Hydrogel with X-ray radiation luminescence performance and preparation method thereof

Abstract

The invention discloses hydrogel with X-ray radiation luminescence performance and a preparation method thereof, and belongs to the technical field of hydrogel materials.The preparation method comprises the steps that firstly, vinyl monomers containing stilbene units are synthesized, copolymerization reaction is conducted on the vinyl monomers containing the stilbene units and water-soluble monomers through free radical polymerization reaction, and the hydrogel with the X-ray radiation luminescence performance is obtained; a polymer A is obtained. Then synthesizing a vinyl monomer containing a cyclodextrin unit, and carrying out a copolymerization reaction on the vinyl monomer containing the cyclodextrin unit and a water-soluble monomer through a free radical polymerization reaction to obtain a polymer B; and synthesizing the supramolecular hydrogel with the X-ray radiation luminescence property by utilizing the host-guest interaction of the polymer A and the polymer B. The prepared hydrogel emits green visible fluorescence under X-ray radiation, does not contain metal elements, is high in water content, and is green and environment-friendly.

Description

Technical Field

[0001] This invention belongs to the field of hydrogel materials technology, and particularly relates to a hydrogel with X-ray luminescence properties and its preparation method. Background Technology

[0002] X-ray imaging is one of the core technologies in modern medical diagnostics. Its core principle is to convert X-ray signals into visual images using a rigid X-ray scintillator screen, providing crucial information for clinical diagnosis. However, traditional rigid scintillator screens have significant limitations: poor fit to non-planar objects, poor image quality, and inability to meet the practical needs of dynamic imaging of non-planar objects. Therefore, the development of flexible X-ray scintillator screens has become a research hotspot in related fields in recent years. Their ability to be fabricated into arbitrary shapes and adaptable to non-planar objects provides a new solution for dynamic real-time monitoring.

[0003] Currently, mainstream X-ray scintillator materials are mainly inorganic crystals. Although these materials have excellent luminescent properties, they are inherently rigid structures and difficult to process into flexible forms. At the same time, they have poor water solubility and poor compatibility with polymer materials. If they are attempted to be incorporated into hydrogels, it is difficult to achieve uniform dispersion, which ultimately affects the imaging effect.

[0004] Existing technologies have yet to overcome the aforementioned bottlenecks: Patent CN 118027968 discloses a modified Y2MgTiO6 material doped with trivalent bismuth and trivalent europium ions. This material can emit yellow-red visible light under X-ray irradiation and exhibits good stability, but it is still a rigid crystalline material and cannot be processed into a flexible radiative luminescent material; Patent CN 118407136 discloses a lead-containing organic-inorganic hybrid material Bmpip2PbBr4, which can convert various radiation signals such as X-rays and gamma rays into visible light and exhibits excellent stability, but due to the presence of highly toxic lead, it is difficult to apply in the biomedical field; The technology reported in Nature (2021, 590, 410–415) involves doping inorganic scintillator nanoparticles into a polymer film, demonstrating the imaging advantages of flexible materials for aspherical objects, but this composite imaging screen is a heterogeneous material, and the imaging effect is easily affected by the compatibility of the components.

[0005] In summary, existing X-ray luminescence materials generally suffer from two major problems: either they contain toxic metal elements, limiting their application in biomedical scenarios; or their rigid structures are difficult to process into flexible forms, making them unsuitable for dynamic imaging of non-planar objects. Therefore, developing a metal-free material with flexible bonding properties and X-ray luminescence performance has become a key and challenging issue in this field. Hydrogels, as high-water-content polymeric three-dimensional network materials, possess excellent shape adaptability, biocompatibility, and high transparency, perfectly meeting the substrate requirements of flexible X-ray scintillator screens and providing an ideal solution to the aforementioned problems. Summary of the Invention

[0006] To address the aforementioned technical problems, this invention proposes a hydrogel with X-ray radioluminescence properties and its preparation method.

[0007] To achieve the above objectives, the present invention provides the following technical solution: One objective of this invention is to provide a method for preparing a hydrogel with X-ray radioluminescence properties, comprising the following steps: (1) p-Aldehydebenzoic acid, N,N-dimethylformamide and thionyl chloride were reacted under heating conditions. After the reaction was completed, the unreacted thionyl chloride was removed. Hydroxyethyl methacrylate, tetrahydrofuran and triethylamine were added in an ice-water bath and the reaction was continued to obtain the crude product. Compound 1 was obtained by column chromatography. (2) Compound 1, sodium hydride, N,N-dimethylformamide and diethyl 4-bromobenzyl phosphite were stirred and reacted to obtain a crude product, which was then separated by column chromatography to obtain compound 2. (3) The compound 2, N-hydroxymethylacrylamide, azobisisobutyronitrile and N,N-dimethylformamide were reacted under heating conditions. After the reaction was completed, a precipitant was used for anti-precipitation treatment to obtain polymer A. (4) Dissolve cyclodextrin and potassium hydroxide in water, add acryloyl chloride in an ice-water bath and stir to react. After the reaction is complete, use a precipitant to perform reverse precipitation treatment to obtain compound CD-Ac; (5) The compound CD-Ac, acrylamide, potassium persulfate and dimethyl sulfoxide are reacted under heating conditions. After the reaction is completed, a precipitant is used for anti-precipitation treatment to obtain polymer B. (6) Mix the polymer A and the polymer B in water, stir evenly, and let stand to form a hydrogel; The structural formulas of compound 1, compound 2, polymer A, compound CD-Ac, and polymer B are as follows: , , , and ; n and m represent the number of repeating units on the left and right sides of polymer A, respectively, and x and y represent the number of repeating units on the left and right sides of polymer B, respectively.

[0008] This invention first synthesizes a vinyl monomer containing stilbene units, and then copolymerizes this vinyl monomer with a water-soluble monomer via free radical polymerization to obtain polymer A. Next, it synthesizes a vinyl monomer containing cyclodextrin units, and then copolymerizes this vinyl monomer with a water-soluble monomer via free radical polymerization to obtain polymer B. Utilizing the host-guest interaction between polymers A and B, a supramolecular hydrogel with X-ray luminescence properties is synthesized.

[0009] Further, in step (1), the mass ratio of p-aldehyde benzoic acid to thionyl chloride is 1:(4-20), preferably 1:(6-17); The amount of N,N-dimethylformamide used is 1-5% of the mass of p-aldehyde benzoic acid, preferably 1.5-4%; The heating temperature is 50-80℃, preferably 55-75℃; the heating time is 1-5 hours, preferably 1-4 hours; The mass ratio of p-aldehyde benzoic acid, hydroxyethyl methacrylate, tetrahydrofuran, and triethylamine is 1:(0.5-4):(4-20):(0.5-4); preferably 1:(1-4):(6-17):(1-4). The temperature for the continued reaction is 50-80℃, preferably 55-75℃; the time is 8-15 hours, preferably 9-14 hours.

[0010] This invention specifies the mass ratio of aldehyde benzoic acid to each reagent, the reaction temperature, and the reaction time to ensure the efficient synthesis and high purity of compound 1. By optimizing the acylation and esterification reaction conditions, the stability of the monomer structure is improved, thus ensuring the luminescent properties of the subsequent polymer A.

[0011] Further, in step (2), the mass ratio of compound 1, sodium hydride, N,N-dimethylformamide and diethyl 4-bromobenzyl phosphite is 1:(0.05-0.3):(10-30):(0.5-4); preferably 1:(0.05-0.25):(12-25):(1-4); The stirring reaction time is 8-15 hours, preferably 9-14 hours.

[0012] This invention specifies the ratio and reaction time of compound 1 with raw materials such as diethyl 4-bromobenzyl phosphite to ensure the successful formation of compound 2 (stilbene derivative monomer). By precisely controlling the reaction conditions, byproducts are avoided, the reactivity of the monomer is guaranteed, and the foundation for the copolymerization reaction of polymer A is laid.

[0013] Further, in step (3), the mass ratio of compound 2, N-hydroxymethylacrylamide, azobisisobutyronitrile and N,N-dimethylformamide is 1:(1-5):(0.01-0.20):(20-60); preferably 1:(1-4):(0.02-0.20):(30-60); The heating temperature is 50-80℃, preferably 55-75℃, and the heating time is 8-15 hours, preferably 9-14 hours; The precipitant is selected from acetone, methanol, diethyl ether and petroleum ether, preferably acetone or methanol.

[0014] This invention specifies the copolymerization ratio of compound 2 with N-hydroxymethylacrylamide, the amount of initiator, and the reaction conditions to achieve controlled polymerization of polymer A. By optimizing the polymerization reaction parameters, the molecular weight uniformity of polymer A is improved, and the host-guest interaction efficiency between polymer A and polymer B is enhanced.

[0015] Further, in step (4), the mass ratio of cyclodextrin to potassium hydroxide is 1:(0.1-0.5); preferably 1:(0.2-0.5). The cyclodextrin is one of α-cyclodextrin, β-cyclodextrin, and γ-cyclodextrin; preferably γ-cyclodextrin. The mass ratio of cyclodextrin to acryloyl chloride is 1:(0.1-0.5); preferably 1:(0.2-0.5). The temperature of the stirring reaction is 20-40℃, preferably 22-35℃, and the time is 3-12 hours, preferably 4-10 hours; The precipitant is selected from acetone, methanol, diethyl ether and petroleum ether, preferably acetone or methanol.

[0016] This invention specifies the type of cyclodextrin and its ratio with potassium hydroxide and acryloyl chloride to ensure the successful synthesis of compound CD-Ac (acryloyl-substituted cyclodextrin). By controlling the reaction temperature and time, the degree of substitution of the cyclodextrin is ensured to provide a stable host recognition site for polymer B.

[0017] Further, in step (5), the mass ratio of the compound CD-Ac, acrylamide, potassium persulfate and dimethyl sulfoxide is 1:(0.01-0.5):(0.01-0.5):(10-50); preferably 1:(0.02-0.5):(0.02-0.5):(20-50); The heating temperature is 50-80℃, preferably 55-75℃, and the heating time is 8-15 hours, preferably 9-14 hours; This invention clarifies the copolymerization ratio and reaction conditions of CD-Ac and acrylamide, achieving efficient synthesis of polymer B. By optimizing the polymerization system parameters, the water solubility and dispersibility of polymer B are improved, ensuring the formation of a uniform hydrogel network after mixing with polymer A.

[0018] The precipitant is selected from acetone, methanol, diethyl ether and petroleum ether, preferably acetone or methanol.

[0019] This invention limits the precipitant to common solvents such as acetone and methanol, achieving efficient purification of polymer A, CD-Ac, and polymer B. By selecting a green, environmentally friendly, and easily recyclable precipitant, the environmental impact of the preparation process is reduced, aligning with the advantages of "green and environmentally friendly" practices.

[0020] Further, in step (6), the mass ratio of polymer A, polymer B and water is 1:(0.5-4):(4-30); preferably 1:(0.5-3):(4-25). The settling time is 8-15 hours, preferably 9-14 hours.

[0021] This invention specifies the mass ratio of polymers A and B to water and the settling time to ensure sufficient host-guest interaction and the formation of a stable hydrogel. By optimizing the mixing and settling conditions, the homogeneity and mechanical stability of the hydrogel are improved, ensuring its flexible adhesion and consistent imaging.

[0022] The second objective of this invention is to provide a hydrogel prepared using the above-described preparation method.

[0023] This invention directly protects the hydrogel product prepared by the above method, whose core advantages include: no metal elements, high water content, and environmental friendliness. This hydrogel exhibits green visible fluorescence emission under X-ray irradiation, and also possesses good biocompatibility and shape adaptability, breaking through the limitations of traditional materials.

[0024] The third objective of this invention is to provide an application of hydrogel in the field of flexible X-ray imaging, used to prepare flexible X-ray scintillator screens, which are adapted for dynamic real-time X-ray monitoring of non-planar objects.

[0025] This invention clarifies the application of hydrogels in flexible X-ray imaging, specifically addressing the need for dynamic imaging of non-planar objects. By focusing on core application scenarios, this invention highlights the practical value of the product and provides an ideal material solution for the development of flexible X-ray scintillator screens.

[0026] Compared with the prior art, the present invention has the following advantages and technical effects: The hydrogel prepared by this invention has the advantages of X-ray luminescence properties and does not contain highly toxic metal elements.

[0027] The final step of this invention uses water as the reaction solvent and the dispersion medium for the final product, which has the advantage of being green and environmentally friendly. Attached Figure Description

[0028] The accompanying drawings, which form part of this invention, are used to provide a further understanding of the invention. The illustrative embodiments of the invention and their descriptions are used to explain the invention and do not constitute an undue limitation of the invention. In the drawings: Figure 1 This is a synthetic route diagram for compound 1 in Example 1; Figure 2 This is the synthetic route diagram for compound 2 in Example 2; Figure 3 This is a synthetic route diagram for polymer A in Example 3; Figure 4 The 1H NMR spectrum of compound 1 synthesized in Example 1; Figure 5 The carbon NMR spectrum of compound 1 synthesized in Example 1; Figure 6 The 1H NMR spectrum of compound 2 synthesized in Example 2; Figure 7 The carbon NMR spectrum of compound 2 synthesized in Example 2; Figure 8 The 1H NMR spectrum of polymer A synthesized in Example 3; Figure 9 The 1H NMR spectrum of the γ-CD-Ac synthesized in Example 4; Figure 10 The carbon NMR spectrum of γ-CD-Ac synthesized in Example 4; Figure 11 The 1H NMR spectrum of polymer B synthesized in Example 5; Figure 12 A photograph of the hydrogel prepared in Example 6; Figure 13 The image shows the X-ray excitation fluorescence spectrum of the hydrogel prepared in Example 6. Detailed Implementation

[0029] Various exemplary embodiments of the present invention will now be described in detail. This detailed description should not be considered as a limitation of the present invention, but rather as a more detailed description of certain aspects, features, and embodiments of the present invention.

[0030] It should be understood that the terminology used in this invention is merely for describing particular embodiments and is not intended to limit the invention. Furthermore, with respect to numerical ranges in this invention, it should be understood that each intermediate value between the upper and lower limits of the range is also specifically disclosed. Every smaller range between any stated value or intermediate value within a stated range, and any other stated value or intermediate value within said range, is also included in this invention. The upper and lower limits of these smaller ranges may be independently included or excluded from the range.

[0031] Unless otherwise stated, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art. While only preferred methods and materials have been described herein, any methods and materials similar or equivalent to those described herein may be used in the implementation or testing of this invention. All references to this specification are incorporated by way of citation to disclose and describe methods and / or materials associated with those references. In the event of any conflict with any incorporated reference, the content of this specification shall prevail.

[0032] Various modifications and variations can be made to the specific embodiments described in this specification without departing from the scope or spirit of the invention, as will be apparent to those skilled in the art. Other embodiments derived from this specification will also be apparent to those skilled in the art. This specification and embodiments are merely exemplary.

[0033] The terms “include,” “including,” “have,” “contain,” etc., used in this article are all open-ended terms, meaning that they include but are not limited to.

[0034] This invention provides a method for preparing a hydrogel with X-ray radioluminescence properties, comprising the following steps: 1) Preparation of compound 1: p-Aldehydebenzoic acid, thionyl chloride, and N,N-dimethylformamide (N,N-dimethylformamide amount is 1-5% of the mass of p-Aldehydebenzoic acid) were added to a reaction flask containing a reflux system at a mass ratio of 1:(4-20):(0.01-0.05) and reacted at 50-80℃ for 1-5 hours. After the reaction was completed, the mixture was cooled to room temperature, and unreacted thionyl chloride was removed by rotary evaporation. Hydroxyethyl methacrylate, tetrahydrofuran, and triethylamine were added in an ice-water bath at a mass ratio of p-Aldehydebenzoic acid:hydroxyethyl methacrylate:tetrahydrofuran:triethylamine = 1:(0.5-4):(4-20):(0.5-4). The mixture was further reacted at 50-80℃ for 8-15 hours to obtain the crude product, which was then separated by column chromatography to obtain compound 1.

[0035] 2) Preparation of compound 2: Compound 1, sodium hydride, N,N-dimethylformamide and diethyl 4-bromobenzyl phosphite were added to a flask in a mass ratio of 1:(0.05-0.3):(10-30):(0.5-4) and stirred for 8-15 hours to obtain the crude product. Compound 2 was obtained by column chromatography.

[0036] 3) Synthesis of Polymer A: Compound 2, N-hydroxymethylacrylamide, azobisisobutyronitrile, and N,N-dimethylformamide were added to a flask in a mass ratio of 1:(1-5):(0.01-0.20):(20-60) and reacted at 50-80℃ for 8-15 hours. After the reaction was completed, the reaction system was subjected to reverse precipitation treatment using acetone, methanol, diethyl ether, or petroleum ether as a precipitant to obtain polymer A.

[0037] 4) Synthesis of compound CD-Ac (acryloyl-substituted cyclodextrin): Cyclodextrin and potassium hydroxide were dissolved in water at a mass ratio of 1:(0.1-0.5) and stirred until completely dissolved. One of α-cyclodextrin, β-cyclodextrin, or γ-cyclodextrin was selected. Acryloyl chloride was added in an ice-water bath at a mass ratio of 1:(0.1-0.5) and the reaction was stirred at 20-40℃ for 3-12 hours. After the reaction was completed, one of acetone, methanol, diethyl ether, or petroleum ether was used as a precipitant for reverse precipitation to obtain compound CD-Ac.

[0038] 5) Synthesis of polymer B (acryloyl-substituted cyclodextrin-acrylamide copolymer): Compound CD-Ac, acrylamide, potassium persulfate, and dimethyl sulfoxide were added to a flask in a mass ratio of 1:(0.01-0.5):(0.01-0.5):(10-50) and reacted at 50-80℃ for 8-15 hours. After the reaction was completed, the reaction system was subjected to reverse precipitation treatment using acetone, methanol, diethyl ether, or petroleum ether as a precipitant to obtain polymer B.

[0039] 6) Preparation of hydrogel: Take polymer A, polymer B and water in a mass ratio of 1:(0.5-4):(4-30). Mix polymer A and polymer B in water, stir evenly and let stand for 8-15 hours to form hydrogel.

[0040] For example, in the following preferred embodiments of the present invention, in step (1), the mass ratio of p-aldehyde benzoic acid to thionyl chloride is 1:16.4, the amount of N,N-dimethylformamide is 1% of the mass of p-aldehyde benzoic acid, the initial reaction temperature is 60°C and the time is 3 hours; the mass ratio of p-aldehyde benzoic acid to hydroxyethyl methacrylate, tetrahydrofuran and triethylamine is 1:1:9:1, and the reaction continues at 60°C for 12 hours.

[0041] For example, in the following preferred embodiments of the present invention, in step (2), the mass ratio of compound 1 to sodium hydride, N,N-dimethylformamide and diethyl 4-bromobenzyl phosphite is 1:0.15:20:1, and the reaction time is 12 hours.

[0042] For example, in the following preferred embodiments of the present invention, in step (3), the mass ratio of compound 2 to N-hydroxymethylacrylamide, azobisisobutyronitrile, and N,N-dimethylformamide is 1:2.4:0.2:38, the reaction temperature is 70°C, the reaction time is 12 hours, and the precipitant is acetone.

[0043] For example, in the following preferred embodiments of the present invention, in step (4), the mass ratio of cyclodextrin to potassium hydroxide is 1:0.15, the cyclodextrin is γ-cyclodextrin, the mass ratio of cyclodextrin to acryloyl chloride is 1:0.3, the reaction temperature is 25°C, the reaction time is 6 hours, and the precipitant is methanol.

[0044] For example, in the following preferred embodiments of the present invention, in step (5), the mass ratio of CD-Ac to acrylamide, potassium persulfate and dimethyl sulfoxide is 1:0.32:0.1:22, the reaction temperature is 70°C and the time is 12 hours, and the precipitant is acetone.

[0045] For example, in the following preferred embodiments of the present invention, in step (6), the mass ratio of polymer A, polymer B and water is 1:1:4, and the settling time is 12 hours.

[0046] The hydrogel with X-ray luminescence properties prepared by the above preparation method is formed by the host-guest interaction between polymer A and polymer B. It does not contain metal elements, emits green visible fluorescence under X-ray irradiation, and has good shape self-adaptation ability, biocompatibility and high transparency.

[0047] The above-mentioned hydrogel is used in the field of flexible X-ray imaging, specifically to prepare flexible X-ray scintillator screens, which can be adapted to non-planar objects and realize dynamic real-time X-ray monitoring.

[0048] Unless otherwise specified, "room temperature" in this invention refers to 25±2℃.

[0049] The raw materials or reagents used in this invention can be purchased commercially. Specifically, p-aldehyde benzoic acid was purchased from Shanghai Titan Technology Co., Ltd., with a purity of 99.9%; hydroxyethyl methacrylate was purchased from Shanghai Aladdin Biochemical Technology Co., Ltd., with a purity of 99.9%; diethyl 4-bromobenzyl phosphite was purchased from Shanghai Titan Technology Co., Ltd., with a purity of 98%; sodium hydride was purchased from Shanghai Anaiji Pharmaceutical Chemical Co., Ltd., with a purity of 99%; thionyl chloride was purchased from Tianjin Jindong Tianzheng Fine Chemical Reagent Factory, with a purity of 99.9%; γ-cyclodextrin was purchased from Shanghai Titan Technology Co., Ltd., with a purity of 99%; N-hydroxymethylacrylamide was purchased from Shanghai Aladdin Biochemical Technology Co., Ltd., with a purity of 99%; triethylamine was purchased from Tianjin Kemio Chemical Technology Co., Ltd., with a purity of 99.9%; and organic solvents such as tetrahydrofuran, N,N-dimethylformamide, and methanol were purchased from Tianjin Kemio Chemical Technology Co., Ltd., with a purity of 99.9%. The water used in the preparation process was Wahaha purified water. Using similar reagents from other sources can also yield the same results.

[0050] The processes and methods not described in detail in the following embodiments are conventional methods known in the art.

[0051] The technical solution of the present invention will be further illustrated by the following embodiments.

[0052] Example 1: Synthesis of Compound 1 (preparation flowchart as shown) Figure 1 (As shown) 1 g of p-aldehyde benzoic acid, 10 mg of N,N-dimethylformamide (DMF), and 10 mL of thionyl chloride (SOCl2) were added to a reaction flask containing a reflux system, and the reaction was carried out at 60 °C for 3 hours. After the reaction was completed, the mixture was cooled to room temperature, and unreacted thionyl chloride was removed using a rotary evaporator. 0.96 g of hydroxyethyl methacrylate was added in an ice-water bath, followed by 10 mL of tetrahydrofuran (THF) and 1.5 mL of triethylamine. The reaction was continued at 60 °C for 12 hours. After the reaction was completed, the reaction mixture was poured into an aqueous solution in a separatory funnel, and dichloromethane was added to extract the dichloromethane and water mixture. After multiple extractions, the dichloromethane organic phases were combined, dried over anhydrous sodium sulfate for 12 hours, and the organic phase solvent was removed using a rotary evaporator to obtain the crude product. The crude product was then separated and purified using petroleum ether / ethyl acetate (volume ratio 6:1) as the eluent. The purified product was collected to obtain compound 1.

[0053] Example 2: Synthesis of Compound 2 (preparation flowchart as shown) Figure 2 (As shown) 1 g of compound 1, 150 mg of sodium hydride (NaH), and 20 g of N,N-dimethylformamide (DMF) were added to a reaction flask and stirred for 20 min under nitrogen protection in an ice-water bath. 1 g of diethyl 4-bromobenzyl phosphite was dissolved in 10 mL of N,N-dimethylformamide and added dropwise to the reaction system using a syringe. The addition was completed over 30 min, and the reaction was stirred for 12 hours. After the reaction was complete, the dichloromethane and water mixture was extracted. After multiple extractions, the dichloromethane organic phases were combined, dried over anhydrous sodium sulfate for 12 hours, and the organic phase solvent was removed using a rotary evaporator to obtain the crude product. The crude product was purified by column chromatography using petroleum ether / ethyl acetate (4:1 v / v) as the eluent. The purified product was collected to obtain compound 2.

[0054] Example 3: Synthesis of Polymer A (Preparation flowchart as shown) Figure 3 (As shown) 0.05 g of compound 2, 0.12 g of N-hydroxymethylacrylamide, 10 mg of azobisisobutyronitrile (AIBN), and 2 mL of N,N-dimethylformamide (DMF) were added to a reaction flask, and the mixture was reacted at 70 °C for 12 hours. After the reaction was completed, the reaction solution was added dropwise to acetone solution, and a white precipitate formed. The precipitate was obtained by centrifugation, yielding a white solid polymer A.

[0055] Example 4: Synthesis of Cyclodextrin-containing Monomers 0.5 g of γ-cyclodextrin (γ-CD) and 0.15 g of potassium hydroxide were dissolved in 7 mL of water and stirred until completely dissolved. 150 mg of acryloyl chloride was added in an ice-water bath, and the mixture was stirred at 25 °C for 6 hours. After the reaction was complete, the aqueous solution of the polymer was added dropwise to methanol, resulting in a white solid precipitate. The precipitate was obtained by centrifugation, yielding a white solid γ-CD-Ac.

[0056] Example 5: Synthesis of Polymer B 0.100 g of γ-CD-Ac, 0.032 g of acrylamide, 0.010 g of potassium persulfate, and 2 mL of dimethyl sulfoxide were added to a reaction flask, and the reaction was carried out at 70 °C for 12 hours. After the reaction was completed, the polymer aqueous solution was added dropwise to acetone solution, and a white precipitate was formed. The precipitate, identified as polymer B, was obtained by centrifugation.

[0057] Example 6: Synthesis of Hydrogel Mix 100 mg of polymer A and 100 mg of polymer B and add to 0.4 mL of water. Let stand in a flat-bottomed cylindrical glass bottle for 12 hours to obtain a hydrogel.

[0058] The product obtained above was subjected to the following structural characterization and performance tests.

[0059] 1. Nuclear magnetic resonance analysis Compound 1 and polymer A were dissolved in deuterated dimethyl sulfoxide, compound 2 was dissolved in deuterated chloroform, and the synthesized γ-CD-Ac was dissolved in deuterated water. The results were analyzed using a Bruker 400M nuclear magnetic resonance spectrometer. 1 H NMR and 13 The results of the C NMR analysis are as follows: Compound 1: 1 H NMR (400 MHz, d 6-DMSO) δ 10.10 (s, 1H), 8.13 (d, 2H), 8.04(d, 2H), 6.03 (s, 1H), 5.68 (d, 1H), 4.64 – 4.52 (m, 2H), 4.50 – 4.41 (m,2H), 1.86 (s, 3H). 13 C NMR (100 MHz, DMSO) δ 193.38, 166.87, 165.33, 139.67, 136.05, 134.57, 130.22, 126.62, 63.63, 62.76, 39.95, 18.39. Compound 2: 1 H NMR (400 MHz, CDCl3) δ 8.03 (d, 2H), 7.56 (d, 2H), 7.50 (d,2H), 7.40 (d, 2H), 7.13 (d, 2H), 6.15 (s, 1H), 5.60 (d, 1H), 4.60 – 4.54 (m,2H), 4.50 (dd, 2H), 1.96 (s, 3H). 13 C NMR (101 MHz, CDCl3) δ 167.21, 166.07,141.69, 131.97, 130.16, 128.56, 126.45, 126.15, 122.15, 82.01, 73.82, 62.57,18.33. γ-CD-Ac: 1 H NMR (400 MHz, D2O) δ 6.07- 6.0(CH2=CH2), 5.94 - 5.89(CH2=CH2), 5.57 - 5.54(CH2=CH2), 5.02(O-CH-O), 3.89 – 3.67(C-CH-OH and C-CH2-OH),3.61 – 3.44(C-CH-O).13 C NMR (101 MHz, D2O) δ 133.72, 126.49, 101.64, 80.40,72.90, 72.28, 71.73, 66.56, 60.18, 57.4. Figure 4 The image shows the hydrogen nuclear magnetic resonance spectrum of compound 1 synthesized in Example 1. Figure 5 The image shows the carbon NMR spectrum of compound 1 synthesized in Example 1.

[0060] Figure 4 The signal peak at 10.1 ppm is attributed to the aldehyde hydrogen (Ha); the peaks at 8.14-8.03 ppm are attributed to hydrogen on the benzene ring (Hb); the peaks at 4.59-4.46 ppm are attributed to methylene hydrogen (Hc) on the ester chain; the peaks at 8.05-6.03 ppm are attributed to hydrogen on the alkyl chain double bond (Hd); and the peak at 1.86 ppm is attributed to the terminal methyl hydrogen (He) on the alkyl chain. This is consistent with... Figure 1 The reaction mechanism shown proves that compound 1 was successfully synthesized.

[0061] Figure 6 The image shows the hydrogen nuclear magnetic resonance spectrum of compound 2 synthesized in Example 2. Figure 7 The image shows the carbon NMR spectrum of compound 2 synthesized in Example 2.

[0062] Figure 6 The signal peaks at 8.04-7.13 ppm are attributed to aryl hydrogens (Ha, Hc); the signal peak at 7.14-7.13 ppm belongs to hydrogens (Hb) on the double bond between the two benzene rings; the signal peaks at 4.59-4.49 ppm belong to the two methylene hydrogens (Hd) on the ester chain; the two signal peaks at 6.15-5.60 ppm belong to hydrogens (He) on the double bond of the alkyl chain; and the signal peak at 1.93 ppm belongs to the methyl hydrogen (Hf) at the end of the alkyl chain. The signal peak at 10.1 ppm disappears, and a new signal peak for the benzene ring appears in the 8.04-7.13 ppm range. This is consistent with... Figure 2 The reaction mechanism shown proves that compound 2 was successfully synthesized.

[0063] Figure 8 The image shows the 1H NMR spectrum of polymer A synthesized in Example 3. Figure 8The broad signal peaks in the 8.17-7.4 ppm range are attributed to the -NH hydrogen polymerization peaks on the amide group and the hydrogen (Ha) polymerization peaks on the benzene ring, forming a broad multiple signal peak. The hydrogen (Hb) polymerization of the double bond between the two benzene rings forms a broad signal peak at 5.47 ppm. The two methylene hydrogen polymerization peaks on the ester chain, the methylene hydrogen polymerization peak on the hydroxymethyl group, and the hydroxyl hydrogen (Hc) polymerization peak on the hydroxymethyl group collectively constitute a broad signal peak at 4.5 ppm. The broad multiple signal peaks in the 2.33-0.97 ppm range are attributed to the signal peaks generated by the methylene hydrogen (Hb) polymerization on the alkyl chain. Figure 8 The nuclear magnetic resonance (NMR) spectra show that the functional groups in the generated stilbene derivative polymer correspond one-to-one with N-hydroxymethylacrylamide and stilbene derivatives. Figure 3 The reaction mechanism shown is consistent with the expected product polymer A, indicating that polymer A was synthesized.

[0064] Figure 9 The image shows the 1H NMR spectrum of the γ-CD-Ac synthesized in Example 4.

[0065] Figure 10 The image shows the carbon NMR spectrum of the γ-CD-Ac synthesized in Example 4.

[0066] Figure 11 The image shows the 1H NMR spectrum of polymer B synthesized in Example 5.

[0067] Figure 12 This is a photograph of the hydrogel prepared in Example 6.

[0068] 2. Investigation of photophysical properties The fluorescence emission spectrum of the nanocomposite material was tested using an Andor SR500i X-ray source. The hydrogel sample prepared in Example 6 was fixed on a specially designed mold, and the instrument parameters were adjusted to a standard current of 30 mA and a standard voltage of 40 kV before irradiation. The photoluminescence intensity and wavelength were collected using a fiber optic detector, and the results are shown below. Figure 13 As shown.

[0069] Figure 13 The image shows the X-ray excitation fluorescence spectrum of the hydrogel prepared in Example 6. As can be seen from the image, the sample exhibits an emission peak near 432 nm, displaying typical X-ray luminescence properties.

[0070] The above are merely preferred embodiments of the present invention, but the scope of protection of the present invention is not limited thereto. Any variations or substitutions that can be easily conceived by those skilled in the art within the scope of the technology disclosed in the present invention should be included within the scope of protection of the present invention. Therefore, the scope of protection of the present invention should be determined by the scope of the claims.

Claims

1. A method for preparing a hydrogel with X-ray radioluminescence properties, characterized in that, Includes the following steps: (1) p-Aldehydebenzoic acid, N,N-dimethylformamide and thionyl chloride were reacted under heating conditions. After the reaction was completed, the unreacted thionyl chloride was removed. Hydroxyethyl methacrylate, tetrahydrofuran and triethylamine were added in an ice-water bath and the reaction was continued to obtain the crude product. Compound 1 was obtained by column chromatography. (2) Compound 1, sodium hydride, N,N-dimethylformamide and diethyl 4-bromobenzyl phosphite were stirred and reacted to obtain a crude product, which was then separated by column chromatography to obtain compound 2. (3) The compound 2, N-hydroxymethylacrylamide, azobisisobutyronitrile and N,N-dimethylformamide were reacted under heating conditions. After the reaction was completed, a precipitant was used for anti-precipitation treatment to obtain polymer A. (4) Dissolve cyclodextrin and potassium hydroxide in water, add acryloyl chloride in an ice-water bath and stir to react. After the reaction is complete, use a precipitant to perform reverse precipitation treatment to obtain compound CD-Ac; (5) The compound CD-Ac, acrylamide, potassium persulfate and dimethyl sulfoxide are reacted under heating conditions. After the reaction is completed, a precipitant is used for anti-precipitation treatment to obtain polymer B. (6) Mix the polymer A and the polymer B in water, stir evenly, and let stand to form a hydrogel; The structural formulas of compound 1, compound 2, polymer A, compound CD-Ac, and polymer B are as follows: , , , and ； n and m represent the number of repeating units on the left and right sides of polymer A, respectively; x and y represent the number of repeating units on the left and right sides of polymer B, respectively.

2. The preparation method according to claim 1, characterized in that, In step (1), the mass ratio of p-aldehyde benzoic acid to thionyl chloride is 1:(4-20); and / or, The amount of N,N-dimethylformamide used is 1-5% of the mass of p-aldehyde benzoic acid; and / or, The heating temperature is 50-80℃, and the time is 1-5 hours; and / or, The mass ratio of p-aldehyde benzoic acid, hydroxyethyl methacrylate, tetrahydrofuran, and triethylamine is 1:(0.5-4):(4-20):(0.5-4); and / or, The continued reaction is carried out at a temperature of 50-80°C for 8-15 hours.

3. The preparation method according to claim 1, characterized in that, In step (2), the mass ratio of compound 1, sodium hydride, N,N-dimethylformamide, and diethyl 4-bromobenzyl phosphite is 1:(0.05-0.3):(10-30):(0.5-4); and / or, The stirring reaction takes 8-15 hours.

4. The preparation method according to claim 1, characterized in that, In step (3), the mass ratio of compound 2, N-hydroxymethylacrylamide, azobisisobutyronitrile, and N,N-dimethylformamide is 1:(1-5):(0.01-0.20):(20-60); and / or, The heating temperature is 50-80℃, and the time is 8-15 hours.

5. The preparation method according to claim 1, characterized in that, In step (4), the mass ratio of cyclodextrin to potassium hydroxide is 1:(0.1-0.5); and / or, The cyclodextrin is one of α-cyclodextrin, β-cyclodextrin, and γ-cyclodextrin; and / or, The mass ratio of the cyclodextrin to acryloyl chloride is 1:(0.1-0.5); and / or, The stirring reaction is carried out at a temperature of 20-40℃ for 3-12 hours.

6. The preparation method according to claim 1, characterized in that, In step (5), the mass ratio of the compound CD-Ac, acrylamide, potassium persulfate, and dimethyl sulfoxide is 1:(0.01-0.5):(0.01-0.5):(10-50); and / or, The heating temperature is 50-80℃, and the time is 8-15 hours.

7. The preparation method according to claim 1, characterized in that, In steps (3), (4), and (5), the precipitant is selected from one of acetone, methanol, diethyl ether, and petroleum ether.

8. The preparation method according to claim 1, characterized in that, In step (6), the mass ratio of polymer A, polymer B, and water is 1:(0.5-4):(4-30); and / or, The settling time is 8-15 hours.

9. A hydrogel prepared by the preparation method according to any one of claims 1-8.

10. An application of the hydrogel as described in claim 9 in the field of flexible X-ray imaging.

Images