A biologically skin-responsive halide light emitting fiber film, and a preparation method and application thereof

Abstract

The application discloses a kind of biological skin response halide luminescent fiber membrane and its preparation method and application.It is by metal halide and the amino-containing polymer resin solution using electrospinning technology obtained;The amino-containing polymer resin solution includes one or several of thermoplastic polyurethane solution, aqueous polyurethane solution or high-temperature polyurethane solution;The chemical formula of the metal halide is ABX3;A in the ABX3 It is selected from Cs + , MA + Or FA + , B is selected from Pb 2+ , Cu 2+ , Ag + Or Sn 2+ , X is selected from Cl-, Br- or I-.The fiber membrane is high in recognition, high in sensitivity and good in stability;Its preparation method raw material is easy to obtain, simple to operate, low in cost, and can be industrialized mass production.In practical application, the luminescent fiber membrane can be used in fingerprint identification, identity verification, medical detection, criminal investigation and security, etc.

Description

Technical Field

[0001] This invention relates to a bio-skin-responsive halide luminescent fiber membrane, its preparation method, and its application, belonging to the field of bio-skin-responsive luminescent materials. Background Technology

[0002] In recent decades, traditional sweat pore development techniques have been continuously improved and updated, while emerging technologies have also made significant progress, demonstrating outstanding performance in terms of sensitivity, development conditions, efficiency, and effectiveness. Particularly in the development of old, trace-level sweat latent fingerprints, these technologies have broken through the bottlenecks of traditional techniques, ushering in a new era for sweat latent fingerprint development. However, these emerging methods rely heavily on instruments and new materials, which are expensive and have high operating costs, making them difficult to meet the needs of large-scale field use. Furthermore, the new technologies have strict operational requirements; therefore, simplifying the development process and reducing the cost of the technology are the development trends for sweat latent fingerprint testing.

[0003] Metal halide materials, due to their excellent properties such as tunable band gap, high absorption coefficient, high fluorescence quantum yield, high color purity, high carrier mobility, and long carrier diffusion distance, have shown promising application prospects in light-emitting and display lighting devices, solar cells, and detection imaging. Among the many metal halide luminescent materials with different compositions, metal halide quantum dots have advantages such as high luminous efficiency, easily tunable emission wavelength, and narrow half-maximum width at half-maximum (HWHM), making them a star material for light-emitting and display devices. Electrospinning is a spinning technique in which fluid flows and deforms under a high-voltage electric field to obtain fibrous materials. This technique can produce a wide variety of nanofibers, and the manufacturing equipment is simple and the spinning cost is low, thus having wide applications in the field of materials science and technology. By combining electrospinning with supramolecular encapsulation technology, metal halides can be effectively functionalized, allowing them to maintain high luminescent performance even after prolonged exposure to high humidity conditions or immersion in polar solvents. However, the application of electrospinning combined with metal halides for fingerprint and other pore recognition technologies has not yet been reported. Summary of the Invention

[0004] Purpose of the invention: The technical problem to be solved by the present invention is to provide a biological skin-responsive halide luminescent fiber membrane with high sensitivity, high recognition, simple preparation and low cost, as well as its preparation method and application.

[0005] Technical Solution: To solve the above-mentioned technical problems, this invention provides a bio-skin-responsive halide luminescent fiber membrane, which is obtained by electrospinning a metal halide and an amino-containing polymer resin solution; the amino-containing polymer resin solution includes one or more of thermoplastic polyurethane solution, aqueous polyurethane solution, or high-temperature polyurethane solution; the chemical formula of the metal halide is ABX3; and the A in ABX3 is selected from Cs. + MA + or FA + B is selected from Pb 2+ Cu 2 + Ag + or Sn 2+ X is selected from Cl - , Br - or I - .

[0006] The present invention also provides a method for preparing the bio-skin-responsive halide luminescent fiber membrane, comprising the following steps:

[0007] (1) Dissolve halides, halide salts and biomacrocyclic molecules with cavity structures in a strongly polar organic solvent to obtain a metal halide precursor solution;

[0008] (2) The metal halide precursor solution described in step (1) is injected into a polymer resin solution containing amino groups, and a halide luminescent fiber membrane is obtained by electrospinning. The polymer resin solution containing amino groups includes a thermoplastic polyurethane solution, an aqueous polyurethane solution, or a high-temperature polyurethane solution.

[0009] The challenge of combining metal halides with electrospinning lies in the fact that metal halide materials are typically in powder form, requiring their bonding with electrospinning fibers to form a homogeneous composite material. Furthermore, the composite material combining electrospinning and metal halides needs to possess good stability to ensure it does not decompose or fail during use.

[0010] To overcome these technical challenges, new technologies and methods need to be developed to improve the performance and stability of electrospun metal halide composites. The method combines electrospun fibers with metal halide materials to rapidly synthesize large-area luminescent fiber membranes capable of quickly responding to biological skin at room temperature.

[0011] The halide mentioned in step (1) includes one or more of PbBr2, PbI2, SnCl2, CuCl2, PbCl2 or CuBr2.

[0012] The halide salt mentioned in step (1) includes one or more of CsBr, CsCl, CsI, CH3NH2Br or MABr.

[0013] The hollow-structured biomacrocyclic molecule mentioned in step (1) includes one or more of cyclodextrins, methylcellulose, crown ethers, or calixarenes.

[0014] The strongly polar organic solvent mentioned in step (1) includes one or more of dimethyl sulfoxide, N,N-dimethylformamide or N,N-dimethylacetamide. The use of strongly polar organic solvents facilitates the rapid coordination of halides, halide salts and biomacrocyclic molecules.

[0015] In step (1), the mass-to-volume ratio of the halide to the strongly polar organic solvent is 1 to 5:2.5.

[0016] In step (2), the concentration of the metal halide precursor solution is 0.1–0.5 M.

[0017] In step (2), the mass ratio of the amino-containing polymer resin to the strongly polar organic solvent in step (1) is 10% to 20%.

[0018] The present invention also provides the application of the halide luminescent fiber membrane in sweat pore identification.

[0019] Beneficial effects: Compared with the prior art, the present invention has the following significant advantages: 1. The bio-skin responsive luminescent fiber membrane has the characteristics of high sensitivity, high recognition, simple preparation and low cost; 2. It has certain heat resistance and water resistance, and has rich application prospects in criminal investigation and other fields in the future; 3. The preparation method is simple, the synthesis rate is fast, and it can respond quickly to fingerprints. Attached Figure Description

[0020] Figure 1 The image shows a luminescent fiber membrane captured using a fluorescence microscope.

[0021] Figure 2 To prepare a bio-skin-responsive luminescent fiber membrane;

[0022] Figure 3 A bioluminescent fiber membrane that responds to biological skin after being heated to 100 degrees Celsius for half an hour;

[0023] Figure 4 A luminescent fiber membrane that responds to biological skin after being exposed to water vapor for two minutes;

[0024] Figure 5 This refers to a luminescent fiber membrane spun by adding metal halides to a PS resin solution.

[0025] Figure 6SEM image of a bioluminescent fiber membrane in response to fingerprints.

[0026] Figure 7 SEM image of a bioluminescent fiber membrane in response to fingerprint contact. Detailed Implementation

[0027] The technical solution of the present invention will be further described below with reference to the accompanying drawings.

[0028] Example 1: A method for preparing a bio-skin-responsive halide luminescent fiber membrane

[0029] The specific preparation method includes the following steps: Taking the preparation of a bio-skin-responsive CsPbBr3 luminescent fiber membrane as an example:

[0030] (1) Weigh 0.3M CsBr and 0.3M PbBr2 and 20mg 2-hydroxypropyl-β-cyclodextrin (HPβCD), grind for 1-2 minutes, then add 0.5ml dimethyl sulfoxide (DMSO) and 0.25ml N,N-dimethylformamide (DMF), stir thoroughly and let stand, take the supernatant as the precursor solution CsPbBr3.

[0031] (2) Prepare a TPU (thermoplastic polyurethane, molecular weight 1000) resin solution with a mass fraction of 13% in a strongly polar solvent, using 0.5 ml of acetone and 0.1 ml of DMF as solvents. Then add 100 μL of a 0.3 M precursor solution to the above TPU resin solution to obtain the spinning solution.

[0032] (3) Load the spinning solution into a syringe, then load the syringe into the delivery device. Attach a layer of fiber cloth or aluminum foil to the rotating shaft or receiving plate. Use an electrospinning machine to spin the spinning solution at a rotation speed of 500 rpm, a spinning solution delivery rate of 0.5 ml / h, an initial distance of 10 cm between the needle and the rotating shaft, a needle diameter of 2 mm, a voltage of 15 kV, and a temperature of 25 °C. Maintain ventilation during spinning. Finally, a large-area bio-skin responsive luminescent fiber membrane with dimensions of 15 × 25 cm is prepared. 2 .

[0033] When excited by blue light, the fingerprint patterns and sweat pores in the fabricated bio-skin-responsive luminescent fiber membrane exhibited significantly stronger green fluorescence than other parts. Figure 1 Under bright-field ultraviolet light, the areas where sweat pores are identified emit strong fluorescence, while the background shows no fluorescence interference, thus allowing for a clear image of the identified sweat pores. Figure 2 Compared to the halide luminescent fiber membrane before fingerprint contact (). Figure 6 The film becomes significantly more cross-linked after contact with fingerprints. Figure 7 Even after heating at 100 degrees Celsius for half an hour, the sweat pore images remained stable. Figure 3 After being exposed to steam for two minutes, the sweat pore pattern remained stable. Figure 4 This indicates that the bio-skin-responsive luminescent fiber membrane has the characteristics of high sensitivity, high recognition, simple preparation, low cost, and easy operation, and has rich application prospects in fields such as criminal investigation in the future.

[0034] Example 2: A method for preparing a bio-skin-responsive halide luminescent fiber membrane

[0035] The specific preparation method includes the following steps: Taking the preparation of a bio-skin-responsive CsPbCl3 luminescent fiber membrane as an example:

[0036] (1) Weigh 0.1M CsCl, 0.1M PbCl2 and 20mg methylcellulose, grind for 1-2 minutes, then add 0.5ml dimethyl sulfoxide (DMSO) and 0.25ml N,N-dimethylformamide (DMF), stir thoroughly and let stand, take the supernatant as the precursor solution CsPbCl3.

[0037] (2) Prepare a solution of waterborne polyurethane resin (molecular weight 1000) with a mass fraction of 10% in a strongly polar solvent, using 0.5 ml of acetone and 0.1 ml of DMF as solvents. Then add 100 μL of a 0.1 M precursor solution to the above resin solution to obtain a spinning solution.

[0038] (3) Load the spinning solution into a syringe, then load the syringe into the delivery device. Attach a layer of fiber cloth or aluminum foil to the rotating shaft or receiving plate. Use an electrospinning machine to spin the spinning solution at a rotation speed of 500 rpm, a spinning solution delivery rate of 0.5 ml / h, an initial distance of 10 cm between the needle and the rotating shaft, a needle diameter of 2 mm, a voltage of 15 kV, and a temperature of 25 °C. Maintain ventilation during spinning. Finally, a large-area bio-skin responsive luminescent fiber membrane with dimensions of 15 × 25 cm is prepared. 2 .

[0039] The prepared bio-skin-responsive luminescent fiber membrane emits strong fluorescence at the sweat pore identification sites under ultraviolet light irradiation, with no background fluorescence interference, thus allowing for clear image acquisition of the identified sweat pores. This indicates that the bio-skin-responsive luminescent fiber membrane possesses the characteristics of high sensitivity, high recognition accuracy, simple preparation, low cost, and ease of operation, and has promising applications in fields such as criminal investigation.

[0040] Example 3: A method for preparing a bio-skin-responsive halide luminescent fiber membrane

[0041] The specific preparation method includes the following steps: Taking the preparation of a bio-skin-responsive MACuBr3 luminescent fiber membrane as an example:

[0042] (1) Weigh out 0.5M MABr, 0.5M CuBr2, and 20mg of calixarene (C 42 H 36 After grinding O6 for 1-2 minutes, add 0.5 ml of dimethyl sulfoxide (DMSO) and 0.25 ml of N,N-dimethylacetamide (DMAr), stir thoroughly, let stand, and take the supernatant as the precursor solution MACuBr3.

[0043] (2) Prepare a high-temperature polyurethane resin (molecular weight 1000) solution with a mass fraction of 20% in a strongly polar solvent, using 0.5 ml acetone and 0.1 ml DMF as solvents. Then add 100 μl of a 0.5 M precursor solution to the above resin solution to obtain a spinning solution.

[0044] (3) Load the spinning solution into a syringe, then load the syringe into the delivery device. Attach a layer of fiber cloth or aluminum foil to the rotating shaft or receiving plate. Use an electrospinning machine to spin the spinning solution at a rotation speed of 500 rpm, a spinning solution delivery rate of 0.5 ml / h, an initial distance of 10 cm between the needle and the rotating shaft, a needle diameter of 2 mm, a voltage of 15 kV, and a temperature of 25 °C. Maintain ventilation during spinning. Finally, a large-area bio-skin responsive luminescent fiber membrane with dimensions of 15 × 25 cm is prepared. 2 .

[0045] The prepared bio-skin-responsive luminescent fiber membrane emits strong fluorescence at the sweat pore identification sites under ultraviolet light irradiation, with no background fluorescence interference, thus allowing for clear image acquisition of the identified sweat pores. This indicates that the bio-skin-responsive luminescent fiber membrane possesses the characteristics of high sensitivity, high recognition accuracy, simple preparation, low cost, and ease of operation, and has promising applications in fields such as criminal investigation.

[0046] Comparative Example 1: A method for preparing a bio-skin-responsive halide luminescent fiber membrane

[0047] The specific preparation method includes the following steps:

[0048] (1) Weigh 0.3M CsBr, 0.3M PbBr2 and 20mg HPβCD, grind for 1-2 minutes, then add 0.5ml dimethyl sulfoxide (DMSO) and 0.25ml DMF, stir thoroughly and let stand, take the supernatant as the precursor solution.

[0049] (2) Prepare a PS resin (molecular weight 130) solution with a mass fraction of 13% using 0.5 ml acetone and 0.1 ml DMF as solvents. Then add 100 μl of a 0.3 M precursor solution to 1 ml of the PS resin solution to obtain the spinning solution.

[0050] (3) Load the spinning solution into a syringe, then load the syringe into the delivery device. Attach a layer of fiber cloth or aluminum foil to the rotating shaft or receiving plate. Use an electrospinning machine to spin the spinning solution, with a rotation speed of 500 rad / min, a spinning solution delivery rate of 0.5 ml / h, an initial distance of 10 cm between the needle and the rotating shaft, a needle diameter of 2 mm, a voltage of 15 kV, and a temperature of 25 °C. Maintain ventilation during spinning. Finally, a large-area bio-skin responsive luminescent fiber membrane with dimensions of 15 × 25 cm is prepared. 2 .

[0051] When the resin was replaced with PS, although there was uniform fluorescence, the spun fiber membrane lacked the ability to identify pores. Figure 5 This indicates that only polyurethanes with multiple amino groups can recognize pore images when interacting with metal halides. This is primarily because amino esters are compounds containing amino groups, while metal halides are materials with special photoelectric properties composed of cations and anions. When amino esters interact with metal halides, electron-donating processes occur, leading to chemical passivation and the formation of new structures. This mechanism involves the formation or breaking of chemical bonds, electron transfer, or surface adsorption, depending on the specific properties and structures of the amino esters and metal halides, as well as their interaction patterns. In the example mentioned above, the interaction between amino esters and metal halides results in the formation of a specific structure, thus enabling the material to recognize pore images.

[0052] As can be seen from Example 1 and Comparative Example 1, sweat pore images can only be identified when polyurethane and metal halide work together.

Claims

1. A biologically skin-responsive halide light emitting fiber film, characterized by, It is obtained by using electrospinning technology from a metal halide and a high-molecular resin solution containing amino group; the high-molecular resin solution containing amino group includes one or several of thermoplastic polyurethane solution, aqueous polyurethane solution or high-temperature polyurethane solution; the chemical formula of the metal halide is ABX3; A in the ABX3 is selected from Cs + , MA + or FA + , B is selected from Pb 2+ , Cu 2+ , Ag + or Sn 2+ , and X is selected from Cl - , Br - or I - .

2. A method of preparing the bio-skin responsive halide light emitting fiber film of claim 1, characterized by, The method comprises the following steps: (1) dissolving halide, halide salt and biological macrocyclic molecule with cavity structure in strong polar organic solvent to obtain metal halide precursor solution; the halide comprises one or more of PbBr2, PbI2, SnCl2, CuCl2, PbCl2 or CuBr2; the halide salt comprises one or more of CsBr, CsCl, CsI or MABr; the biological macrocyclic molecule with cavity structure comprises one or more of cyclodextrin, methyl cellulose, crown ether or calixarene; (2) injecting the metal halide precursor solution in step (1) into amino-containing polymer resin solution to obtain halide luminescent fiber film by electrospinning technology; the amino-containing polymer resin solution comprises thermoplastic polyurethane solution, aqueous polyurethane solution or high-temperature polyurethane solution.

3. The method of claim 2, wherein, The strong polar organic solvent in step (1) comprises one or more of dimethyl sulfoxide, N,N-dimethylformamide or N,N-dimethylacetamide.

4. The method of claim 2, wherein, The mass-volume ratio of the halide to the strong polar organic solvent in step (1) is 1-5:2.

5.

5. The method of claim 2, wherein, The concentration of the metal halide precursor solution in step (2) is 0.1-0.5 M.

6. The method of claim 2, wherein, The mass ratio of the amino-containing polymer resin in step (2) to the strong polar organic solvent in step (1) is 10%-20%.

7. Application of the biological skin-responsive halide luminescent fiber film in step 1 in sweat pore identification.

Images