Magnetic fluorescent bifunctional composite material powder and preparation method and application thereof

Abstract

The application discloses a kind of magnetic fluorescent bifunctional composite material powder and its preparation method and application, the composite material powder includes polymer, perovskite quantum dot and magnetic nanopowder;The polymer is coated with the perovskite quantum dot and the magnetic nanopowder;The perovskite quantum dot and the magnetic nanopowder are dispersed in the polymer.This preparation method makes that perovskite quantum dot is completed synthesis in drying process, so as to have the advantages of simple synthesis process, low preparation cost;The polymer in the composite material powder will be completely coated with magnetic nanopowder and perovskite quantum dot, internal nanoparticle will not contact target inspection object, avoid the influence of toxicity and microsphere surface can be further modified processing;The composite powder has excellent optical performance and strong magnetism, the material can respond to external magnetic field quickly, so the material has certain application prospect in separation sensing, medical diagnosis and biological imaging etc.

Description

TECHNICAL FIELD

[0001] The application relates to a magnetic fluorescent bifunctional composite material powder and a preparation method and application thereof, and belongs to the field of composite material powder preparation. BACKGROUND

[0002] Perovskite quantum dots have the characteristics of simple preparation process, low cost, high quantum yield, etc., and have become a research hotspot in the fields of chemistry and materials. Great progress has been made in the fields of solar cells, high-sensitivity photodetectors and display, and many companies have launched their own products, gradually moving from the laboratory to the production road. Due to the advantages of perovskite quantum dots, their applications are gradually expanding to the interdisciplinary fields of biology and medicine, such as biological labeling, cell recognition and biological imaging. Biological labeling and biological tracing have always been important in the field of biological analysis, and there is a deep accumulation of experience in the research of related content. The most commonly used is organic fluorescent dye, but due to its wide emission peak, different organic dyes require different excitation light sources, which greatly limits the wide application of organic dyes. Quantum dot technology-based biological tracing technology has gradually entered this field, and is widely used in the fields of medicine and pharmacy due to its rapid observation, high sensitivity and low price.

[0003] The method for preparing magnetic fluorescent microspheres using perovskite quantum dots includes: adsorbing quantum dots on magnetic materials to form nanometer microspheres, and coating the magnetic particles and perovskite quantum dots with polymers. In the patent CN 112924667A, perovskite quantum dots are adsorbed on the surface of microspheres by magnetic nanoparticles to obtain composite nanomaterials, but the perovskite quantum dots are directly in contact with the target inspection object, which is easy to cause toxicity. In the patents CN 111100628 A, CN 1539913 A and CN 111849478 A, perovskite quantum dots and magnetic nanoparticles are coated by using the swelling process of polymer spheres in solvents, and high-molecular polymer-coated magnetic fluorescent particles are obtained. This coating process is to first synthesize perovskite quantum dots and magnetic nanoparticles, and then use polymer swelling adsorption. The synthesis process is complex, and part of the quantum dots and magnetic particles are still located on the surface of the microspheres, which is not conducive to the next application. In the patent 1693411A, the fluorescent particles and magnetic nanoparticles are embedded in the high-molecular microspheres by using the spray drying method, and the ball forming and embedding are completed in one step. The method is relatively simple. In the patent, the fluorescent particles and magnetic nanoparticles are synthesized and then embedded in the high-molecular microspheres by using the spray drying method. The process flow of the separate synthesis process is relatively complex. SUMMARY

[0004] According to one aspect of the present application, a magnetic fluorescent dual-functional composite material powder is provided, wherein a polymer in the composite material powder coats a magnetic nano-powder and a perovskite quantum dot, the internal nano-particles cannot contact a target object, and the influence of toxicity is avoided; since the composite powder is wrapped by the polymer, the polymer has better biocompatibility than inorganic substances, and is more widely used in biological applications; moreover, the composite powder is more easily surface-modified in the presence of the polymer surface, and its application is further expanded; the composite material powder has optical and magnetic properties, and can rapidly respond to an external magnetic field, so that the material can further introduce different functional groups on the polymer surface to connect different types of receptor molecules on the microsphere surface, lay a foundation for subsequent biological experiments, and has certain application prospects in the fields of separation sensing, medical diagnosis and biological imaging.

[0005] A magnetic fluorescent dual-functional composite material powder, comprising a polymer, perovskite quantum dots and magnetic nano-powder.

[0006] The polymer coats the perovskite quantum dots and the magnetic nano-powder.

[0007] The perovskite quantum dots and the magnetic nano-powder are dispersed in the polymer.

[0008] The perovskite quantum dots and the magnetic nano-powder are uniformly dispersed in the polymer, and the polymer completely coats the perovskite quantum dots and the magnetic nano-powder.

[0009] Optionally, the particle size of the composite material powder is 0.1 μm-100 μm.

[0010] Preferably, the particle size of the composite material powder is 0.2 μm-5 μm.

[0011] Optionally, the particle size of the composite material powder is independently selected from any value or a range value between any two of 0.1 μm, 0.5 μm, 1 μm, 5 μm, 10 μm, 20 μm, 30 μm, 40 μm, 50 μm, 60 μm, 70 μm, 80 μm, 90 μm and 100 μm.

[0012] Optionally, the particle size of the magnetic nano-powder is 1 nm-100 nm.

[0013] Preferably, the particle size of the magnetic nano-powder is 3 nm-10 nm.

[0014] Optionally, the magnetic nanopowder particle size is independently selected from any value or a range between any two values of 1 nm, 5 nm, 10 nm, 15 nm, 20 nm, 30 nm, 40 nm, 50 nm, 60 nm, 70 nm, 80 nm, 90 nm, 100 nm.

[0015] The surface of the magnetic nanopowder can be modified by hydrophilic or oleophilic molecules.

[0016] Optionally, the polymer is selected from at least one of polyvinylidene fluoride, polyvinylidene fluoride, trifluoroethylene copolymer, polyacrylonitrile, polyvinyl acetate, cellulose acetate, cyano cellulose, polysulfone, aromatic polyamide, polyimide, polycarbonate, polystyrene, polymethyl methacrylate, poly lauryl methacrylate.

[0017] Optionally, in the perovskite quantum dot:

[0018] The perovskite quantum dot is at least one of the structural formula ABX3, A3B2X9, A2BX6;

[0019] wherein A is selected from at least one of NH2CHNH2 + , CH3NH3 + , Cs + , Rb + , K + ;

[0020] B is selected from at least one of Pb 2+ , Sn 2+ , Bi 3+ , Ti 3+ , Zn 2+ , Ni 2+ , Cd 2+ , Al 3+ , Mn 2+ , Mn 4+ , Ge 3+ ;

[0021] C is selected from an aromatic group or a C3-C 18 alkyl organic amine cation;

[0022] X is selected from at least one of Br - , I - , SCN - , carboxylate.

[0023] Preferably, the surface ligand structural formula is CX;

[0024] C is selected from an aromatic group or a C3-C 18 alkyl organic amine cation;

[0025] X is selected from Br- 、I - 、SCN - 、carboxylate, at least one of them.

[0026] Optionally, the magnetic nanopowder is selected from at least one of Fe3O4, Fe2O3.

[0027] According to yet another aspect of the present application, a method for preparing a magnetic fluorescent dual-functional composite powder is provided.

[0028] The magnetic fluorescent polymer powder of polymer-coated perovskite quantum dots and magnetic nanopowder is prepared by a one-step method using a spray drying method. In the method, the perovskite quantum dots are synthesized during the drying process, thereby achieving a simple synthesis process and low preparation cost.

[0029] The method for preparing the composite powder comprises the following steps:

[0030] The mixed solution containing the solvent, the precursor raw material, the polymer, and the magnetic nanopowder is atomized and dried to obtain the composite powder.

[0031] Optionally, the solvent is selected from at least one of dimethyl sulfoxide, n-hexane, cyclohexane, n-octane, octadecene, ethanol, methanol, trimethyl phosphate, triethyl phosphate, N-methyl pyrrolidone, dimethylacetamide, N,N-dimethylformamide, isopropyl alcohol, ethyl acetate, toluene, and acetone.

[0032] Optionally, the precursor raw material comprises a precursor AX, a precursor BX m , and a precursor CX.

[0033] wherein A is selected from at least one of NH2CHNH 2+ , CH3NH 3+ , Cs + , Rb + , K + .

[0034] B is selected from at least one of Pb 2+ , Sn 2+ , Bi 3+ , Ti 3+ , Zn 2+ , Ni 2+ , Cd 2+ , Al 3+ , Mn 2+ , Mn 4+ , Ge 3+ .

[0035] C is selected from an aromatic group or a C3-C 18 alkyl organic amine cation.

[0036] X is selected from Br - , I - , SCN - , at least one of carboxylate;

[0037] m = 2, 3 or 4.

[0038] Optionally, the molar ratio of precursor AX and precursor BX m is 0.5-10:1.

[0039] Optionally, the molar ratio of precursor BX m and precursor CX is 1:0.3-10.

[0040] Optionally, the mass ratio of the precursor raw material to the polymer is 0.01:1-0.2:1.

[0041] Optionally, the mass ratio of the magnetic nanopowder to the polymer is 0.01:1-0.2:1.

[0042] Optionally, the mass ratio of the magnetic nanopowder to the polymer is independently selected from any value or a range value between any two of 0.01, 0.02, 0.03, 0.04, 0.05, 0.07, 0.10, 0.12, 0.14, 0.16, 0.18, 0.2.

[0043] Optionally, the conditions of atomization are as follows:

[0044] Solution feed rate: 50 ml / h-50000 ml / h;

[0045] Preferably, the solution feed rate is 100 ml / h-400 ml / h.

[0046] Optionally, the gas inlet rate is 15 L / min-100 L / min;

[0047] Preferably, the gas inlet rate is 25 L / min-35 L / min.

[0048] Optionally, the conditions of drying are as follows:

[0049] Air inlet temperature: 50°C-200°C;

[0050] Preferably, the air inlet temperature is 70°C-110°C.

[0051] Optionally, the air inlet temperature is independently selected from any value or a range value between any two of 50°C, 70°C, 100°C, 120°C, 140°C, 160°C, 180°C, 200°C.

[0052] According to a third aspect of the present application, there is provided an application of the magnetic fluorescent bifunctional composite material powder.

[0053] The composite material powder and / or the composite material powder prepared by the preparation method of the composite material powder are applied in biomolecule labeling, cell recognition analysis and medical diagnosis.

[0054] The schematic diagram of the device for preparing the composite material powder by spray drying is shown in the figure. Figure 6 The solvent, the precursor raw material, the polymer and the magnetic nano powder are mixed uniformly to form a precursor solution, the perovskite quantum dots are placed in a precursor tank (1), the perovskite quantum dot precursor solution is atomized into small droplets in a drying tower (3) by an atomizer (2). Hot air produced by a hot air blower (9) is introduced into the drying tower to dry the atomized small droplets to generate the magnetic fluorescent polymer powder. The magnetic fluorescent polymer powder generated in the drying tower and solvent vapor enter a cyclone separator (4) for dry-wet separation, and the magnetic fluorescent polymer powder is collected from a powder outlet (5) below the cyclone separator. The moisture in the cyclone separator enters a condensing tower (8) through an induced draft fan (6) to condense the solvent, the solvent is collected from a solvent recovery port (7), and the air is discharged. The spray drying method in-situ prepares the magnetic fluorescent polymer powder raw material into the product, the solvent can be recycled, there is no waste gas discharged throughout the process, the cost of the product is reduced, and the environmental protection requirements are met.

[0055] In the present application, C3-C 18 Refers to the number of carbon atoms contained in the group.

[0056] The beneficial effects that can be produced by the present application include:

[0057] 1) The magnetic fluorescent bifunctional composite material powder provided by the present application has excellent optical and magnetic properties and a wide range of applications. The polymer in the composite material powder completely covers the magnetic nano powder and the perovskite quantum dots, the internal nano particles will not come into contact with the target object, and the influence of toxicity is avoided. The polymer surface of the microspheres has good biocompatibility and can be easily subjected to further surface organic modification treatment.

[0058] 2) The preparation method of the magnetic fluorescent bifunctional composite material powder provided by the present application enables the perovskite quantum dots to be synthesized during the drying process, thereby having the advantages of simple synthesis process and low preparation cost. BRIEF DESCRIPTION OF DRAWINGS

[0059] Figure 1 The figure is a process flowchart of the present application.

[0060] Figure 2It is a schematic diagram of the composite powder of the present application. Wherein, 1 represents perovskite quantum dots; 2 represents magnetic nano powder; 3 represents polymer.

[0061] Figure 3 It is a real photo of the composite powder prepared in Example 1.

[0062] Figure 4 It is a photoluminescence spectrum of the composite powder prepared in Example 1.

[0063] Figure 5 It is a scanning electron microscope picture of the composite powder prepared in Example 1.

[0064] Figure 6 It is a schematic diagram of the device for preparing the composite powder by spray drying in Examples 1-3 of the present application;

[0065] Parts and list of reference numerals: 1, precursor tank; 2, atomizer; 3, drying tower; 4, cyclone separator; 5, powder outlet; 6, induced draft fan; 7, solvent recovery port; 8, condensation tower; 9, hot air blower. DETAILED DESCRIPTION

[0066] The present application will be described in detail below in conjunction with examples, but the present application is not limited to these examples.

[0067] In the examples of the present application, the raw materials are all purchased through commercial channels, unless otherwise specified.

[0068] The polyvinylidene fluoride has a molecular weight of 100000-1000000.

[0069] The polymethyl methacrylate has a molecular weight of 30000-200000.

[0070] In the examples of the present application, the analysis methods are as follows:

[0071] The electron microscope analysis is performed by using a Hitachi SU8220 cold field emission scanning electron microscope.

[0072] The fluorescence emission spectrum analysis is performed by using a spectral colorimeter of Admesy company; the excitation light source is a blue LED with a wavelength of 455 nm.

[0073] Example 1

[0074] In this embodiment, tetrapropyl ammonium bromide-MAPbBr3 perovskite quantum dots and polymethyl methacrylate, ferroferric oxide nano powder are selected for spray drying to prepare a composite powder. 0.58 g of perovskite quantum dot precursor raw material (composition: MABr, PbBr2, tetrapropyl ammonium bromide, molar ratio 1 mmol: 1 mmol: 0.4 mmol) is dissolved in 300 ml of N, N dimethylformamide (DMF), and then 15 g of polymethyl methacrylate is added to form a precursor solution. After 2 hours of stirring and dissolution, 0.015 g of ferroferric oxide nano powder (i.e. the mass ratio of magnetic nano powder to polymer is 0.001) is added for spray drying to prepare a powder. The spray drying parameters are set as follows: the feeding speed of the solution is 500 ml / h, the inlet gas pressure is 0.08 MPa, the inlet gas speed is 60 L / min, and the inlet air temperature of the dryer is 85 degrees Celsius.

[0075] The prepared magnetic nano-polymer powder is bright green as shown in Figure 3 , and its luminescence spectrum is as shown in Figure 4 . Figure 4 It can be seen that the luminescence peak of the perovskite quantum dots is located at 525 nm, and the half-peak width is 24 nm. The scanning electron microscope photo of the composite material powder is as shown in Figure 5 , and the powder particle size is 1 micron.

[0076] Example 2

[0077] In this embodiment, tetrapropyl ammonium bromide-MAPbBr3 perovskite quantum dots and polymethyl methacrylate, ferroferric oxide nano powder are selected for spray drying to prepare a composite powder. 0.58 g of perovskite quantum dot precursor raw material (composition: MABr, PbBr2, tetrapropyl ammonium bromide, molar ratio 1 mmol: 1 mmol: 0.4 mmol) is dissolved in 300 ml of N, N dimethylformamide (DMF), and then 15 g of polymethyl methacrylate is added to form a precursor solution. After 2 hours of stirring and dissolution, 0.015 g of ferroferric oxide nano powder (i.e. the mass ratio of magnetic nano powder to polymer is 0.001) is added for spray drying to prepare a powder. The spray drying parameters are set as follows: the feeding speed of the solution is 500 ml / h, the inlet gas pressure is 0.08 MPa, the inlet gas speed is 60 L / min, and the inlet air temperature of the dryer is 85 degrees Celsius.

[0078] Example 3

[0079] In this embodiment, dodecyl dimethyl benzyl ammonium bromide-CsPbBr3 perovskite quantum dots and polyvinylidene fluoride, ferric oxide nano powder are selected for spray drying. 0.73 g of perovskite quantum dot precursor raw material (composition: CsBr, PbBr2, dodecyl dimethyl benzyl ammonium bromide, molar ratio 1 mmol: 1 mmol: 0.4 mmol) is dissolved in 300 ml of N, N dimethylformamide, then 25 g of polyvinylidene fluoride is added to form a precursor solution. After stirring and dissolving for 2 hours, 0.1 g of ferric oxide nano powder (i.e. the mass ratio of ferric oxide nano powder to polymer is 0.004) is added for spray drying to prepare a powder. The spray drying parameters are set as follows: the feeding speed of the solution is 500 ml / h, the inlet pressure is 0.08 MPa, the inlet speed is 60 L / min, and the inlet temperature of the dryer is 80 degrees Celsius.

[0080] The above is only a few embodiments of the present application, and does not limit the present application in any form. Although the preferred embodiments are disclosed above, the present application is not limited thereto. Any person skilled in the art can make some changes or modifications to the above disclosed technical contents without departing from the scope of the present application, and such changes or modifications are equivalent to equivalent embodiments, and all of them are within the scope of the technical solution.

Claims

1. A method for producing a magnetic fluorescent bifunctional composite powder, characterized by, The method comprises the following steps: The mixed solution containing solvent, precursor raw material, polymer, magnetic nano powder is atomized and dried to obtain the composite powder; The atomization conditions are: solution feeding speed 50ml / h~50000ml / h, air inlet speed 15L / min~100L / min; The drying conditions are: air inlet temperature 50℃~200℃; The precursor raw material includes a precursor AX, a precursor BX m and a precursor CX; wherein A is selected from NH2CHNH2 + , CH3NH3 + , Cs + , Rb + , K + at least one of B is selected from at least one of Pb 2+ , Sn 2+ , Zn 2+ , Ni 2+ , Cd 2+ , Mn 2+ . C is selected from aryl or C3-Ci2alkyl; 18 alkyl organic amine cation; X is selected from the group consisting of Br - , I - , SCN - , at least one of carboxylate. m=2； The composite powder comprises polymer, perovskite quantum dots and magnetic nano powder; The polymer coats the perovskite quantum dots and the magnetic nano powder; The perovskite quantum dots and the magnetic nano powder are dispersed in the polymer; The polymer is at least one selected from polyvinylidene fluoride, polyvinylidene fluoride, trifluoroethylene copolymer, polyacrylonitrile, polyvinyl acetate, cellulose acetate, cyano cellulose, polysulfone, aromatic polyamide, polyimide, polycarbonate, polystyrene, polymethyl methacrylate, polymethyl lauryl methacrylate; The perovskite quantum dots have ABX3 structure; The magnetic nano powder is at least one selected from ferroferric oxide and diiron trioxide; The composite powder particle size is 0.1μm~100μm; The magnetic nano powder particle size is 1nm~100nm.

2. The production method according to claim 1, characterized by, The composite powder particle size is 0.2μm~5μm.

3. The preparation method according to claim 1, characterized in that, The magnetic nano powder particle size is 3nm~10nm.

4. The method of claim 1, wherein, The solvent is at least one selected from dimethyl sulfoxide, n-hexane, cyclohexane, n-octane, octadecene, ethanol, methanol, trimethyl phosphate, triethyl phosphate, N-methyl pyrrolidone, dimethylacetamide, N,N-dimethylformamide, isopropyl alcohol, ethyl acetate, toluene, acetone.

5. The preparation method according to claim 1, characterized in that, Precursor AX and Precursor BX m at a molar ratio of 0.5-10:

1.

6. The method of claim 1, wherein, Precursor BX m and the molar ratio of the precursor CX is 1:0.3~10.

7. The preparation method according to claim 1, characterized in that, The mass ratio of the precursor raw material to the polymer is 0.01:1~0.2:

1.

8. The method of claim 1, wherein, The mass ratio of the magnetic nano powder to the polymer is 0.01:1~0.2:

1.

9. The method of claim 1, wherein, Solution feeding speed: 100ml / h~400ml / h.

10. The method of claim 1, wherein, Air inlet speed: 25L / min~35L / min.

11. The method of claim 1, wherein, Air inlet temperature: 70℃~110℃.

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