodiments further includes the following steps, as shown in step S03 in fig. 4:
the composite photo-thermal material is prepared into dispersion liquid, the dispersion liquid and the targeting agent are mixed, and the targeting agent is combined on the two-dimensional stibene and/or the nano silver particles.
In step S03, during the mixing process of the targeting agent and the composite photothermal material in step S02, the targeting agent adsorbs and binds to the two-dimensional antimonene and/or nano silver particles, such as a targeting agent coating layer can be formed, but not only, the coating layer can be continuous or discontinuous, and the amount of the targeting agent can be determined according to the actual amount of the adsorbed and bound targeting agent. Therefore, due to the existence of the targeting agent, the prepared composite photo-thermal material has accurate targeting on the basis of having the photo-thermal/photodynamic synergistic treatment effect.
In addition, the targeting agent in step S03 is targeting agent 3 contained in the above composite photothermal material. Therefore, the type, loading amount, etc. of the targeting agent in this step S03 are the same as those of the targeting agent 3 contained in the above composite photothermal material. For economy of disclosure, the description of the targeting agent in step S02 is omitted here. As in the embodiment, the mixing ratio of the dispersion liquid and the targeting agent ensures that the molar ratio of the two-dimensional stibene to the targeting agent is 1: 0.05-1: 0.2 on the prepared composite photo-thermal material. The target property of the composite photo-thermal material is improved by controlling and optimizing the load of the target agent on the composite photo-thermal material.
Therefore, the preparation method of the composite photo-thermal material in each embodiment can effectively prepare the composite photo-thermal material with the composite structure, and can control the particle size of the prepared composite photo-thermal material, the morphology, the particle size, the loading amount and the like of the nano silver-loaded particles by controlling the preparation conditions, so that the photo-thermal/photodynamic synergistic treatment effect of the prepared composite photo-thermal material is improved. Or further, the type of the targeting agent and the mixing ratio of the targeting agent and the two-dimensional stibene composite photo-thermal material loaded with the nano-silver particles are controlled, so that the load of the targeting agent on the prepared composite photo-thermal material is controlled, the precise targeting property of the composite photo-thermal material is endowed and improved, and different targeted precise dosing or photo-thermal treatment is realized and improved.
In a third aspect, embodiments of the present application provide applications of the above composite photothermal material. Based on the components contained in the composite photo-thermal material and the structure formed by the components in the embodiment of the application, the composite photo-thermal material has a photo-thermal/photodynamic cooperative treatment effect or further has accurate targeting, so that the application effect and the field of the composite photo-thermal material in the embodiment of the application are effectively enhanced. The composite photo-thermal material can be directly used as a photo-thermal agent to kill focus viruses or cancer cells and realize the action of photo-thermal and photodynamic therapy. The composite photo-thermal material provided by the embodiment of the application can also be used as a drug carrier of a certain active drug, so that accurate targeted drug delivery of the active drug is realized, and the synergistic treatment effect and effect of the active drug and photo-thermal and photodynamic therapy are realized. Of course, based on the structure and characteristics of the composite photo-thermal material in the embodiments of the present application, the composite photo-thermal material can also be applied to photo-thermal catalysis or photo-thermal power generation materials.
The composite photothermal material and the preparation method thereof according to the embodiments of the present application are illustrated by a plurality of specific examples.
Example 1
The embodiment provides a composite photo-thermal material and a preparation method thereof. The composite photo-thermal material comprises two-dimensional stibene and sub-nanometer silver clusters growing on the two-dimensional stibene in situ.
The preparation method of the composite photo-thermal material comprises the following steps:
s1, preparing an antimonene nanosheet by using an ultrasonic-assisted liquid phase stripping method:
and (3) putting the antimony metal block into a mortar for crushing, adding sec-butyl alcohol, and uniformly grinding for 1 hour along the same direction to fully strip the antimony metal block. Then moving the mixed solution into an ultrasonic bottle, and carrying out ultrasonic treatment on the mixed solution for 6 hours in an ice-water bath by using a probe to obtain a mixed solution containing the stibene and the surfactant; centrifuging at 5000rpm for 10 minutes to remove blocky metal antimony and large-size antimonene, centrifuging the filtrate at 10000rpm for 20 minutes to obtain small-size surfactant surface-modified antimonene, washing the antimonene with deionized water for multiple times, and dispersing the antimonene into the deionized water to obtain antimonene dispersion liquid;
s2, loading sub-nano silver clusters on the stibene nanosheets:
mixing silver nitrate aqueous solution and n-butylamine in a molar ratio of 1:2, adding the silver-ammonia complex solution into the antimonene dispersion liquid according to the proportion, fully mixing, adding excessive formaldehyde solution, and then continuing stirring, wherein due to the fact that the stripped antimonene surface has a plurality of active sites, the reduced silver atoms can be continuously deposited on the active sites on the antimonene surface, a strong chemical bond is formed, and sub-nano silver clusters are deposited on the two-dimensional antimonene.
The detection proves that the average thickness of the two-dimensional stibene, namely stibene nano-sheet is 500nm, and the average area is 1500nm2(ii) a The average particle size of the sub-nano silver cluster is 50nm, and the molar ratio of the two-dimensional stibene to the sub-nano silver cluster is 1:0.2 on average.
Example 2
The embodiment provides a composite photo-thermal material and a preparation method thereof. The composite photo-thermal material comprises two-dimensional stibene and sub-nano silver clusters growing on the two-dimensional stibene in situ, wherein RGD polypeptide is also combined on the two-dimensional stibene and the sub-nano silver clusters.
The preparation method of the composite photo-thermal material comprises the following steps:
s1, preparing an antimonene nanosheet according to step S1 in example 1;
s2, loading sub-nano silver clusters on the stibene nanosheets according to the step S1 in the example 1:
s3, centrifugally washing the synthesized nano compound, dispersing the nano compound into deionized water again, adding a targeting reagent RGD polypeptide, and continuously stirring the mixture overnight to enable the mixture to fully wrap the nano compound; and finally, centrifugally washing the product to obtain the final composite photo-thermal material.
According to detection, the molar contents of the two-dimensional stibene and the sub-nano silver cluster and between the two-dimensional stibene and the sub-nano silver cluster are all as in example 1, and the average molar ratio of the two-dimensional stibene to the RGD polypeptide is 1: 0.1.
Example 3
The embodiment provides a composite photo-thermal material and a preparation method thereof. The composite photo-thermal material comprises two-dimensional antimonene and a sub-nano silver cluster growing on the two-dimensional antimonene in situ, and VEGFR2 targeting agents are further combined on the two-dimensional antimonene and the sub-nano silver cluster.
The preparation method of the composite photo-thermal material of this example refers to the preparation method of example 2. The difference lies in that the prepared composite photo-thermal material contains the antimonene nanosheet and the sub-nano silver cluster by controlling the preparation conditions of the antimonene nanosheet and the sub-nano silver cluster and the condition control of the loaded targeting agent
The average thickness of the two-dimensional stibene, namely stibene nano-sheets is 900nm, and the average area is 2500nm2(ii) a Flat of sub-nano silver clusterThe average grain diameter is 1nm, and the average molar ratio of the two-dimensional stibene to the sub-nano silver clusters is 1: 0.1.
Example 4
The embodiment provides a composite photo-thermal material and a preparation method thereof. The composite photo-thermal material comprises two-dimensional antimonene and a sub-nano silver cluster growing on the two-dimensional antimonene in situ, and T-DM1 breast cancer targeting drugs are combined on the two-dimensional antimonene and the sub-nano silver cluster.
The preparation method of the composite photo-thermal material of this example refers to the preparation method of example 2. The difference lies in that the prepared composite photo-thermal material contains the antimonene nanosheet and the sub-nano silver cluster by controlling the preparation conditions of the antimonene nanosheet and the sub-nano silver cluster and the condition control of the loaded targeting agent
The average thickness of the two-dimensional stibene, namely stibene nano-sheets is 1nm, and the average area is 100nm2(ii) a The average grain diameter of the sub-nano silver cluster is 0.6nm, and the average molar ratio of the two-dimensional stibene to the sub-nano silver cluster is 1:0.5
Comparative example 1
This comparative example provides a two-dimensional antimonene. Compared with the example 1, the method is different from the method in that the method does not contain the sub-nano silver clusters, namely, the two-dimensional stibene is not loaded with the sub-nano silver clusters.
Experiment of relevant properties of composite photo-thermal material
The composite photothermal materials provided in examples 1 to 4 and the photothermal material provided in comparative example 1 were subjected to the relevant property test as follows:
1. and (3) researching the photothermal effect based on stibene:
(1) photo-thermal performance experiment:
the two-dimensional antimonene distribution in examples 1 to 4 and comparative example 1 was prepared into aqueous dispersion solutions with different concentrations of 2 μ g/mL, 5 μ g/mL and 10 μ g/mL based on the mass of the two-dimensional antimonene, water was used as a blank test group (the concentration of the two-dimensional antimonene was 0 μ g/mL), 2mL of the aqueous dispersion solutions with different concentrations were added into a 32-well plate, then near-infrared laser irradiation was performed at 808nm, the temperature of the aqueous dispersion solution was recorded every 30 seconds, the laser irradiation was turned off after continuous recording for 30 minutes, the changes of the cooling temperature and time of the aqueous dispersion solution were recorded immediately, and finally, the change curve of the temperature change of the aqueous dispersion solution with the near-infrared irradiation time at different concentrations was obtained. The temperature change curve of the different aqueous dispersions of two-dimensional antimonylene in comparative example 1 with the irradiation time of near infrared light is shown as a in FIG. 6. As can be seen from the a diagram in figure 6, the two-dimensional antimonene has excellent photo-thermal performance. In addition, the temperature change curves of the aqueous dispersions of different composite photo-thermal materials of examples 1 to 4 with the irradiation time of near infrared light are substantially the same as the graph a in fig. 6. Therefore, the composite photo-thermal material disclosed by the embodiment of the application has a good photo-thermal effect, and the loaded sub-nano silver clusters and the targeting agent hardly influence the exertion of the photo-thermal property of the two-dimensional antimonene.
(2) Photothermal stability test:
and (3) after the photothermal performance test in the step (1) is finished, turning on the laser again for irradiation, repeating the irradiation for 3 to 5 times, and recording the temperature rise and temperature drop curves of the aqueous dispersion. Among them, the temperature change curve of the aqueous dispersion of the two-dimensional antimonene with the concentration of 5 mug/ml in the comparative example 1 along with the laser on and off is shown in the b diagram in fig. 6, and it can be seen from the b diagram in fig. 6 that the two-dimensional antimonene has excellent photo-thermal sensitivity and good photo-thermal effect stability. The temperature profile of the different aqueous dispersions of examples 1 to 4 with the laser switched on and off is substantially the same as that of graph b in fig. 6. Therefore, the composite photo-thermal material disclosed by the embodiment of the application has excellent photo-thermal sensitivity and good photo-thermal effect stability, and the loaded sub-nano silver clusters and the targeting agent hardly influence the performance of the photo-thermal performance of the two-dimensional antimonene.
2. Research on ROS generated by light-operated release and dissociation of the composite photo-thermal material:
respectively preparing dispersion liquids with the same concentration from the composite photo-thermal materials in the embodiments 1 to 4 and the two-dimensional antimonene in the comparative example 1, irradiating the dispersion liquids by using near-infrared laser with the wavelength of 808nm, taking out quantitative samples for different irradiation times, centrifuging the samples, and carrying out ICP (inductively coupled plasma) detection on the filtrate to determine a change curve of the amount of the silver clusters dissociated by irradiation along with the irradiation time.
Changes in ROS generated by dissociation of silver clusters were studied using 1, 3-Diphenylisobenzofuran (DPBF). The specific method comprises the following steps: and (3) fully mixing the prepared dispersion liquid with DPBF, irradiating by 808nm near-infrared laser, taking a quantitative solution every minute, centrifuging, measuring the UV-vis absorption spectrum of the filtrate, and researching the change curve of the ROS amount generated by silver cluster dissociation under the illumination condition. While a blank solution was used as a blank group. The curves of the ROS content of example 1, comparative example 1 and blank are shown in fig. 7. As can be seen from fig. 7, the amount of ROS generated by the dissociation of silver clusters in the light condition of the composite photothermal material provided in example 1 significantly increases with time, while the two-dimensional stibene and the blank group in comparative example 1 remain substantially unchanged, i.e., almost no ROS are generated in the light condition. In addition, the ROS amount generated by the dissociation of the silver clusters of the composite photo-thermal material provided by other examples under the illumination condition is the same as that of the ROS amount generated by the dissociation of the silver clusters in the illumination condition in the example 1, and the ROS amount is obviously increased along with the time.
3. The composite photo-thermal material is used for in vivo tumor treatment research.
The tumorigenic nude mice were randomly divided into 8 groups, treated in the following manner:
group 1: intravenous PBS;
group 2: injecting PBS intravenously and irradiating by 808nm laser;
group 3: injecting a PBS solution of antimonene (which is a composite photo-thermal material compared with the composite photo-thermal material in the embodiment 2 and does not contain silver clusters) with the surface modified with RGD polypeptide into a vein without irradiating the solution by near-infrared laser;
group 4: injecting a PBS solution of antimonene (which is a composite photo-thermal material compared with the composite photo-thermal material in the embodiment 2 and does not contain silver clusters) with the surface modified with RGD polypeptide into a vein, and irradiating the solution by using laser of 808 nm;
group 5: injecting a PBS solution of a silver cluster (relative to the composite photo-thermal material in the example 2, and without two-dimensional antimonene) with the surface modified with RGD polypeptide into a vein without irradiating the solution with near-infrared laser;
group 6: injecting PBS solution of silver clusters (compared with the composite photo-thermal material in the embodiment 2, and without two-dimensional stibene) with RGD polypeptides modified on the surface through vein, and irradiating by 808nm laser;
group 7: injecting PBS solution of silver cluster/stibene compound (composite photo-thermal material in example 2) with RGD polypeptide modified on the surface through vein without near infrared laser irradiation;
group 8: PBS solution of silver cluster/stibene compound (composite photo-thermal material of example 2) with RGD polypeptide surface modified is injected intravenously and irradiated by 808nm laser.
The dose, laser source and irradiation time were the same between groups, and were administered intravenously every 3 days for a total of 3-5 times. Tumor volume was measured every 3 days, mice were weighed every 3 days, and survival of mice was recorded every day until all PBS control mice died. One representative mouse per group was selected after one week of discontinuation of dosing, sacrificed and tumors were extirpated and their volume was measured to evaluate the status of tumor treatment. The results of the experiment are shown in table 1:
TABLE 1
As can be seen from the table 1, the group 8 is compared with the group 7, and the composite photo-thermal material can effectively play the role of photo-thermal/photodynamic cooperative therapy of the two-dimensional stibene and the silver clusters under the irradiation of the infrared laser, so that the tumor cells can be effectively killed. The killing effect is significantly higher for group 8 than for group 7.
Compared with the group 6 and the group 4, the group 8 shows that although the single silver cluster in the group 6 and the single stibene in the group 4 respectively have a certain effect of killing tumor cells under the irradiation of infrared laser, the group 6 and the group 4 have a remarkable effect of killing tumor cells lower than that of the group 8, so that the effect of effectively killing the tumor cells is effectively lower than that of the group 8, and therefore, the synergistic effect is effectively achieved between the stibene and the silver cluster in the composite photothermal material, the photothermal/photodynamic synergistic treatment effect is achieved, and the composite photothermal material is remarkably improved. The targeting agent loaded by the composite photo-thermal material can further realize accurate targeting drug delivery and release active drug components.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents and improvements made within the spirit and principle of the present invention are intended to be included within the scope of the present invention.
Claims (11)
1. The composite photo-thermal material comprises a two-dimensional photo-thermal material matrix, and is characterized in that: the two-dimensional photo-thermal material matrix is two-dimensional stibene, and nano silver particles are loaded on the two-dimensional stibene.
2. The composite photothermal material of claim 1, wherein: the thickness of the two-dimensional stibene is 0.5 nm-1 μm; and/or
The planar area of the two-dimensional stibene is 50nm2～3000nm2。
3. The composite photothermal material of claim 1, wherein: the nano silver particles are grown on the two-dimensional stibene in situ; and/or
The nano silver particles are sub-nano silver clusters; and/or
The particle size of the nano silver particles is 0.5 nm-100 nm; and/or
The molar ratio of the two-dimensional stibene to the nano silver particles is 1: 0.05-1: 0.5.
4. The composite photothermal material of any of claims 1 to 3, wherein: the surface active agent is modified and combined on the two-dimensional stibene; and/or
Also included are targeting agents bound to the two-dimensional antimonene and/or nanosilver particles.
5. The composite photothermal material of claim 4, wherein: the targeting agent comprises at least one of targeting polypeptide, growth factor and targeting agent; and/or
The molar ratio of the two-dimensional stibene to the targeting agent is 1: 0.05-1: 0.2.
6. The composite photothermal material of claim 5, wherein: the targeting polypeptide comprises at least one of RGD-PEG-PLA targeting polypeptide, DSPE-PEG-OTC growth inhibitory receptor targeting polypeptide, temperature-responsive elastin-like polypeptide, arginine-rich polypeptide, DSPE-PEG5000-RGD | phospholipid-PEG-targeting peptide and paclitaxel CSNRDARRC-PCL-PGA/TPGS polypeptide;
the growth factors include specific targeting VEGFR 2;
the targeting agent comprises at least one of an Evimos targeting agent and a T-DM1 breast cancer targeting drug.
7. The composite photothermal material of claim 4, wherein: the surfactant comprises at least one of polyethylene glycol, polyvinylpyrrolidone and Tween; and/or
The molar ratio of the two-dimensional stibene to the surfactant is 1: 0.2-1: 2.
8. The preparation method of the composite photo-thermal material is characterized by comprising the following steps of:
providing a two-dimensional stibene;
and forming nano silver particles on the two-dimensional stibene, so that the nano silver particles are loaded on the two-dimensional stibene to obtain the composite photo-thermal material.
9. The method of claim 8, wherein: the method for forming the nano silver particles on the two-dimensional stibene comprises the following steps:
preparing two-dimensional antimonene modified by a surfactant into a two-dimensional antimonene dispersion liquid;
adding a silver salt and a reducing agent into the two-dimensional stibene dispersion liquid, carrying out mixing treatment and reduction reaction, and depositing the nano-silver particles on the two-dimensional stibene in situ;
and/or
Also comprises the following steps:
and (2) preparing the composite photo-thermal material into dispersion, mixing the dispersion with a targeting agent, and combining the targeting agent on the two-dimensional stibene and/or nano-silver particles.
10. The method of claim 9, wherein: the two-dimensional antimonene dispersion liquid and the silver salt are mixed according to the molar ratio of the two-dimensional antimonene to the silver ions of 1: 0.05-1: 0.5; and/or
The silver salt is a silver ion complex; and/or
The mixing ratio of the dispersion liquid to the targeting agent ensures that the molar ratio of the two-dimensional stibene to the targeting agent is 1: 0.05-1: 0.2 on the prepared composite photo-thermal material.
11. Use of the composite photothermal material of any one of claims 1 to 7 in photothermal agents, drug carriers, photothermal catalysis or photothermal power generation materials.
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