Temperature and X-ray dual-response AIE hydrogel film and preparation method thereof

Abstract

The invention discloses a temperature and X-ray dual-response AIE hydrogel film and a preparation method thereof, and belongs to the technical field of hydrogel preparation. The volume of the NPR microgel prepared by the method can be reduced along with the rise of the temperature, and the colorimetric fluorescence signal intensity (F430 / F580) of the NPR microgel and the NPR / PVA film is enhanced due to the change. The volume of the NPR microgel is increased along with the increase of the dosage, the fluorescence color of the NPR-SS hydrogel film is changed from bluish violet to purple red under the X-ray of 0-80 Gy, and the sensitivity is 0.032 Gy <-1 >. The hydrogel film prepared by the invention can realize dual response of temperature and X-ray dose, constructs a linear relationship between fluorescence intensity and response, has strong adhesion, high sensitivity and low detection lower limit, is easy to observe by naked eyes, and provides a new strategy for wearable sensors.

Description

Technical Field

[0001] The invention belongs to the technical field of hydrogel preparation, and specifically relates to a temperature and X-ray dual-responsive AIE hydrogel film and a preparation method thereof. Background Art

[0002] Traditional thermometers, especially mercury thermometers, are accurate, but have some disadvantages. The mercury in the thermometer is toxic, and once broken, the mercury vapor may be harmful to human health. In addition, the measurement speed of mercury thermometers is relatively slow, and it usually takes several minutes to get an accurate reading. Skill is also required when operating to ensure the accuracy of the reading. In medical and industrial applications, X-ray dosimeters are often used to measure radiation doses, but they have some limitations. For example, traditional X-ray dosimeters may require a lot of money and manpower, and some require regular calibration to ensure the accuracy of the measurement results. In general, traditional thermometers or X-ray dosimeters are often made of hard materials and are difficult to fit the skin, limiting their application in wearable devices. Summary of the invention

[0003] The purpose of this section is to summarize some aspects of embodiments of the present invention and briefly introduce some preferred embodiments. Some simplifications or omissions may be made in this section and the specification abstract and the invention title of this application to avoid blurring the purpose of this section, the specification abstract and the invention title, and such simplifications or omissions cannot be used to limit the scope of the present invention.

[0004] The present invention discloses a method for synthesizing a temperature and X-ray dual-responsive AIE (aggregation-induced emission) hydrogel film, and solves the following technical problems:

[0005] First, the traditional mercury thermometer is not only slow in measurement, but also requires certain operating skills to ensure the accuracy of the reading. In contrast, the present invention uses N-isopropylacrylamide (NIPA m) as the basic material to develop a hydrogel film that can quickly sense changes in ambient temperature and change color accordingly, thereby achieving a rapid response to temperature.

[0006] Secondly, there is a common problem with existing X-ray dosimeters: dose changes are not easy to observe directly. In addition, traditional X-ray dosimeters are usually made of hard materials and are difficult to fit closely to the skin, which limits their application in areas such as radiotherapy. Our hydrogel film not only establishes a linear relationship between fluorescence intensity and dose, but also has good skin adhesion, thus expanding the application range of dosimeters.

[0007] In summary, the present invention has developed a flexible thin film sensor based on AIE hydrogel, which realizes dual sensing detection of temperature and X-ray dose by fluorescence colorimetry. Combined with image analysis technology, we found that this AIE hydrogel thin film sensor exhibits good linear response to ambient temperature of 20-45°C and X-ray dose of 0-80Gy. It has the characteristics of high sensitivity, low detection limit, and is easy to observe with the naked eye, providing new material options for the development of future wearable devices.

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

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

[0010] In order to solve the above technical problems, the present invention provides the following technical solutions, including:

[0011] Synthesis of hydrogel: N-isopropylacrylamide, crosslinker, N-(3-aminopropyl) methacrylate hydrochloride, 4-phenoxy-N-allyl-1,8-naphthalimide, and RhB-APMA solution were dissolved in deionized water and heated to 60-80°C; after continuous stirring for 1-2 hours under a nitrogen atmosphere, an initiator was added to initiate monomer polymerization. After 4-5 hours, P(NIPAm-co-PhAN-co-RhB-APMA) microgel was obtained, which was recorded as NPR microgel.

[0012] Preparation of NPR / PVA hydrogel film: Add PVA aqueous solution to the above NPR microgel, stir for 2 to 4 hours, pour into a mold and let stand at -20°C for 10 to 14 hours, then thaw at room temperature for 2 to 4 hours to obtain NPR / PVA hydrogel film.

[0013] As a preferred scheme for the preparation method of the temperature and X-ray dual-responsive AIE hydrogel film of the present invention, the cross-linking agent includes one or more of N,N'-methylenebisacrylamide (BIS) containing a carbon-carbon double bond, N,N'-bis(acryloyl)cystamine containing a sulfur-sulfur bond, and diselenidediylbis(butane-4,1-diyl)bis(methacrylate) containing a selenium-selenium bond.

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

[0015] Rhodamine B, 1-ethyl-3-(3-dimethylaminopropyl) carbodiimide hydrochloride, N-hydroxysuccinimide, and MES buffer solution were stirred for 1 to 2 hours; then, N-(3-aminopropyl) methacrylate hydrochloride was dissolved in PBS buffer solution and added to the above mixed solution, and stirring was continued for 3 to 4 hours to obtain RhB-APMA solution.

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

[0017] As a preferred embodiment of the method for preparing the temperature and X-ray dual-responsive 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 scheme for the preparation method of the temperature and X-ray dual-responsive AIE hydrogel film of the present invention, each 1L of the NPR microgel contains 120-130mmol N-isopropylacrylamide, 10-20mmol of a cross-linking agent, 1-2mmol N-(3-aminopropyl) methacrylic acid hydrochloride, 1-2mmol 4-phenoxy-N-allyl-1,8-naphthalene diimide, 10-50mL RhB-APMA solution and 2-10mmol initiator.

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

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

[0021] Mix polyvinyl alcohol and deionized water, stir for 8 to 10 hours, and then continue stirring in an oil bath at 85 to 95° C. for 3 to 5 hours to obtain a PVA aqueous solution.

[0022] As a preferred solution of the method for preparing the temperature and X-ray dual-responsive 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 object of the present invention is to overcome the deficiencies in the prior art and provide a temperature and X-ray dual-responsive AIE hydrogel film.

[0024] Beneficial effects of the present invention:

[0025] (1) As the temperature increases, the volume of NPR microgels decreases. This change causes the colorimetric fluorescence signal intensity (F 430 / F 580 ) is enhanced. Specifically, when the temperature rises from 20°C to 45°C, the fluorescence color of the film changes from blue-purple to blue. By sticking the hydrogel film on the surface of a water cup or gloves, the temperature can be intuitively sensed through the change of the fluorescence signal.

[0026] (2) As the dose increases, the volume of the NPR microgel increases. Under 0-80 Gy X-rays, the fluorescence color of the NPR-SS hydrogel film changes from blue-purple to purple-red, with a sensitivity of 0.032 Gy. -1 The X-ray detection range of NPR-SeSe hydrogel film is 0-8Gy, and the sensitivity is 0.278Gy. -1 , the fluorescent color also changes from blue-purple to purple-red.

[0027] (3) The hydrogel film prepared by the present invention can achieve dual response to temperature and X-ray dose, and construct 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. BRIEF DESCRIPTION OF THE DRAWINGS

[0028] In order to more clearly illustrate the technical solutions of the embodiments of the present invention, the following briefly introduces the drawings required for describing the embodiments. Obviously, the drawings described below are only some embodiments of the present invention. For ordinary technicians in this field, other drawings can be obtained based on these drawings without creative work. Among them:

[0029] Figure 1 Schematic diagram of the synthesis of NPR microgel of the present invention.

[0030] Figure 2 This is the product picture of NPR / PVA hydrogel film.

[0031] Figure 3 Schematic diagram of the temperature response mechanism of NPR-SS microgel.

[0032] Figure 4Fluorescence emission spectra of NPR-SS / PVA hydrogel sensing film at different temperatures (20-45°C): (a) on the first day; (b) on the third day. The corresponding fluorescence intensity ratio F 430 / F 580 The relationship curve with temperature (λ ex =365nm): (c) first day; (d) third day.

[0033] Figure 5 These are infrared thermal imaging photos of NPR-SS / PVA hydrogel attached to a person's hand / the outer wall of a water cup at different temperatures and photos taken under 365nm UV light.

[0034] Figure 6 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 =365nm); (d) fluorescence intensity ratio F 430 / F 580 - Radiation dose relationship curve.

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

[0037] In order to make the above-mentioned objects, features and advantages of the present invention more obvious and easy to understand, the specific implementation methods of the present invention are described in detail below in conjunction with the embodiments of the specification.

[0038] In the following description, many specific details are set forth to facilitate a full understanding of the present invention, but the present invention may also be implemented in other ways different from those described herein, and those skilled in the art may make similar generalizations without violating the connotation of the present invention. Therefore, the present 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 term "in one embodiment" that appears in different places in this specification does not necessarily refer to the same embodiment, nor does it refer to a separate or selective embodiment that is mutually exclusive with other embodiments.

[0040] The raw materials used in the present invention are all commercially available unless otherwise specified.

[0041] The raw materials are referred to as follows:

[0042] N-isopropylacrylamide (NIPAm), rhodamine B (RhB), 1-ethyl-3-(3-dimethylaminopropyl) carbodiimide hydrochloride (EDC), N-hydroxysuccinimide (NHS), MES, N-(3-aminopropyl) methacrylate hydrochloride (APMA), N,N'-methylenebisacrylamide (BIS), N,N'-bis(acryloyl)cystamine (BAC), diselenide bis(butane-4,1-diyl) bis(methacrylate) (BMASe), N-(3-aminopropyl) methacrylate hydrochloride (CTAB), 4-phenoxy-N-allyl-1,8-naphthalimide (PhAN), azobisisobutyramidine hydrochloride (V50), polyvinyl alcohol (PVA), N,N'-bis(acryloyl)cystamine (BAC).

[0043] The performance of the material prepared in the embodiment of the present invention was tested as follows:

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

[0045] Example 1

[0046] This embodiment provides a method for preparing a temperature and X-ray dual-responsive AIE hydrogel film. Figure 1 ), specifically:

[0047] 1. Synthetic hydrogel:

[0048] Rhodamine B (RhB) 0.5mmol, 1-ethyl-3-(3-dimethylaminopropyl) carbodiimide hydrochloride (EDC) 1mmol, N-hydroxysuccinimide (NHS) 0.5mmol, 5mL MES buffer solution (0.1M, pH=5.5) were stirred at room temperature for 1h. Then, N-(3-aminopropyl) methacrylic acid hydrochloride (APMA) 1mmol was dissolved in 20mL PBS buffer solution (0.1M, pH=7.4) and added to the above mixed solution, and stirred at room temperature for 3h to obtain RhB-APMA solution.

[0049] In a flask, 12 mmol NIPAm, 1 mmol N,N'-bis(acryloyl)cystamine (BAC) containing sulfur-sulfur bonds, 0.1 mmol N-(3-aminopropyl)methacrylic acid hydrochloride (CTAB), 0.1 mmol 4-phenoxy-N-allyl-1,8-naphthalimide (PhAN), 1 mL of the above RhB-APMA solution and 96 mL of deionized water were mixed and heated to 70°C. After continuous stirring for 1 h under a nitrogen atmosphere, 0.2 mmol azobisisobutylamidine hydrochloride (V50) initiator was added to initiate monomer polymerization. After 4 h, p(NIPAm-co-Ph AN-co-RhB-APMA) microgel was obtained, which was recorded as NPR-BAC microgel.

[0050] 2. Preparation of NPR / PVA hydrogel film

[0051] Mix 15g of polyvinyl alcohol with 100mL of deionized water, stir at room temperature for 8h, and continue stirring in a 90℃ oil bath for 3h to obtain a PVA aqueous solution. Take 20mL of PVA aqueous solution and add 5mL of NPR-SS microgel solution, stir for 2h. Pour the above mixture into a mold, let it stand at -20℃ for 12h, and then thaw at room temperature for 3h. Obtain an NPR-SS / PVA hydrogel film with a thickness of 3mm and a diameter of 3.5cm.

[0052] Example 2

[0053] The difference between this embodiment and embodiment 1 is that the type of crosslinking agent is adjusted to N,N'-methylenebisacrylamide (BIS) containing a carbon-carbon double bond, and the rest of the preparation process is the same as that of embodiment 1 to prepare NPR-CC / PVA hydrogel film.

[0054] Example 3

[0055] The difference between this embodiment and embodiment 1 is that the type of cross-linking agent is adjusted to a cross-linking agent containing selenium-selenium bonds, diselenide di(butyl-4,1-diyl) bis(methacrylate) (BMASe), and the rest of the preparation process is the same as that of embodiment 1 to obtain NPR-SeSe / PVA hydrogel film.

[0056] Figure 3 Figure 3 is a schematic diagram of the temperature response mechanism of NPR-SS microgels. The temperature responsiveness of NPR-SS microgels is because as the temperature of the microgel solution increases, the internal pNIPAm molecular chains shrink and the volume decreases, which leads to an enhancement in the restricted rotation effect of the PhAN molecules and an increase in the fluorescence intensity.

[0057] Figure 4Figure 2 is the fluorescence emission spectra of NPR-SS / PVA hydrogel sensing film at different temperatures (20-45°C). It can be seen that as the temperature rises from 20°C to 45°C, the fluorescence emission spectra of NPR-SS / PVA 430 Gradually increasing, F 580 This results in F 430 / F 580 The LCSTFL of NPR-SS / PVA was 30.63℃ after fitting with the Boltzmann equation, which is almost the same as the LCSTFL of NPR-SS microgel. FL Therefore, NPR-SS can achieve temperature responsiveness in PVA hydrogel. After three days of storage, it has a similar trend.

[0058] Figure 5 The infrared thermal imaging photos of NPR-SS / PVA hydrogel attached to a human hand / the outer wall of a water cup at different temperatures and the photos taken under 365nm UV light show that when NPR-SS / PVA hydrogel detects a low-temperature object, its fluorescence appears blue-purple; as the temperature of the object rises, its fluorescence gradually turns to blue. The RGB values ​​of the fluorescence photos at 20, 25, 30, 35, 40 and 45℃ were further analyzed using Photoshop software, and the corresponding linear relationship can be obtained.

[0059] Figure 6 Schematic diagram of the X-ray response mechanism of NPR-based microgels. The ·OH generated after irradiation can break the SS and Se-Se bonds on the crosslinker, thereby reducing the crosslinking points and causing the microgel to swell. This leads to a weakening of the fluorescence intensity of PhAN, while the fluorescence of RhB-APMA is less affected, ultimately leading to a change in the fluorescence color of the microgel solution.

[0060] Figure 7 Figure 2 is the X-ray responsiveness of the NPR / PVA hydrogel sensing film. It can be seen that with the increase of radiation dose (0-80 Gy), the emission of NPR-SS / PVA at 430 nm gradually decreases, and the emission at 580 nm remains almost unchanged. 430 / F 580 Linear fitting can be performed to satisfy the equation: y = -0.0236x + 3.236 (R 2 =0.976). The radiation response range of the hydrogel is 0-80Gy, and the sensitivity is 0.0236Gy -1 , which is close to that of NPR-SS / H2O microgel solution. Furthermore, the radiation response range of NPR-SeSe / PVA is 0-8Gy, and the sensitivity is 0.273Gy -1 .

[0061] Figure 8These are photos of the NPR / PVA hydrogel sensing film under white light and after irradiation under 365nm UV light. It can be seen that the dosage of the constructed NPR-based / PVA composite hydrogel array can be observed with the naked eye.

[0062] The performance of the material prepared in the above embodiment was tested, and the comparison results with those in Example 1 are shown in Table 1.

[0063] Table 1

[0064] Temperature detection range (℃) 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

[0065] As can be seen from the above table, adjusting the type of cross-linking agent has a significant effect on the material properties. This is because the chemical bond energies of SS, CC, and Se-Se in the cross-linking agent are different, which affects the microstructure of the hydrogel, such as phase separation and entanglement. These microstructural changes directly affect the macroscopic properties of the hydrogel. According to the results in the above table, the best technical effect can be obtained when the cross-linking agent in the present invention is BAC.

[0066] Example 4

[0067] The difference between this embodiment and embodiment 1 is that APMA is adjusted to ferrocene, and the rest of the preparation process is the same as that of embodiment 1 to prepare NPR / PVA hydrogel film.

[0068] Example 5

[0069] The difference between this embodiment and embodiment 1 is that APMA is changed to acrylic acid, and the rest of the preparation process is the same as that of embodiment 1 to prepare NPR / PVA hydrogel film.

[0070] The performance of the material prepared in the above embodiment was tested, and the comparison results with those in Example 1 are shown in Table 2.

[0071] Table 2

[0072]

[0073]

[0074] It can be seen from the above table that adjusting the polymerization monomer has a significant effect on the material properties. This is because different polymerization monomers will also affect the cross-linking points of the microgel. According to the results in the above table, Example 1 in the present invention can obtain the best technical effect.

[0075] Comparative Example 1

[0076] This comparative example provides a method for preparing a hydrogel film, specifically:

[0077] Mix 15g of polyvinyl alcohol (PVA) with 100mL of deionized water, stir at room temperature for 8h, and continue stirring in a 90℃ oil bath for 3h to obtain a PVA aqueous solution. Take 20mL of PVA aqueous solution and add 5mL of NPR-SS microgel solution, stir for 2h. Pour the above mixture into a mold, let it stand at -20℃ for 12h, and then thaw at room temperature for 3h. Obtain an NPR-SS / PVA hydrogel film with a thickness of 3mm and a diameter of 3.5cm.

[0078] Comparative Example 2

[0079] The difference between this embodiment and embodiment 1 is that the PVA content is adjusted to 10 g, and the rest of the preparation process is the same as that of embodiment 1, and the NPR-SS / PVA hydrogel film cannot be prepared.

[0080] Comparative Example 3

[0081] The difference between this embodiment and embodiment 1 is that the PVA content is adjusted to 5 g, and the rest of the preparation process is the same as that of embodiment 1, and the NPR-SS / PVA hydrogel film cannot be prepared.

[0082] Comparative Example 4

[0083] The difference between this embodiment and embodiment 1 is that the stirring time at room temperature is adjusted to 3 hours, and the rest of the preparation process is the same as that of embodiment 1, and the NPR-SS / PVA hydrogel film cannot be prepared.

[0084] Comparative Example 5

[0085] The difference between this embodiment and embodiment 1 is that the stirring time at room temperature is adjusted to 1 hour, and the rest of the preparation process is the same as that of embodiment 1, and the NPR-SS / PVA hydrogel film cannot be prepared.

[0086] The performance of the material obtained in the above comparative example was tested, and the comparison results with those of Example 1 are shown in Table 3.

[0087] Table 3

[0088]

[0089]

[0090] It can be seen from the above table that the PVA concentration cannot be lower than 5%, otherwise the hydrogel film cannot be prepared. PVA and microgel need to be fully stirred. Too little time will lead to uneven stirring, so the hydrogel film cannot be prepared.

[0091] In summary, the present invention has developed a flexible thin film sensor based on AIE hydrogel, which realizes dual sensing detection of temperature and X-ray dose by fluorescence colorimetry. Combined with image analysis technology, we found that this AIE hydrogel thin film sensor exhibits good linear response to ambient temperature of 20-45°C and X-ray dose of 0-80Gy. It has high sensitivity, low detection limit, and is easy to observe with the naked eye, providing new material options for the development of future wearable devices.

[0092] It should be noted that the above embodiments are only used to illustrate the technical solutions of the present invention rather than to limit it. Although the present invention has been described in detail with reference to the preferred embodiments, those skilled in the art should understand that the technical solutions of the present invention may be modified or replaced by equivalents without departing from the spirit and scope of the technical solutions of the present invention, which should all be included in the scope of the claims of the present invention.

Claims

1. A method for preparing a temperature and X-ray dual-responsive AIE hydrogel film, characterized in that: include, Synthesis of hydrogel: N-isopropylacrylamide, crosslinker, N-(3-aminopropyl)methacrylic acid hydrochloride, 4-phenoxy-N-allyl-1,8-naphthalimide, and RhB-APMA solution were dissolved in deionized water and heated to 60-80°C; the initiator was added to initiate monomer polymerization after continuous stirring for 1-2 hours under a nitrogen atmosphere, and after 4-5 hours, P(NIPAm-co-PhAN-co-RhB-APMA) microgel was obtained, which was recorded as NPR microgel; Preparation of NPR / PVA hydrogel film: Add PVA aqueous solution to the above NPR microgel, stir for 2 to 4 hours, pour into a mold and let stand at -20°C for 10 to 14 hours, then thaw at room temperature for 2 to 4 hours to obtain NPR / PVA hydrogel film.

2. The method for preparing the temperature and X-ray dual-responsive AIE hydrogel film according to claim 1, characterized in that: The crosslinking agent includes one or more of N,N'-methylenebisacrylamide containing carbon-carbon double bonds, N,N'-bis(acryloyl)cystamine containing sulfur-sulfur bonds, and diselenidediylbis(butane-4,1-diyl)bis(methacrylate) containing selenium-selenium bonds.

3. The method for preparing the temperature and X-ray dual-responsive AIE hydrogel film according to claim 1, characterized in that: The method for preparing the RhB-APMA solution comprises: Rhodamine B, 1-ethyl-3-(3-dimethylaminopropyl) carbodiimide hydrochloride, N-hydroxysuccinimide, and MES buffer solution were stirred for 1 to 2 hours; then, N-(3-aminopropyl) methacrylate hydrochloride was dissolved in PBS buffer solution and added to the above mixed solution, and stirring was continued for 3 to 4 hours to obtain RhB-APMA solution.

4. The method for preparing the temperature and X-ray dual-responsive AIE hydrogel film according to claim 1, characterized in that: Each 1L of the RhB-APMA solution contains 20-50mmol rhodamine B, 20-50mmol 1-ethyl-3-(3-dimethylaminopropyl) carbodiimide hydrochloride, 20-50mmol N-hydroxysuccinimide, 5-7mL MES buffer solution, 20-50mmol N-(3-aminopropyl) methacrylic acid hydrochloride, and 20-30mL PBS buffer solution.

5. The method for preparing the temperature and X-ray dual-responsive AIE hydrogel film according to claim 1, characterized in that: The initiator includes one or more of azobisisobutylamidine hydrochloride, ammonium persulfate, and potassium persulfate.

6. The method for preparing the temperature and X-ray dual-responsive AIE hydrogel film according to claim 1, characterized in that: Each 1L of the NPR microgel contains 120-130mmol of N-isopropylacrylamide, 10-20mmol of a crosslinking agent, 1-2mmol of N-(3-aminopropyl)methacrylic acid hydrochloride, 1-2mmol of 4-phenoxy-N-allyl-1,8-naphthalimide, 10-50mL of a RhB-APMA solution and 2-10mmol of an initiator.

7. The method for preparing the temperature and X-ray dual-responsive AIE hydrogel film according to claim 1, characterized in that: The concentration of the PVA aqueous solution is 7.5% to 20%.

8. The method for preparing the temperature and X-ray dual-responsive AIE hydrogel film according to claim 7, characterized in that: The method for preparing the PVA aqueous solution comprises: Mix polyvinyl alcohol and deionized water, stir for 8 to 10 hours, and then continue stirring in an oil bath at 85 to 95°C for 3 to 5 hours to obtain a PVA aqueous solution.

9. The method for preparing the temperature and X-ray dual-responsive AIE hydrogel film according to claim 1, characterized in that: The volume ratio of the PVA aqueous solution to the NPR microgel is 4-6:1-2.

10. A temperature and X-ray dual-responsive AIE hydrogel film prepared by the preparation method according to any one of claims 1 to 9.

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