Temperature and x-ray dual-responsive aie hydrogel film and preparation method thereof

Abstract

The application discloses a kind of temperature and X ray dual response AIE hydrogel film and preparation method thereof, belong to hydrogel preparation technical field.The volume of NPR microgel prepared in the application will decrease with the increase of temperature, the change leads to the colorimetric fluorescence signal intensity (F 430 / F 580 ) of NPR microgel and NPR / PVA film is enhanced.The volume of NPR microgel will increase with the increase of dose, under 0~80Gy X ray, the fluorescence color of NPR-SS hydrogel film changes from blue purple to purple red, and the sensitivity is 0.032Gy ‑1 .The hydrogel film prepared in the application can realize the dual response of temperature and X ray dose, and the linear relationship between fluorescence intensity and response is constructed, and the film has strong adhesion, high sensitivity, low detection limit and easy naked eye observation, which provides a new strategy for wearable sensor.

Description

Technical Field

[0001] This invention belongs to the field of hydrogel preparation technology, specifically relating to a temperature and X-ray dual-response AIE hydrogel film and its preparation method. Background Technology

[0002] Traditional thermometers, especially mercury thermometers, while accurate, have several drawbacks. The mercury inside is toxic, and if broken, mercury vapor can be harmful to human health. Furthermore, mercury thermometers are relatively slow, typically requiring several minutes to obtain an accurate reading. Operational skill is also required to ensure accuracy. In medical and industrial applications, X-ray dosimeters are often used to measure radiation dose, but they have limitations. For example, traditional X-ray dosimeters can be expensive and labor-intensive, and some require regular calibration to ensure accuracy. Overall, traditional thermometers or X-ray dosimeters are often made of rigid materials, making them difficult to fit against the skin, limiting their application in wearable devices. Summary of the Invention

[0003] The purpose of this section is to outline some aspects of embodiments of the present invention and to briefly describe some preferred embodiments. Simplifications or omissions may be made in this section, as well as in the abstract and title of this application, to avoid obscuring the purpose of these documents; however, such simplifications or omissions should not be construed as limiting the scope of the invention.

[0004] This invention discloses a method for synthesizing temperature- and X-ray dual-response AIE (aggregation-induced emission) hydrogel films, which solves the following technical problems:

[0005] First, traditional mercury thermometers are not only slow to measure temperature, but also require a certain level of skill to ensure accurate readings. In contrast, this invention uses N-isopropylacrylamide (NIPAm) as a base material to develop a hydrogel film that can rapidly sense changes in ambient temperature and change color accordingly, thus achieving a rapid temperature response.

[0006] Secondly, a common problem with existing X-ray dosimeters is that dose changes are not easily observed directly. Furthermore, traditional X-ray dosimeters are typically made of rigid materials, making it difficult to fit snugly against the skin, which limits their application in fields such as radiotherapy. Our hydrogel film not only establishes a linear relationship between fluorescence intensity and dose but also exhibits excellent skin adhesion, thus expanding the application range of the dosimeter.

[0007] In summary, this invention, based on AIE hydrogel, develops a flexible thin-film sensor that achieves dual sensing and detection of temperature and X-ray dose using fluorescence colorimetry. Combined with image analysis techniques, we found that this AIE hydrogel thin-film sensor exhibits excellent linear response to ambient temperatures of 20-45°C and X-ray doses of 0-80 Gy. It features high sensitivity, a low detection limit, and is easily observed with the naked eye, providing a new material option for the development of future wearable devices.

[0008] In view of the problems existing in the above and / or prior art, the present invention is proposed.

[0009] Therefore, the purpose of this invention is to overcome the shortcomings of the prior art and provide a method for preparing a temperature and X-ray dual-response AIE hydrogel film.

[0010] To solve the above-mentioned technical problems, the present invention provides the following technical solutions, including:

[0011] Synthesis of hydrogels: N-isopropylacrylamide, crosslinking agent, N-(3-aminopropyl)methacrylamide hydrochloride, 4-phenoxy-N-allyl-1,8-naphthalenediamide, and RhB-APMA solution were dissolved in deionized water and heated to 60-80℃. After stirring continuously for 1-2 h under a nitrogen atmosphere, an initiator was added to initiate monomer polymerization. After 4-5 h, P(NIPAm-co-PhAN-co-RhB-APMA) microgels were obtained, denoted as NPR microgels.

[0012] Preparation of NPR / PVA hydrogel film: PVA aqueous solution is added to the above NPR microgel, stirred for 2-4 h, poured into a mold and left to stand at -20℃ for 10-14 h, and then thawed at room temperature for 2-4 h to obtain NPR / PVA hydrogel film.

[0013] In a preferred embodiment of the method for preparing the temperature and X-ray dual-response AIE hydrogel film of the present invention, the crosslinking agent includes one or more of N,N'-methylenebisacrylamide (BIS) containing carbon-carbon double bonds, N,N'-bis(acryloyl)cysteine ​​containing sulfur-sulfur bonds, and diselenodimethylbis(but-4,1-dimethyl)bis(methacrylate) containing selenium-selenium bonds.

[0014] As a preferred embodiment of the method for preparing the temperature and X-ray dual-response AIE hydrogel film of the present invention, the method for preparing the RhB-APMA solution includes:

[0015] Rhodamine B, 1-ethyl-(3-dimethylaminopropyl)carbodiimide hydrochloride, N-hydroxysuccinimide, and MES buffer solution were stirred for 1-2 h. Then, N-(3-aminopropyl)methacrylamide hydrochloride was dissolved in PBS buffer solution and added to the above mixture. Stirring was continued for 3-4 h to obtain RhB-APMA solution.

[0016] As a preferred embodiment of the method for preparing the temperature and X-ray dual-response AIE hydrogel film of the present invention, each 1L of the RhB-APMA solution contains 20-50 mmol Rhodamine B, 20-50 mmol 1-ethyl-(3-dimethylaminopropyl)carbodiimide hydrochloride, 20-50 mmol N-hydroxysuccinimide, 5-7 mL MES buffer solution, 20-50 mmol N-(3-aminopropyl)methacrylamide hydrochloride, and 20-30 mL PBS buffer solution.

[0017] In a preferred embodiment of the method for preparing the temperature and X-ray dual-response AIE hydrogel film of the present invention, the initiator includes one or more of azobisisobutyramidine hydrochloride, ammonium persulfate, and potassium persulfate.

[0018] As a preferred embodiment of the method for preparing the temperature and X-ray dual-response AIE hydrogel film of the present invention, each 1L of the NPR microgel contains 120~130 mmol N-isopropylacrylamide, 10~20 mmol crosslinking agent, 1~2 mmol N-(3-aminopropyl)methacrylamide hydrochloride, 1~2 mmol 4-phenoxy-N-allyl-1,8-naphthalenediamide, 10~50 mL RhB-APMA solution and 2~10 mmol initiator.

[0019] In a preferred embodiment of the method for preparing the temperature and X-ray dual-response AIE hydrogel film of the present invention, the concentration of the PVA aqueous solution is 7.5%~20%.

[0020] In a preferred embodiment of the method for preparing the temperature and X-ray dual-response AIE hydrogel film of the present invention, the method for preparing the PVA aqueous solution includes:

[0021] Polyvinyl alcohol is mixed with deionized water and stirred for 8-10 hours. Then, it is stirred in an oil bath at 85-95°C for 3-5 hours to obtain a PVA aqueous solution.

[0022] In a preferred embodiment of the method for preparing the temperature and X-ray dual-response AIE hydrogel film of the present invention, the volume ratio of the PVA aqueous solution to the NPR microgel is 4~6:1~2.

[0023] Another objective of this invention is to overcome the shortcomings of the prior art and provide a temperature and X-ray dual-response AIE hydrogel film.

[0024] Beneficial effects of this invention:

[0025] As temperature increases, the volume of NPR microgels decreases, a change that affects the colorimetric fluorescence signal intensity (F) of both the NPR microgels and the NPR / PVA film. 430 / F 580 The fluorescence color of the film changes from blue-violet to blue when the temperature rises from 20°C to 45°C. By attaching the hydrogel film to the surface of a water cup or glove, the change in fluorescence signal can be used to intuitively sense and detect the temperature.

[0026] With increasing dosage, the volume of NPR microgels increases. Under X-rays ranging from 0 to 80 Gy, the fluorescence color of the NPR-SS hydrogel film changes from blue-violet to purplish-red, with a sensitivity of 0.032 Gy. -1 The NPR-SeSe hydrogel film has an X-ray detection range of 0–8 Gy and a sensitivity of 0.278 Gy. -1 The fluorescent color also changed from blue-purple to purplish-red.

[0027] The hydrogel film prepared by this invention can achieve dual response to temperature and X-ray dose, and establishes a linear relationship between fluorescence intensity and response. This film has strong adhesion, high sensitivity, low detection limit, and is easy to observe with the naked eye, providing a new strategy for wearable sensors. Attached Figure Description

[0028] To more clearly illustrate the technical solutions of the embodiments of the present invention, the accompanying drawings used in the description of the embodiments will be briefly introduced below. Obviously, the drawings described below are only some embodiments of the present invention. For those skilled in the art, other drawings can be obtained based on these drawings without creative effort. Wherein:

[0029] Figure 1 This is a schematic diagram illustrating the synthesis of the NPR microgel of the present invention.

[0030] Figure 2 This is a product image of NPR / PVA hydrogel film.

[0031] Figure 3 This is a schematic diagram of the temperature response mechanism of NPR-SS microgels.

[0032] Figure 4Fluorescence emission spectra of NPR-SS / PVA hydrogel sensing films at different temperatures (20-45℃): (a) Day 1; (b) Day 3. Corresponding fluorescence intensity ratios to Fo. 430 / F 580 Relationship curve with temperature (λ) ex = 365 nm): (c) Day 1; (d) Day 3.

[0033] Figure 5 Infrared thermal images and 365 nm UV light images of NPR-SS / PVA hydrogel applied to a person's hand / the outer wall of a water cup at different temperatures.

[0034] Figure 6 This is a schematic diagram of the X-ray response mechanism of NPR-based microgels.

[0035] Figure 7 X-ray responsiveness of NPR / PVA hydrogel sensing films: fluorescence emission spectra (λ) of (a) NPR-SS / PVA, (b) NPR-SeSe / PVA and (c) NPR-BIS / PVA. ex = 365 nm); (d) Fluorescence intensity ratio F 430 / F 580 - Radiation dose relationship curve.

[0036] Figure 8 These are photographs of the NPR / PVA hydrogel sensing film under white light and after irradiation under 365 nm UV light. Detailed Implementation

[0037] To make the above-mentioned objects, features and advantages of the present invention more apparent and understandable, the specific embodiments of the present invention will be described in detail below with reference to the examples in the specification.

[0038] Many specific details are set forth in the following description in order to provide a full understanding of the invention. However, the invention may also be practiced in other ways different from those described herein, and those skilled in the art can make similar extensions without departing from the spirit of the invention. Therefore, the invention is not limited to the specific embodiments disclosed below.

[0039] Secondly, the term "one embodiment" or "embodiment" as used herein refers to a specific feature, structure, or characteristic that may be included in at least one implementation of the present invention. The phrase "in one embodiment" appearing in different places in this specification does not necessarily refer to the same embodiment, nor is it a single or selective embodiment that is mutually exclusive with other embodiments.

[0040] Unless otherwise specified, all raw materials used in this invention are commercially available.

[0041] The raw materials are abbreviated as follows:

[0042] N-Isopropylacrylamide (NIPAm), Rhodamine B (RhB), 1-Ethyl-(3-dimethylaminopropyl)carbodiimide hydrochloride (EDC), N-hydroxysuccinimide (NHS), MES, N-(3-aminopropyl)methacrylamide hydrochloride (APMA), N,N'-methylenebisacrylamide (BIS), N,N'-bis(acryloyl)cysteine ​​(BAC), diselenodimethylbis(but-4,1-diyl)bis(methacrylate) (BMASe), cetyltrimethylammonium bromide (CTAB), 4-phenoxy-N-allyl-1,8-naphthalenediamine (PhAN), azobisisobutyramidine hydrochloride (V50), polyvinyl alcohol (PVA), N,N'-bis(acryloyl)cysteine ​​(BAC).

[0043] The materials obtained in the embodiments of the present invention were subjected to performance testing according to the following method:

[0044] The prepared hydrogel film was placed at different temperatures or irradiated with different doses, and the fluorescence spectrum was measured after a certain period of time to establish a linear relationship between fluorescence intensity and temperature or dose. Example

[0045] This embodiment provides a method for preparing a temperature- and X-ray dual-response AIE hydrogel film, as shown in the synthesis schematic diagram ( Figure 1 Specifically:

[0046] 1. Synthesizing hydrogels:

[0047] Rhodamine B (RhB) 0.5 mmol, 1-ethyl-(3-dimethylaminopropyl)carbodiimide hydrochloride (EDC) 1 mmol, N-hydroxysuccinimide (NHS) 0.5 mmol, and 5 mL of MES buffer (0.1 M, pH=5.5) were stirred at room temperature for 1 h. Then, 1 mmol of N-(3-aminopropyl)methacrylamide hydrochloride (APMA) was dissolved in 20 mL of PBS buffer (0.1 M, pH=7.4) and added to the above mixture. The mixture was stirred at room temperature for another 3 h to obtain the RhB-APMA solution.

[0048] In a flask, 12 mmol NIPAm, 1 mmol N,N'-bis(acryloyl)cysteine ​​(BAC) containing sulfur-sulfur bonds, 0.1 mmol hexadecyltrimethylammonium bromide (CTAB), 0.1 mmol 4-phenoxy-N-allyl-1,8-naphthalenediamide (PhAN), 1 mL of the above RhB-APMA solution, and 96 mL of deionized water were mixed and heated to 70 °C. After stirring continuously for 1 h under a nitrogen atmosphere, 0.2 mmol azobisisobutyramidine hydrochloride (V50) initiator was added to initiate monomer polymerization. After 4 h, p(NIPAm-co-PhAN-co-RhB-APMA) microgel was obtained, denoted as NPR-BAC microgel.

[0049] 2. Preparation of NPR / PVA hydrogel films

[0050] Mix 15 g of polyvinyl alcohol with 100 mL of deionized water, stir at room temperature for 8 h, and then continue stirring at 90 °C. o The PVA aqueous solution was obtained by stirring in an oil bath for 3 h. 20 mL of the PVA aqueous solution was taken and 5 mL of NPR-SS microgel solution was added, and the mixture was stirred for 2 h. The mixture was poured into a mold and allowed to stand at -20°C for 12 h, then thawed at room temperature for 3 h. An NPR-SS / PVA hydrogel film with a thickness of 3 mm and a diameter of 3.5 cm was obtained. Example

[0051] The difference between this embodiment and Example 1 is that the type of crosslinking agent is changed to N,N'-methylenebisacrylamide (BIS), a crosslinking agent containing carbon-carbon double bonds. The rest of the preparation process is the same as in Example 1, and an NPR-CC / PVA hydrogel film is obtained. Example

[0052] The difference between this embodiment and Example 1 is that the type of crosslinking agent is adjusted to be diselenodimethylbis(but-4,1-dimethyl)bis(methacrylate) (BMASe), which contains selenium-selenium bonds. The rest of the preparation process is the same as in Example 1, and NPR-SeSe / PVA hydrogel film is obtained.

[0053] Figure 3 The diagram illustrates the temperature response mechanism of NPR-SS microgels. The temperature responsiveness of NPR-SS microgels is due to the shrinkage of the internal pNIPAm molecular chains and the reduction in volume as the temperature of the microgel solution increases. This leads to an enhanced rotational confinement effect within the PhAN molecule, resulting in an increase in fluorescence intensity.

[0054] Figure 4The fluorescence emission spectra of the NPR-SS / PVA hydrogel sensing film at different temperatures (20~45℃) are shown. It can be seen that as the temperature increases from 20℃ to 45℃, the fluorescence emission of NPR-SS / PVA... 430 Gradually increase, F 580 Almost unchanged, which leads to F 430 / F 580 The value increased from 2.51 to 5.08. After fitting using the Boltzmann equation, the LCSTFL of NPR-SS / PVA was found to be 30.63. o C, almost equivalent to LCST of NPR-SS microgel FL Therefore, NPR-SS can achieve temperature responsiveness in PVA hydrogel. A similar trend was observed after three days of incubation.

[0055] Figure 5 Infrared thermal images and 365nm UV light images of NPR-SS / PVA hydrogel applied to a human hand and the outer wall of a water cup at different temperatures show that when the NPR-SS / PVA hydrogel detects a low-temperature object, its fluorescence appears blue-violet; as the object's temperature increases, its fluorescence gradually changes to blue. Further analysis of the RGB values ​​of the fluorescence images at 20, 25, 30, 35, 40, and 45℃ using Photoshop software reveals the corresponding linear relationship.

[0056] Figure 6 This diagram illustrates the X-ray response mechanism of NPR-based microgels. The ·OH generated after irradiation breaks the SS and Se-Se bonds on the crosslinking agent, reducing the number of crosslinking points and causing the microgel to swell. This leads to a decrease in PhAN fluorescence intensity, while RhB-APMA fluorescence is less affected, ultimately resulting in a change in the fluorescence color of the microgel solution.

[0057] Figure 7 The X-ray responsiveness of the NPR / PVA hydrogel sensing film shows that with increasing radiation dose (0–80 Gy), the emission of NPR-SS / PVA at 430 nm gradually decreases, while the emission at 580 nm remains almost unchanged. Its fluorescence emission intensity ratio F0... 430 / F 580 It can be linearly fitted, satisfying the equation: y = -0.0236x + 3.236 (R²) 2 =0.976). The hydrogel has a radiation response range of 0–80 Gy and a sensitivity of 0.0236 Gy. -1 The results are similar to those of NPR-SS / H2O microgel solutions. Furthermore, the radiation response range of NPR-SeSe / PVA is 0–8 Gy, with a sensitivity of 0.273 Gy. -1 .

[0058] Figure 8 The images show the NPR / PVA hydrogel sensing film under white light and after irradiation under 365 nm UV light. It can be seen that the dose of the constructed NPR-based / PVA composite hydrogel array can be observed with the naked eye.

[0059] The performance of the materials prepared in the above embodiments was tested, and the comparison results with those of Example 1 are shown in Table 1.

[0060] Table 1

[0061] Temperature detection range (°C) X-ray detection range (Gy) <![CDATA[Sensitivity (Gy -1 )]]> Example 1 20~45 0~80 0.0218 Example 2 20~45 0 0 Example 3 20~45 0~8 0.278

[0062] As can be seen from the table above, adjusting the type of crosslinking agent has a significant impact on the material properties. This is because the chemical bond energies of SS, CC, and Se-Se present in the crosslinking agent differ, affecting the microstructure of the hydrogel, such as phase separation and entanglement. These changes in microstructure directly affect the macroscopic properties of the hydrogel. According to the results in the table above, the best technical effect can be obtained when BAC is used as the crosslinking agent in this invention. Example

[0063] The difference between this embodiment and Example 1 is that APMA is changed to ferrocene, while the rest of the preparation process is the same as in Example 1, and an NPR / PVA hydrogel film is obtained. Example

[0064] The difference between this embodiment and Example 1 is that APMA is replaced with acrylic acid, while the rest of the preparation process is the same as in Example 1, to obtain an NPR / PVA hydrogel film.

[0065] The performance of the materials prepared in the above embodiments was tested, and the results compared with those of Example 1 are shown in Table 2.

[0066] Table 2

[0067] Temperature detection range (°C) X-ray detection range (Gy) <![CDATA[Sensitivity (Gy -1 )]]> Example 1 20~45 0~80 0.0218 Example 4 20~45 0~20 2.56 Example 5 20~45 0~10 1.43

[0068] As can be seen from the table above, adjusting the polymer monomer has a significant impact on the material properties. This is because different polymer monomers also affect the crosslinking points of the microgel. According to the results in the table above, Example 1 of this invention can achieve the best technical effect.

[0069] This comparative example provides a method for preparing a hydrogel film, specifically as follows:

[0070] 15 g of polyvinyl alcohol (PVA) was mixed with 100 mL of deionized water and stirred at room temperature for 8 h, followed by stirring in a 90 °C oil bath for 3 h to obtain an aqueous PVA solution. 20 mL of the PVA solution was taken and 5 mL of NPR-SS microgel solution was added, and the mixture was stirred for 2 h. The mixture was poured into a mold and allowed to stand at -20 °C for 12 h, then thawed at room temperature for 3 h. An NPR-SS / PVA hydrogel film with a thickness of 3 mm and a diameter of 3.5 cm was obtained.

[0071] The difference between this embodiment and Example 1 is that the PVA content is adjusted to 10 g, while the rest of the preparation process is the same as in Example 1. NPR-SS / PVA hydrogel film cannot be obtained.

[0072] The difference between this embodiment and Example 1 is that the PVA content is adjusted to 5 g, while the rest of the preparation process is the same as in Example 1. NPR-SS / PVA hydrogel film cannot be obtained.

[0073] The difference between this embodiment and Example 1 is that the stirring time at room temperature was adjusted to 3 hours, while the rest of the preparation process was the same as in Example 1. NPR-SS / PVA hydrogel films could not be obtained.

[0074] The difference between this embodiment and Example 1 is that the stirring time at room temperature was adjusted to 1 h, while the rest of the preparation process was the same as in Example 1. NPR-SS / PVA hydrogel film could not be obtained.

[0075] The performance of the materials prepared in the above comparative example was tested, and the results compared with those of Example 1 are shown in Table 3.

[0076] Table 3

[0077] Temperature detection range (°C) X-ray detection range (Gy) <![CDATA[Sensitivity (Gy -1 ).]]> Example 1 20~45 0~80 0.0218 Comparative Example 1 0 0 0 Comparative Example 2 0 0 0 Comparative Example 3 0 0 0 Comparative Example 4 0 0 0 Comparative Example 5 0 0 0

[0078] As can be seen from the table above, the PVA concentration cannot be lower than 5%, otherwise hydrogel films cannot be prepared. PVA and microgels need to be stirred thoroughly. Insufficient stirring time will result in uneven stirring, and therefore hydrogel films cannot be prepared.

[0079] In summary, this invention develops a flexible thin-film sensor based on AIE hydrogel, achieving dual sensing and detection of temperature and X-ray dose using fluorescence colorimetry. Combined with image analysis techniques, we found that this AIE hydrogel thin-film sensor exhibits excellent linear response to ambient temperatures of 20-45°C and X-ray doses of 0-80 Gy. It possesses high sensitivity, a low detection limit, and is easily observed with the naked eye, providing a new material option for the development of future wearable devices.

[0080] It should be noted that the above embodiments are only used to illustrate the technical solutions of the present invention and are not intended to limit it. Although the present invention has been described in detail with reference to preferred embodiments, those skilled in the art should understand that modifications or equivalent substitutions can be made to the technical solutions of the present invention without departing from the spirit and scope of the technical solutions of the present invention, and all such modifications or substitutions should be covered within the scope of the claims of the present invention.

Claims

1. A method for preparing a temperature- and X-ray dual-response AIE hydrogel film, characterized in that: include, Synthesis of hydrogels: N-isopropylacrylamide, crosslinking agent, 4-phenoxy-N-allyl-1,8-naphthalenediamide, hexadecyltrimethylammonium bromide, and RhB-APMA solution were dissolved in deionized water and heated to 60-80℃. After stirring continuously under a nitrogen atmosphere for 1-2 h, an initiator was added to initiate monomer polymerization. After 4-5 h, P(NIPAm-co-PhAN-co-RhB-APMA) microgels were obtained, denoted as NPR microgels. Preparation of NPR / PVA hydrogel film: PVA aqueous solution is added to the above NPR microgel, stirred for 2-4 h, poured into a mold and allowed to stand at -20℃ for 10-14 h, and then thawed at room temperature for 2-4 h to obtain NPR / PVA hydrogel film. The crosslinking agent includes N,N'-bis(acryloyl)cystamine containing sulfur-sulfur bonds; The method for preparing the RhB-APMA solution includes, Rhodamine B, 1-ethyl-(3-dimethylaminopropyl)carbodiimide hydrochloride, N-hydroxysuccinimide, and MES buffer solution were stirred for 1-2 h to obtain a mixed solution; then, N-(3-aminopropyl)methacrylamide hydrochloride was dissolved in PBS buffer solution and added to the above mixed solution, and stirring was continued for 3-4 h to obtain RhB-APMA solution; Each 1L of the RhB-APMA solution contains 20-50 mmol Rhodamine B, 20-50 mmol 1-ethyl-(3-dimethylaminopropyl)carbodiimide hydrochloride, 20-50 mmol N-hydroxysuccinimide, 5-7 mL MES buffer solution, 20-50 mmol N-(3-aminopropyl)methacrylamide hydrochloride, and 20-30 mL PBS buffer solution; Each 1L of the NPR microgel contains 120-130 mmol N-isopropylacrylamide, 10-20 mmol crosslinking agent, 1-2 mmol N-(3-aminopropyl)methacrylamide hydrochloride, 1-2 mmol 4-phenoxy-N-allyl-1,8-naphthalenediamide, 10-50 mL RhB-APMA solution and 2-10 mmol initiator; The PVA aqueous solution was prepared by mixing 15 g of polyvinyl alcohol with 100 mL of deionized water. The volume ratio of the PVA aqueous solution to the NPR microgel is 4~6:1~2; The method for preparing the PVA aqueous solution includes, Polyvinyl alcohol is mixed with deionized water and stirred at room temperature for 8-10 hours, then stirred in an oil bath at 85-95°C for 3-5 hours to obtain an aqueous PVA solution.

2. The preparation method according to claim 1, characterized in that: Initiators include one or more of azobisisobutyramidine hydrochloride, ammonium persulfate, and potassium persulfate.

3. A temperature- and X-ray dual-response AIE hydrogel film prepared by any one of the preparation methods of claims 1 to 2.

Images