CN114948995B - Ferro-manganese bimetal monatomic nano material and preparation method thereof - Google Patents

Ferro-manganese bimetal monatomic nano material and preparation method thereof Download PDF

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CN114948995B
CN114948995B CN202210881042.5A CN202210881042A CN114948995B CN 114948995 B CN114948995 B CN 114948995B CN 202210881042 A CN202210881042 A CN 202210881042A CN 114948995 B CN114948995 B CN 114948995B
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manganese
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CN114948995A (en
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张斌
方雪杨
杨德才
李晨曦
聂国辉
刘洋
张愿愿
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Shenzhen Second Peoples Hospital
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    • B82Y40/00—Manufacture or treatment of nanostructures
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    • B82—NANOTECHNOLOGY
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    • B82Y5/00—Nanobiotechnology or nanomedicine, e.g. protein engineering or drug delivery
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    • C01B25/00—Phosphorus; Compounds thereof
    • C01B25/14—Sulfur, selenium, or tellurium compounds of phosphorus
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2002/00—Crystal-structural characteristics
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    • C01—INORGANIC CHEMISTRY
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    • C01P2004/03—Particle morphology depicted by an image obtained by SEM
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    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/20—Particle morphology extending in two dimensions, e.g. plate-like
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    • Y02E60/30—Hydrogen technology
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Abstract

The application belongs to the field of medical materials, and particularly relates to a ferro-manganese bimetal monatomic nano material and a preparation method thereof, wherein the ferro-manganese bimetal monatomic nano material comprises the following steps: a divalent iron monoatomic atom, a divalent manganese monoatomic atom, the divalent iron monoatomic atom and the divalent manganese monoatomic atom forming a hexacoordination with an atom of phosphorus triselenide. The ferro-manganese bimetallic monatomic nano material can play a role in catalyzing in a tumor microenvironment or under high-concentration hydrogen peroxide so as to play a role in treating tumors, so that the ferro-manganese bimetallic monatomic nano material has no harm to normal tissues and organs; the material contains two active sites of iron and manganese, and the synergistic catalytic treatment effect is exerted in the same system, so that the effect can be mutually improved, and more efficient multi-modal tumor treatment is realized; the double active sites of the material act together to improve the catalytic capability and the metal utilization rate.

Description

Ferro-manganese bimetal monatomic nano material and preparation method thereof
Technical Field
The application belongs to the field of medical materials, and particularly relates to a ferro-manganese bimetal monatomic nano material and a preparation method thereof.
Background
Cancer seriously threatens the health of human beings, and people are actively searching for a method for treating cancer. At present, the clinical tumor treatment usually comprises surgical treatment, chemotherapy, radiotherapy and the like, but has the defects of easy relapse after operation, large side effect, high treatment cost and the like. In addition, due to the complexity and heterogeneity of tumors, it is often difficult to achieve the desired effect with a single treatment modality. Therefore, the exploration of a novel efficient and accurate tumor diagnosis and treatment strategy is very important.
In recent years, with the rise of the concept of "nanocatalysis medicine", the concept of the method is based on responding to H in the microenvironment of tumors 2 O 2 The tumor catalytic therapy becomes a popular anti-tumor strategy due to the advantages of specificity, high efficiency, safety and the like, but the catalytic efficiency of the nano catalytic material is limited, so that the catalytic therapy efficiency is low, and the nano catalytic material with higher concentration is often used for achieving better therapeutic effect, thereby inevitably damaging the organism.
The existing Single-atom catalysts (SACs) have excellent catalytic activity and metal utilization rate due to the unique electronic structure, low coordination environment and atomically dispersed metals, and a Fe-monoatomic-supported nano catalyst (PSAF NCs) has been researched and developed to catalyze H highly expressed in tumors under the stimulation of near infrared light 2 O 2 A large amount of toxic OH (hydroxyl free radical) is generated, and the in-situ specific treatment of the tumor is realized; research reports that the Mn-based single-atom nano material catalytic material can catalyze H 2 O 2 Decomposition to O 2 (ii) a The existing hyaluronic acid modified FeCo bimetallic synergistic monatomic catalyst has the defect of high catalytic toxicity.
Disclosure of Invention
The application provides a ferro-manganese bimetallic monatomic nanomaterial to solve the technical problem that the existing bimetallic monatomic nanomaterial is high in toxicity.
In a first aspect, an embodiment of the present application provides a ferrimanganic bimetallic monatomic nanomaterial, including: a divalent iron monoatomic atom, a divalent manganese monoatomic atom, the divalent iron monoatomic atom and the divalent manganese monoatomic atom forming a hexacoordination with an atom of phosphorus triselenide.
In some embodiments of the present application, the grain size of the ferrimanganic bimetallic monatomic nanomaterial is 90-120nm.
In some embodiments of the present application, the fe-mn bimetal monatomic nanomaterial is in a layered form, and the thickness is 9-11nm.
In some embodiments of the present application, in the ferrimanganic bimetallic monatomic nanomaterial, the molar ratio of the iron monatomic, the manganese monatomic, the phosphorus atom, and the selenium atom is 1.
In some embodiments of the present application, the heat transfer efficiency is 100 μ M H 2 O 2 Under an acidic condition, the wavelength of the near-infrared laser is 808nm, and the irradiation power is 1.0W/cm 2 Under the irradiation condition of (3), the oxygen yield of the ferro-manganese bimetallic monatomic nano material is more than or equal to 8.72mg/L.
In a second aspect, embodiments of the present application provide a method for preparing a ferro-manganese bimetallic monatomic nanomaterial, where the method includes the following steps:
providing an iron simple substance, a manganese simple substance, a phosphorus simple substance and a selenium simple substance, wherein the molar ratio is 1;
carrying out reaction under the conditions of vacuumizing and heating to obtain a mixture;
and crushing the mixture, and stripping in an ultrasonic liquid phase to obtain the ferro-manganese bimetallic monatomic nano material.
In some embodiments of the present application, the target temperature of the heating is 700 ℃.
In some embodiments of the present application, the heating rate is greater than or equal to 5 ℃/min.
In some embodiments of the present application, the vacuum degree of the vacuum is less than or equal to 0.001Pa.
In some embodiments of the present application, the solvent in the ultrasound liquid phase comprises polyvinylpyrrolidone or chitosan.
Compared with the prior art, the technical scheme provided by the embodiment of the application has the following advantages:
the utility model provides a ferro-manganese bimetal monatomic nanomaterial, including: the ferromanganese bimetal monatomic nano material can play a catalytic capability in a tumor microenvironment or under high-concentration hydrogen peroxide (the concentration of the hydrogen peroxide is generally 100 mu M), and further has an effect of treating tumors, so that the ferromanganese bimetal monatomic nano material is harmless to normal tissues and organs; the two active sites of iron and manganese in the ferro-manganese bimetallic monatomic nano material play a role in the synergistic catalytic treatment of tumors in the same system, so that the effects can be mutually improved, and more efficient multi-modal treatment of tumors can be realized; in addition, the double active sites act together to improve the catalytic capability and the metal utilization rate.
Drawings
The accompanying drawings, which are incorporated in and constitute a part of this specification, illustrate embodiments consistent with the invention and together with the description, serve to explain the principles of the invention.
In order to more clearly illustrate the embodiments or technical solutions in the prior art of the present invention, the drawings used in the description of the embodiments or prior art will be briefly described below, and it is obvious for those skilled in the art to obtain other drawings without inventive exercise.
Fig. 1 is a morphology and a structural diagram of a ferro-manganese bi-metal single-atom nano material provided in an embodiment of the present application;
FIG. 2 is an X-ray photoelectron spectrum of a bimetallic-iron-manganese monatomic nanomaterial provided in an embodiment of the present application;
FIG. 3 is a graph of photo-thermal and catalytic performance of a FeMn bimetallic monatomic nanomaterial provided in examples herein and a nanomaterial of a comparative example set;
FIG. 4 is a graph showing the tumor catalytic effects of the FeMn bimetal monatomic nanomaterial provided in the example of the present application and the nanomaterial of the comparative example group;
FIG. 5 shows the photothermal effect of the Fe-Mn bimetallic monatomic nanomaterial provided in the examples of the present application and the nanomaterial of the comparative example group on the tumor site of a mouse;
fig. 6 is a graph illustrating the biosafety evaluation effect of the ferrimanganic bimetallic monatomic nanomaterial provided in the embodiment of the present application.
Detailed Description
In order to make the objects, technical solutions and advantages of the embodiments of the present application clearer, the technical solutions in the embodiments of the present application will be clearly and completely described below with reference to the drawings in the embodiments of the present application, and it is obvious that the described embodiments are some embodiments of the present application, but not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present application.
Throughout the specification, unless otherwise specifically noted, terms used herein should be understood as having meanings as commonly used in the art. Accordingly, unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. If there is a conflict, the present specification will control. The terminology used herein is for the purpose of describing particular embodiments only and is not intended to limit the scope of the present invention. For example, room temperature may refer to a temperature in the interval of 10 to 35 ℃.
Unless otherwise specifically stated, various raw materials, reagents, instruments, equipment and the like used in the present invention are commercially available or can be prepared by existing methods.
In order to solve the technical problems, the general idea of the embodiment of the application is as follows:
according to an exemplary embodiment of the present invention, there is provided a ferro manganese bi-metal single atom nano material, including: a divalent iron monoatomic atom, a divalent manganese monoatomic atom, the divalent iron monoatomic atom and the divalent manganese monoatomic atom forming a hexacoordination with an atom of phosphorus triselenide.
In the embodiment of the application, two active sites of divalent iron monoatomic atom and divalent manganese monoatomic atom are used for leadingWhich can efficiently and synergistically catalyze H in the same system 2 O 2 Generation of OH (hydroxyl radical) and O 2 . The bionic double-monoatomic catalytic material utilizes the synergistic catalytic capability of double metals and single atoms to efficiently produce OH and O in a tumor microenvironment 2 And the photothermal effect of the material is combined, so that the tumor can be treated by photothermal/chemodynamics. On the one hand, iron monoatoms catalyze endogenous H of tumor cells by Fenton reaction 2 O 2 Generating toxic OH with higher activity to induce the apoptosis of tumor cells; on the other hand, a manganese single atom may be reacted by catalyzing H 2 O 2 Release a large amount of O 2 Relieving tumor hypoxia state
In the embodiment of the application, the photothermal effect means that after the material is irradiated by light, photon energy and crystal lattice interact, vibration is aggravated, the temperature is increased, the electrical characteristics of substances are caused by the change of the temperature, and the tumor part temperature is increased under the irradiation of near-infrared laser due to the fact that the ferro-manganese bimetal monatomic nano material has the photothermal effect, so that tumor cells are directly necrotized.
In some embodiments, the ferro-manganese bimetallic monatomic nanomaterial has a particle size of 90-120nm.
In the embodiment of the application, the particle size is controlled to be about 100nm, so that the material has the advantages of easy absorption by organisms and good biocompatibility compared with a blocky ferro-manganese bimetallic single-atom material.
In some embodiments, the ferro-manganese bimetallic monatomic nanomaterial is layered and has a thickness of 9-11nm.
In the embodiment of the application, the thickness is controlled to be about 10nm, and compared with a massive ferro-manganese bimetallic monatomic material, the material has a larger specific surface area, and the performance of the bimetallic monatomic material is more easily exerted.
In some embodiments, the molar ratio of iron monoatomic atoms, manganese monoatomic atoms, phosphorus atoms, and selenium atoms in the ferrimanganic bimetallic monatomic nanomaterial is 1.
In the examples of the present application, by controlling the molar ratio of iron monoatomic atoms, manganese monoatomic atoms, phosphorus atoms, and selenium atoms to 1.
In some embodiments, at 100 μ M H 2 O 2 Under an acidic condition, the wavelength of the near-infrared laser is 808nm, and the irradiation power is 1.0W/cm 2 Under the irradiation condition of (3), the oxygen yield of the ferro-manganese bimetallic monatomic nano material is more than or equal to 8.72mg/L.
According to another exemplary embodiment of the present invention, there is provided a method for preparing a bimetal-manganese monatomic nanomaterial, the method comprising the steps of:
s1, providing a simple substance of iron, a simple substance of manganese, a simple substance of phosphorus and a simple substance of selenium, wherein the molar ratio of the simple substance of iron to the simple substance of manganese to the simple substance of phosphorus to the simple substance of selenium is 1;
s2, reacting under the conditions of vacuumizing and heating to obtain a mixture;
and S3, crushing the mixture, and stripping in an ultrasonic liquid phase to obtain the ferro-manganese bimetallic monatomic nano material.
In some embodiments, the target temperature of the heating is ≧ 700 ℃.
In some embodiments, the rate of heating is greater than or equal to 5 deg.C/min.
In some embodiments, the vacuum is less than or equal to 0.001Pa.
In some embodiments, the solvent in the ultrasonic liquid phase comprises polyvinylpyrrolidone or chitosan.
The process of the present invention will be described in detail below with reference to examples, comparative examples and experimental data.
Example 1 preparation of a bimetal-manganese monatomic nanomaterial
High-purity elemental Fe, mn, P, se (1. Heating to 700 ℃ at a heating rate of 5 ℃ per minute, and preserving the heat for 100 hours to ensure that the simple substances fully react to synthesize the required compound. Then naturally cooling to room temperature, breaking the quartz tube to collect the compound (bulk Fe/Mn @ PSe) after the reaction is completed 3 ). Subsequently, the massive multilayer Fe/Mn @ PSe 3 In Polyvinylpyrrolidone (PV)P) to obtain a nano flaky material, namely a ferro-manganese bimetal single atom nano material, namely a product B in the figure 1.
Respectively using Scanning Electron Microscope (SEM), transmission Electron Microscope (TEM), atomic Force Microscope (AFM) and Dynamic Light Scattering (DLS) experiments to prepare the ferro-manganese bimetallic monatomic nanomaterial (Fe/Mn @ PSe) 3 ) The morphology, structure and particle size of (a) were studied and analyzed, and the results are shown in fig. 1: (A) Scanning electron microscope photos of multilayer blocky ferro-manganese bimetal single atoms; as can be seen from A in FIG. 1, the material is a layered two-dimensional structure and forms an ultrathin sheet-like structure after liquid phase stripping, (B) ultrathin two-dimensional Fe/Mn @ PSe 3 Transmission electron microscope photograph of (1); (C) Ultrathin two-dimensional Fe/Mn @ PSe 3 The abscissa is the particle size and the ordinate is the relative percentage of the particle size; as can be seen from C in FIG. 1, the particle size distribution is uniform, and the size is about 100nm (D in FIG. 1), and the ultrathin two-dimensional Fe/Mn @ PSe 3 AFM images of (1); as can be seen from FIG. 1, the Energy Dispersive Spectroscopy (EDS) shows that iron and manganese are present in PSe 3 The two-dimensional carrier is uniformly distributed on the ultrathin two-dimensional Fe/Mn @ PSe 3 Element distribution map of (a); (F) Ultrathin two-dimensional Fe/Mn @ PSe 3 Illustrating Selected Area Electron Diffraction (SAED) confirmed Fe/Mn @ PSe 3 A regular crystal structure. The results of X-ray photoelectron spectroscopy (XPS) measurement are shown in FIG. 2. Shown by A-C in FIG. 2, fe/Mn @ PSe 3 The XPS spectrum of (a), wherein the abscissa is the binding energy of the nuclei and the ordinate is the relative intensity, as shown in fig. 2 a and B, and the abscissa is the binding energy of the nuclei and the ordinate is the relative intensity, i.e., the pulse divided by the second, as shown in fig. 2C; in FIG. 2, D-E is a XANES map, and the abscissa in D-E in FIG. 2 is the binding energy of the nucleus and the ordinate is normalized data; in fig. 2, G-H represent functional relationships illustrating the existence of fe and mn in the state of single atoms, respectively, wherein the abscissa is the distance from the target atom, and the ordinate is the fourier transform of the acquired signal data; in FIG. 2, F-I represents the EXAFS spectrum and the corresponding wavelet analysis spectrum.
As shown in A-C in figure 2, the material is verified to be successfully loaded with the ferro-manganese element, and the iron monoatomic atom and the manganese monoatomic atom exist in a +2 valence state respectively. The valence states of iron and manganese in the material are also obtained by X-ray absorption near-edge structure spectrum (XANES), and the near-edge spectrum shows that the absorption edge of iron in the material is only higher than that of Fe foil, which proves that Fe is coordinated with elements with low electronegativity; d-2 in FIG. 2 also demonstrates that Mn, which is in a lower valence state, is coordinated to an atom with a lower electronegativity. In order to determine whether the iron element and the manganese element exist in the form of a single atom, we performed extended X-ray absorption fine structure (EXAFS) analysis on the material, as shown by F-2 in fig. 2, in which iron is hexacoordinated as Fe-Se and a hexacoordinated Fe-P is further provided at the outer layer, and manganese is coordinated as Fe and as Mn-Se and Mn-P, so that no metallic bond exists between iron and manganese, and both of them exist in the form of a metallic single atom.
Performance detection
1) Photothermal and catalytic performance analysis of bimetallic monatomic material
Simple substance (Fe @ PSe) passing through different proportion 3 Is Fe, P, and the molar ratio of Se is 1; mn @ PSe 3 Is Mn, P, se molar ratio is 1. ) Carrying out reaction under the conditions of vacuumizing and heating to obtain a mixture; crushing the mixture, and stripping in ultrasonic liquid phase to obtain different nano materials, in turn Fe @ PSe 3 (iron alone monoatomic support to PSe) 3 Coordinate bond formation), mn @ PSe 3 (Single manganese monoatomic support to PSe) 3 Forming a coordinate bond) and Fe @ PSe 3 +Mn@PSe 3 (i.e. iron alone is monoatomic to PSe) 3 Formation of coordination bonds and support of a single manganese atom on PSe 3 Formation of coordinate bond, simultaneous treatment with two materials) and the examples of the present application gave Fe/Mn @ PSe 3 The reaction results obtained by performing experiments on the nano material (the ferro-manganese bimetallic single-atom nano material of the application) are as follows.
The experimental method preliminarily investigates the ferro-manganese bimetal monatomic nano material (Fe/Mn @ PSe) 3 ) Photothermal effect and catalytic performance. Under simulated tumor microenvironment conditions (in acidic pH6.5 PBS, 100. Mu.M H) 2 O 2 ) And irradiation with near-infrared laser (808 nm, 1W/cm) 2 ）, Fe/Mn@PSe 3 Exhibits a relatively Fe @ PSe 3 、Mn@PSe 3 And Fe @ PSe 3 +Mn@PSe 3 Superior catalysis of H 2 O 2 Production of O 2 And. OH capacity. As shown in FIG. 3, fe/Mn @ PSe 3 Has good photothermal conversion ability (A-C in FIG. 3): as shown by A-B in FIG. 3, different concentrations of Fe/Mn @ PSe 3 Temperature rise curve of the solution under the irradiation of the same near infrared laser intensity and corresponding thermal imaging graph, wherein the abscissa of FIG. 3A is time, the ordinate is temperature, and the solutions (water), 625ppm, 125ppm, (C in FIG. 3) in the graph are Fe/Mn @ PSe with the same concentration 3 The temperature rise curve chart of the solution under the irradiation of near-infrared laser with different intensities explains Fe/Mn @ PSe 3 The photo-thermal conversion performance is good; FIG. 3D is a graph showing the temperature rise and drop curves of various nanomaterials with or without near-infrared laser irradiation, and it can be seen from the graph D in FIG. 3 that the laser irradiation is started from 0min, the temperature continues to rise, and when 7min, the laser irradiation is stopped, and the temperature drops accordingly; the laser is irradiated again at 14min, the temperature rises again and can still reach 50 ℃, and the circulation is carried out in sequence, thereby showing that the thermal stability is good; (3E-3F) at pH6.5, 100 μ M MH 2 O 2 Under near infrared laser irradiation, fe @ PSe 3 、Mn@PSe 3 、Fe@PSe 3 +Mn@PSe 3 And Fe/Mn @ PSe 3 Catalysis H 2 O 2 Produce O 2 And OH diagram. As shown by E in FIG. 3, fe/Mn @ PSe 3 The oxygen production can reach 8.72mg/L after the catalyst is maintained for 10 minutes, while Fe @ PSe 3 、Mn@PSe 3 And Fe @ PSe 3 +Mn@PSe 3 The concentration of the active ingredients reaches 0.56, 4.93 and 5.31mg/L in sequence. As shown by F in FIG. 3, fe/Mn @ PSe 3 Meanwhile, the product has better OH production capability than other three groups; the blue color of the Methylene Blue (MB) gradually fades due to the degradation of MB by hydroxyl radicals that can react with MB. Thus, H in FIG. 3 indicates that Fe/Mn @ PSe under acidic conditions and laser irradiation 3 The ability of generating hydroxyl radicals with the highest efficiency can be exerted. These experimental results preliminarily illustrate Fe/Mn @ PSe 3 With co-catalysis of H 2 O 2 Produce O 2 And OH, the method lays a preliminary foundation for the project to further explore the multi-modal anti-tumor research of the project at the cellular and animal level.
2) Tumor catalytic treatment capacity of bimetallic monatomic material
Respectively mixing Fe @ PSe 3 、Mn@PSe 3 And Fe @ PSe 3 +Mn@PSe 3 And the examples of the present application gave Fe/Mn @ PSe 3 The nano material is used for experiment, 4 groups of materials are respectively put in CT26 tumor cells to be incubated together for 6 hours, and then near infrared laser irradiation (808 nm, 1.5W/cm) 2 10 min), the following reaction results were obtained after 18 hours of standing in an incubator.
As shown in A-B in FIG. 4, it is tumor cells and Fe @ PSe 3 、Mn@PSe 3 、Fe@PSe 3 +Mn@PSe 3 , Fe/Mn@PSe 3 Co-incubation and survival of cells irradiated with near infrared laser. As shown in A in FIG. 4, green represents live cells and red represents dead cells, so that Fe/Mn @ PSe can be seen 3 Has superior ability to kill tumor than the other three groups. As shown by B in FIG. 4, with increasing drug concentration, fe @ PSe 3 、Mn@PSe 3 、Fe@PSe 3 +Mn@PSe 3 , Fe/Mn@PSe 3 The survival rate of tumor cells shows a descending trend, wherein Fe/Mn @ PSe 3 The effect of (2) is most obvious. In addition, fe/Mn @ PSe was evaluated 3 Effect on intracellular ROS levels, as shown by C in FIG. 4, fe/Mn @ PSe under near Infrared laser irradiation 3 Is more capable of promoting the generation of Reactive Oxygen Species (ROS) in cells (compared with Fe @ PSe) 3 、Mn@PSe 3 、Fe@PSe 3 +Mn@PSe 3 ) These results further confirm that the bimetallic monatomic material can exert a synergistic effect, and realize efficient tumor treatment. In addition, we evaluated the ability of the bimetallic monatomic to catalyze the production of oxygen from hydrogen peroxide in the tumor microenvironment by measuring blood oxygen concentration in tumor tissue. As shown in FIG. 4D-E, fe/Mn @ PSe 3 After the compound is acted on a mouse tumor part, the blood oxygen concentration in tumor tissues is gradually increased along with time, and the hypoxia problem of a tumor microenvironment is relieved.
Fluorescence images and tumor cell presence after staining with Calcein-AM (Calcein-AM, original is green) and propidium iodide (PI dye, release Red, original is Red) as shown in A-B in FIG. 4The activity rate, in FIG. 4A, laser is 808nm near-infrared laser; in FIG. 4B, the abscissa is Fe @ PSe 3 、Mn@PSe 3 、Fe@PSe 3 +Mn@PSe 3 、Fe/Mn@PSe 3 The concentration of the 4 nano materials and the ordinate of the concentration are the survival rate of tumor cells; fluorescence images of Reactive Oxygen Species (ROS) after treatment of tumor cells under laser irradiation in different groups, as shown in fig. 4C; deoxyhemoglobin (HbR) and oxyhemoglobin (HbO) in tumor sites as indicated by D-E in FIG. 4 2 ) The photoacoustic image and the corresponding quantitative analysis of (1) are shown as E in FIG. 4, where the abscissa is time and the ordinate is the oxygen saturation content of blood, illustrating Fe/Mn @ PSe 3 The nanomaterial generates oxygen.
In order to study Fe/Mn @ PSe 3 Photothermal effect at tumor sites of mice, C57BL/6J type mice (age of mice 6 to 8 weeks) were purchased from Guangzhou Qingle Life sciences, inc., and CT26 colon cancer-bearing mice models were constructed. The injection amount of the nano material injected into the tumor part of the mouse is respectively as follows: fe @ PSe 3 Group is 4mg/kg, mn @ PSe 3 Group 4mg/kg, fe @ PSe 3 +Mn@PSe 3 Group 4mg/kg Fe @ PSe 3 With 4mg/kg Mn @ PSe 3 ；Fe/Mn@PSe 3 Group 8mg/kg, which refers to the mass of material per kg of mouse body weight. The injection is administered twice a week for one month, and the tumor site is illuminated (808 nm, 1.5W/cm) 2 10 min), the results shown in FIG. 5 were obtained. As shown in A-B in FIG. 5, it is PBS and Fe/Mn @ PSe under laser irradiation 3 A thermography of the tumor site and a corresponding temperature profile; as shown in A-B in FIG. 5, under the irradiation of near-infrared laser, the temperature of the tumor part of the mouse gradually increases and can reach more than 45 ℃; the abscissa of B in fig. 5 is time and the ordinate is temperature. In FIG. 5, C is a different group under near infrared light irradiation (Fe @ PSe) 3 、Mn@PSe 3 、Fe@PSe 3 +Mn@PSe 3 , Fe/Mn@PSe 3 ) The tumor growth curve of (1.5W/cm) is given twice a week (808 nm laser irradiation after tumor injection 2 10 min) for one month, time on the abscissa and tumor volume on the ordinate; d in FIG. 5 shows tumor-bearing mice of different treatment groupsThe tumor weight after the above treatment, the abscissa is time, and the ordinate is tumor weight. As shown by C-D in FIG. 5, fe/Mn @ PSe 3 The ability of inhibiting the growth of tumors is superior to that of other groups, and the ability of bimetallic synergistic catalysis to treat tumors is further verified.
3) Biosafety assessment of bimetallic monatomic materials
In order to check whether the monoatomic material can damage organs, C57BL/6J mice (mice aged 6 to 8 weeks) are selected, purchased from Guangzhou Qingle Life sciences, inc., and are in good health conditions before administration, randomly divided into four tumor bodies, injected and administered twice a week for one month (after the tumor part is injected with the medicine, the injected medicine irradiates laser 808nm, and the irradiation speed is 1.5W/cm) 2 10 min) group: PBS, PBS + laser, fe/Mn @ PSe 3 , Fe/Mn@PSe 3 + laser, analysis of 3 typical blood biochemical indicators, alanine Aminotransferase (ALT), aspartate Aminotransferase (AST) and Blood Urea Nitrogen (BUN), as shown in fig. 6A-C, are serum biochemical indicators of tumor-bearing mice of different treatment groups (a-C in fig. 6) and HE staining pathology of major organs of mice (D in fig. 6). As shown in A-C in FIG. 6, 1, 2, 3 and 4 are PBS control group, PBS and 808nm near-infrared laser-treated control group, fe/Mn @ PSe 3 Nanomaterial, fe/Mn @ PSe 3 Nano material and 808nm near infrared laser processing group; the ordinate of A in FIG. 6 is the concentration of alanine Aminotransferase (ALT), the ordinate of B in FIG. 6 is the concentration of aspartate Aminotransferase (AST), and the ordinate of C in FIG. 6 is the concentration of Blood Urea Nitrogen (BUN), indicating that no significant abnormality was found between the groups, indicating that Fe/Mn @ PSe of the present application 3 The toxicity of the nano material to normal organs is negligible. Hematoxylin and eosin (H) was administered to major organs such as heart, liver, spleen, lung and kidney of mice in different treatment groups&E) Staining histological analysis, as shown by D in 6, the stained tissues of heart, liver, spleen, lung and kidney are shown in the figure from top to bottom, PBS control group, PBS and 808nm near infrared laser treated control group, fe/Mn @ PSe are shown from left to right 3 Nanomaterial, fe/Mn @ PSe 3 Nano material and 808nm near infrared laser processing group, all of which are not observedTo the obvious pathological abnormality or inflammation, further proves that the Fe/Mn @ PSe of the application 3 Biological safety of the nanomaterial (D in fig. 6).
It is noted that, in this document, relational terms such as "first" and "second," and the like, may be used solely to distinguish one entity or action from another entity or action without necessarily requiring or implying any actual such relationship or order between such entities or actions. Also, the terms "comprises," "comprising," or any other variation thereof, are intended to cover a non-exclusive inclusion, such that a process, method, article, or apparatus that comprises a list of elements does not include only those elements but may include other elements not expressly listed or inherent to such process, method, article, or apparatus. Without further limitation, an element defined by the phrases "comprising a," "8230," "8230," or "comprising" does not exclude the presence of additional like elements in a process, method, article, or apparatus that comprises the element.
The above description is merely illustrative of particular embodiments of the invention that enable those skilled in the art to understand or practice the invention. Various modifications to these embodiments will be readily apparent to those skilled in the art, and the generic principles defined herein may be applied to other embodiments without departing from the spirit or scope of the invention. Thus, the present invention is not intended to be limited to the embodiments shown herein but is to be accorded the widest scope consistent with the principles and novel features disclosed herein.

Claims (9)

1. A ferro-manganese bimetallic monatomic nanomaterial with photothermal effect for catalytic therapy of tumors, comprising: a divalent iron monoatomic atom and a divalent manganese monoatomic atom which independently form hexacoordination with a selenium atom and a phosphorus atom in phosphorus triselenide, respectively, and no metal bond exists between the divalent iron monoatomic atom and the divalent manganese monoatomic atom; the molar ratio of the divalent iron monoatomic atom to the divalent manganese monoatomic atom to the phosphorus atom to the selenium atom is 1.
2. The ferro-manganese bimetallic monatomic nanomaterial of claim 1, wherein the particle size of the ferro-manganese bimetallic monatomic nanomaterial is 90-120nm.
3. The ferro-manganese bimetallic monatomic nanomaterial of claim 1, wherein the ferro-manganese bimetallic monatomic nanomaterial is layered and has a thickness of 9-11nm.
4. The ferro-manganese bi-metal monatomic nanomaterial of claim 1,
at 100 mu M H 2 O 2 Under an acidic condition, the wavelength of the near-infrared laser is 808nm, and the irradiation power is 1.0W/cm 2 Under the irradiation condition of (2), the oxygen yield of the ferro-manganese bimetallic single-atom nano material is more than or equal to 8.72mg/L.
5. A method for preparing the ferro-manganese bimetallic monatomic nanomaterial of any one of claims 1 to 4, characterized in that the method comprises the following steps:
providing an iron simple substance, a manganese simple substance, a phosphorus simple substance and a selenium simple substance, wherein the molar ratio is 1;
carrying out reaction under the conditions of vacuumizing and heating to obtain a mixture;
and crushing the mixture, and stripping in an ultrasonic liquid phase to obtain the ferro-manganese bimetallic monatomic nano material.
6. The method of claim 5, wherein the heating is performed at a target temperature of 700 ℃ or higher.
7. The method of claim 5, wherein the heating rate is greater than or equal to 5 ℃/min.
8. The method of claim 5, wherein the degree of vacuum of the vacuum is less than or equal to 0.001Pa.
9. The method of claim 5, wherein the solvent in the ultrasound liquid phase comprises polyvinylpyrrolidone or chitosan.
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