A controllable response fluorescent polymer material and a preparation method and application thereof

Abstract

The application discloses a controllable response type fluorescent polymer material and a preparation method and application thereof. The controllable response type fluorescent polymer material is prepared by mixing and reacting a fluorescent monomer solution, a solvent, an acrylamide compound, a metal salt, water, a crosslinking agent solution, a promoter and an initiator. The fluorescent detection material is fixed in a three-dimensional network with stable structure in a covalent bond form through a chemical copolymerization technology, so that disordered migration of the fluorescent detection material in a production, storage and detection process is avoided, the stability of detection is effectively improved, and good result reproducibility is ensured.

Description

Technical Field

[0001] This invention belongs to the field of smart materials technology, specifically relating to a controllable responsive fluorescent polymer material, its preparation method, and its application. Background Technology

[0002] Encryption technology can be divided into digital encryption and physical encryption.

[0003] Typically, deciphering physical information relies on external stimuli such as light, pH, solvents, force, and heat as keys to unlock the information. Because these methods require external stimuli, users without specialized chemical knowledge may find it difficult to process coded information by adding chemicals.

[0004] Fluorescent materials play a vital role in modern society due to their wide applications in organic light-emitting diodes (OLEDs), chemical / biological probes, bioimaging, sensors, and information encoding. Fluorescent materials are incorporated into polymer hydrogels to create fluorescent polymer hydrogels (FPHs). FPHs are a type of polymer gel. Due to their unique luminescent properties, FPHs can be viewed as a combination of light and gel, possessing the excellent properties of hydrogels. By adjusting the excited-state chromophores and the environment, the state of FPHs and their emission spectra can be altered, making them significant in fields such as biosensors, fluorescent probes, imaging tracking, and cancer therapy.

[0005] Sessler's team constructed a hydrogel block for information storage using three luminescent agents—coumarin, boron dipyrrole (BODIPY), and rhodamine B—that emit blue, green, and red fluorescence, respectively. (Ji, X.; Wu, RT; Long, L.; Ke, XS; Guo, C.; Ghang, YJ; Lynch, VM; Huang, F.; Sessler, JLE) (Polymeric Hydrogels. Adv. Mater. 2018, 30, No. 1705480); Zhao and colleagues reported preparing hydrogel blocks by adding several photo-switching diarylethene molecules and luminescent rare-earth complexes to a hydrogel matrix, and assembling these hydrogel blocks into multiple hydrogel structures for information encoding (Li, Z.; Chen, H.; Li, B.; Xie, Y.; Gong, X.; Liu, X.; Li, H.; Zhao, Y. Photoresponsive Luminescent Polymeric Hydrogels for Reversible Information Encryption and Decryption. Adv. Sci. 2019, 6, No. 1901529), whose encoded information can be easily read under commercial ultraviolet lamps. Therefore, these existing technical solutions can perform reversible encryption and decryption of confidential information through simple light irradiation, but in terms of encryption methods, the encoding form of information content corresponding to a given message is very complex. Therefore, it is necessary to develop a fluorescent polymer material that can perform information encoding more conveniently. Summary of the Invention

[0006] The purpose of this invention is to overcome the shortcomings of the prior art and provide a controllable responsive fluorescent polymer material.

[0007] Another object of the present invention is to provide a method for preparing the above-mentioned controllable responsive fluorescent polymer material.

[0008] Another object of the present invention is to provide applications of the above-mentioned controllable responsive fluorescent polymer materials.

[0009] The technical solution of the present invention is as follows:

[0010] A controllable responsive fluorescent polymer material, characterized in that it is prepared by mixing and reacting a fluorescent monomer solution, a solvent, an acrylamide compound, a metal salt, water, a crosslinking agent solution, a accelerator, and an initiator, wherein...

[0011] The concentration of the fluorescent monomer solution is 0.04-0.06 wt%. The fluorescent monomer is prepared by reacting a coumarin derivative, sodium hydroxide, anhydrous ethanol, and methacrylyl chloride. The coumarin derivative is at least one selected from 7-hydroxy-4-methylcoumarin, 7-hydroxy-4-methylcoumarin, and 7-amino-4-trifluoromethylcoumarin. The solvent for the fluorescent monomer solution is an aqueous solution of dimethyl sulfoxide.

[0012] The solvent is an aqueous solution of dimethyl sulfoxide and / or a CMCNa solution, wherein the CMCNa solution is a dimethyl sulfoxide aqueous solution.

[0013] The acrylamide compound is at least one selected from acrylamide, methacrylamide, methacryloyloxyethyltrimethylammonium chloride, and N-isopropylacrylamide.

[0014] The metal salt is at least one of NaCl, KCl, LiCl, ZnSO4, FeCl3, and NaSO4.

[0015] The concentration of the crosslinking agent solution is 14-16 wt%, and the crosslinking agent is N,N-methyleneacrylamide and / or epichlorohydrin.

[0016] The accelerator is N,N,N',N'-tetramethyldiethylamine and / or N,N-diethyl-1,3-propanediamine.

[0017] The initiator is at least one of potassium persulfate, sodium bisulfite, potassium bisulfite, and ammonium persulfate.

[0018] In a preferred embodiment of the present invention, the coumarin derivative is 7-hydroxy-4-methyl-coumarin.

[0019] More preferably, the ratio of the coumarin derivative, sodium hydroxide, anhydrous ethanol and methacrylamide chloride is 0.1-0.3g:0.03-0.05g:100mL:1.0-1.2mmol.

[0020] More preferably, the ratio of the coumarin derivative, sodium hydroxide, anhydrous ethanol and methacryloyl chloride is 0.2g:0.04g:100mL:1.1mmol.

[0021] In a preferred embodiment of the present invention, the acrylamide compound is acrylamide, and the metal salt is ZnSO4.

[0022] More preferably, the crosslinking agent is N,N-methyleneacrylamide, the accelerator is N,N,N',N'-tetramethyldiethylamine, and the initiator is ammonium persulfate.

[0023] In a preferred embodiment of the present invention, the ratio of the fluorescent monomer solution, solvent, acrylamide compound, metal salt, water, crosslinking agent solution, accelerator and initiator is 380-410 μL: 1.5-5.5 g: 1.8-2.2 g: 0.25-0.35 g: 9-11 mL: 9-11 μL: 0.8-1.2 μL: 20-25 mg.

[0024] The preparation method of the above-mentioned controllable responsive fluorescent polymer material includes the following steps:

[0025] (1) Preparation of the fluorescent monomer;

[0026] (2) Dissolve the above fluorescent monomer in an aqueous solution of dimethyl sulfoxide to obtain the fluorescent monomer solution;

[0027] (3) The above fluorescent monomer solution, the solvent, the acrylamide compound, the metal salt and water are magnetically stirred and mixed to obtain a homogeneous mixed solution;

[0028] (4) Add the crosslinking agent, the initiator and the accelerator to the above mixed solution, stir and react, then pour the reacted material into a mold and react at 48-55℃ for 4-6 hours to obtain the product.

[0029] In a preferred embodiment of the present invention, step (1) is as follows: the coumarin derivative and sodium hydroxide are dissolved in anhydrous ethanol, stirred at 58-62°C for 25-35 min, cooled to room temperature, and then methacryloyl chloride is added dropwise at 0-5°C. After the addition is complete, the reaction is stirred for another 85-100 min. After the reaction is complete, the resulting product is poured onto crushed ice to form a solid. Then, the product is filtered, washed with cold water, vacuum dried and recrystallized in sequence to obtain the fluorescent monomer.

[0030] The application of the above-mentioned controllable responsive fluorescent polymer materials in the preparation of information encryption and decryption devices.

[0031] The beneficial effects of this invention are:

[0032] 1. The controllable responsive fluorescent polymer material prepared by the present invention uses chemical copolymerization technology to fix the fluorescent detection material in a structurally stable three-dimensional network in the form of covalent bonds, which avoids the disordered migration of fluorescent detection components during production, storage and detection, effectively improves the stability of detection and ensures good result reproducibility.

[0033] 2. The preparation method of the present invention adopts a one-pot free radical polymerization reaction method, which is simple to operate, requires low equipment, and the experimental raw materials are all commonly used chemical products. The production process is safe and reliable, there is no risk of explosion, the price is low, and the economic benefits are high after industrialization.

[0034] 3. For example Figure 1 and 4 As shown, this invention achieves a powerful dual-lock encryption technology by combining two stimuli under different pH and light conditions. This strategy boasts advantages such as high security, large information capacity, simple fabrication, and low cost, opening up broad application prospects for stimuli materials in fields such as information encryption, anti-counterfeiting, pH sensing, and erasable writing. (Reference: Lou, K.; Hu, Z.; Zhang, H.; Li, Q.; Ji, X. Information Storage Based on Stimuli-Responsive Fluorescent 3D Code Materials. Adv. Funct. Mater. 2022, 32, 2113274.) Attached Figure Description

[0035] Figure 1 This diagram illustrates the molecular response mechanism of the controllable responsive fluorescent polymer material of the present invention at different pH values.

[0036] Figure 2 The Fourier transform infrared spectra of the fluorescent monomers prepared in a specific embodiment of the present invention and the raw materials used are shown.

[0037] Figure 3 This is a scanning electron microscope image of the controllable responsive fluorescent polymer material prepared in Example 1 of the present invention.

[0038] Figure 4 This is a schematic diagram illustrating the ion printing and information encryption of the controllable responsive fluorescent polymer material of the present invention.

[0039] Figure 5 The fluorescence response result of the controllable responsive fluorescent polymer material prepared in Example 5 of the present invention is shown as a fluorescence spectrum. Detailed Implementation

[0040] The technical solution of the present invention will be further explained and described below with reference to specific embodiments and accompanying drawings.

[0041] The preparation method of the fluorescent monomer used in the following examples includes: dissolving 0.2 g of 7-hydroxy-4-methyl-coumarin and 0.04 g of sodium hydroxide in 100 mL of anhydrous ethanol, stirring at 60 °C for 30 min, cooling to room temperature, and then adding 1.1 mmol of methacryloyl chloride dropwise at 0-5 °C. After the addition is complete, stirring is continued for 90 min. After the reaction is complete, the resulting product is poured onto crushed ice to form a solid, which is then purified by filtration, cold water washing, vacuum drying at 40 °C, and recrystallization to obtain the product as shown in the examples. Figure 2The fluorescent monomers shown are: 4-MU, which corresponds to 7-hydroxy-4-methyl-coumarin, and MAOMC, which corresponds to the obtained fluorescent monomer. The comparison of the infrared spectra shows that MAOMC was successfully prepared.

[0042] Example 1

[0043] (1) Dissolve the above fluorescent monomer in a 60wt% dimethyl sulfoxide aqueous solution (the mass ratio of dimethyl sulfoxide to water is 3:2) to obtain a fluorescent monomer solution with a concentration of 0.05wt%.

[0044] (2) 400 μL of the above fluorescent monomer solution, 5 g of solvent (60 wt% dimethyl sulfoxide aqueous solution), 2 g of acrylamide and 0.3 g of ZnSO4·7H2O were put into a 20 mL glass bottle, and then a 2 cm magnetic rotor and 10 mL of water were added and magnetically stirred at 1000 rpm for 60 min to obtain a uniform mixed solution.

[0045] (3) Add 10 μL of 15 wt% MBA (N,N-methyleneacrylamide) solution, 24 mg of ammonium persulfate, and 1.0 μL of LTEMED (N,N,N',N'-tetramethyldiethylamine) to the above mixed solution, stir at 1000 rpm for 30 min, then pour the resulting material into a suitable mold and keep it in an oven at 50℃ for 5 h to obtain the product shown below. Figure 3 The controllable responsive fluorescent polymer material shown is described. From Figure 3 It can be seen that the surface and cross-section of this controllable responsive fluorescent polymer material are filled with a large number of voids, indicating that CMCNa forms a semi-interpenetrating network structure in the PAM-MAOMC network, which can effectively resist crack propagation.

[0046] Example 2

[0047] The difference from Example 1 is that 4g of a 60wt% dimethyl sulfoxide aqueous solution and 1g of a 5wt% sodium carboxymethyl cellulose solution (the solvent of the sodium carboxymethyl cellulose solution is a 60wt% dimethyl sulfoxide aqueous solution) are added.

[0048] Example 3

[0049] The difference from Example 1 is that 3g of 60wt% dimethyl sulfoxide aqueous solution and 2g of 5wt% sodium carboxymethyl cellulose solution (the solvent of the sodium carboxymethyl cellulose solution is 60wt% dimethyl sulfoxide aqueous solution) are added.

[0050] Example 4

[0051] The difference from Example 1 is that 2g of 60wt% dimethyl sulfoxide aqueous solution and 3g of 5wt% sodium carboxymethyl cellulose solution (the solvent of the sodium carboxymethyl cellulose solution is 60wt% dimethyl sulfoxide aqueous solution) are added.

[0052] Example 5

[0053] The difference from Example 1 is that 1g of a 60wt% dimethyl sulfoxide aqueous solution and 4g of a 5wt% sodium carboxymethyl cellulose solution (the solvent of the sodium carboxymethyl cellulose solution is a 60wt% dimethyl sulfoxide aqueous solution) are added.

[0054] The controllable responsive fluorescent polymer material prepared in this embodiment was immersed at different pH values ​​to obtain different gel samples for testing. These samples were then tested using a fluorescence lifetime and steady-state fluorescence spectrometer (FLS920).

[0055] After wiping away excess liquid from the surface of the gel sample, the sample was placed in a solid fixture for testing. The excitation wavelength was 365 nm, the excitation slit width was 1.0 nm or 2.5 nm, the emission slit width was 1.0 nm, and the time interval was 0.1 s. The results are as follows. Figure 5 As shown, the fluorescence intensity is highest at pH=12, which means that the controllable responsive fluorescent polymer material prepared in this embodiment has superior performance when performing information encryption.

[0056] like Figure 4 As shown, the pre-cut digital template is soaked in an alkaline solution and then laid flat on the surface of the controllable responsive fluorescent polymer material prepared in Examples 1 to 5. After a period of time, when irradiated with ultraviolet light, the shape of the digital template can be seen to be imprinted on the surface of the gel, realizing the possibility of information encryption.

[0057] The above description is merely a preferred embodiment of the present invention, and therefore should not be construed as limiting the scope of the present invention. All equivalent changes and modifications made in accordance with the scope of the patent and the contents of the specification should still fall within the scope of the present invention.

Claims

1. Use of a controllably responsive fluorescent polymeric material in the preparation of an information encryption / decryption device, characterized in that: This controllable responsive fluorescent polymer material is prepared by mixing and reacting a fluorescent monomer solution, a solvent, an acrylamide compound, a metal salt, water, a crosslinking agent solution, a accelerator, and an initiator. The solvent is a CMCNa solution, and the solvent for the CMCNa solution is an aqueous solution of dimethyl sulfoxide. The concentration of the fluorescent monomer solution is 0.04-0.06 wt%. The fluorescent monomer is prepared by reacting a coumarin derivative, sodium hydroxide, anhydrous ethanol, and methacrylamide chloride. The coumarin derivative is 7-hydroxy-4-methyl-coumarin. The solvent for the fluorescent monomer solution is an aqueous solution of dimethyl sulfoxide. The acrylamide compound is acrylamide, the metal salt is ZnSO4, the concentration of the crosslinking agent solution is 14-16 wt%, the crosslinking agent is N,N-methyleneacrylamide, the accelerator is N,N,N',N'-tetramethyldiethylamine, and the initiator is ammonium persulfate; The preparation method of this controllable responsive fluorescent polymer material includes the following steps: (1) Preparation of the fluorescent monomer; (2) Dissolve the above fluorescent monomer in an aqueous solution of dimethyl sulfoxide to obtain the fluorescent monomer solution; (3) The above fluorescent monomer solution, the solvent, the acrylamide compound, the metal salt and water are magnetically stirred and mixed to obtain a homogeneous mixed solution; (4) Add the crosslinking agent solution, the initiator and the accelerator to the above mixed solution, stir and react, then pour the reacted material into a mold and react at 48-55℃ for 4-6 hours to obtain the product.

2. Use according to claim 1, characterized in that: The ratio of the coumarin derivative, sodium hydroxide, anhydrous ethanol, and methacryloyl chloride is 0.1-0.3g: 0.03-0.05g: 100mL: 1.0-1.2mmol.

3. Use according to claim 2, characterized in that: The ratio of the coumarin derivative, sodium hydroxide, anhydrous ethanol, and methacryloyl chloride is 0.2 g: 0.04 g: 100 mL: 1.1 mmol.

4. Use according to any one of claims 1 to 3, characterized in that: The ratio of the fluorescent monomer solution, solvent, acrylamide compound, metal salt, water, crosslinking agent solution, accelerator and initiator is 380-410 μL: 1.5-5.5 g: 1.8-2.2 g: 0.25-0.35 g: 9-11 mL: 9-11 μL: 0.8-1.2 μL: 20-25 mg.

5. The use according to claim 4, wherein: Step (1) is as follows: the coumarin derivative and sodium hydroxide are dissolved in anhydrous ethanol and stirred at 58-62℃ for 25-35 min. After cooling to room temperature, methacryloyl chloride is added dropwise at 0-5℃. After the addition is complete, the reaction is stirred for 85-100 min. After the reaction is complete, the product is poured onto crushed ice to form a solid. Then, the product is filtered, washed with cold water, vacuum dried and recrystallized in sequence to obtain the fluorescent monomer.

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