A fluorescent flexible fiber membrane dosimeter, its preparation method and application

Abstract

This invention relates to a fluorescent flexible fiber membrane dosimeter, its preparation method, and its application. The method includes the following steps: First, 0.01-0.02 parts of quinoline fluorescent dye are added to a mixed solvent of 100 parts of tetrahydrofuran and N,N-dimethylformamide and stirred at room temperature for 30 minutes. Then, 10-15 parts of polyvinyl chloride powder are added and stirred at 50°C for 2 hours. After complete dissolution, the mixture is allowed to stand at room temperature to remove air bubbles, finally obtaining a uniform spinning solution. The spinning solution is then used to prepare a fluorescent flexible fiber membrane dosimeter using electrospinning technology. The electrospinning parameters are: voltage 10-18 kV, spinning distance 13-15 cm, spinning solution flow rate 3.5-5.5 ml / h, and temperature 20-40°C. The fluorescent flexible fiber membrane dosimeter has a fiber diameter of 100 nm to 900 nm and a linear response range of 0 to 350 Gy, and can be applied to ionizing radiation.

Description

Technical Field

[0001] This invention belongs to the field of polymer radiation chemistry technology, specifically relating to a fluorescent flexible fiber membrane dosimeter, its preparation method, and its application. Background Technology

[0002] Since its discovery, X-rays have been widely used in medicine, industrial inspection, sterilization, security checks, and scientific research. Simultaneously, radiation protection for personnel has become a pressing global issue. To accurately calibrate doses, many dosimeters have been invented. For example, ionization chamber dosimeters offer good accuracy and direct dose readings, but require connecting cables and high voltage. Thermoluminescent dosimeters can be used for point dose measurement, but their pretreatment and operating procedures are overly complex, requiring significant time for reading and calibration. However, for medical personnel, aircraft maintenance workers, and astronauts working in space who are chronically exposed to ionizing radiation, their limbs and chest are the most exposed areas. Commercially available personal dosimeters are not only inconvenient to observe or uncomfortable to wear, but they can only monitor ambient doses and cannot accurately measure these vital areas of the body. If they could detect changes in the fluorescent color of their clothing or gloves, they could promptly avoid danger. Therefore, a flexible, wearable fluorescent X-ray dosimeter is urgently needed.

[0003] Polymer fluorescent thin-film dosimeters are solid films whose fluorescence color changes upon exposure to a certain dose of ionizing radiation. Due to their high sensitivity, wide dose response range, and ease of manufacture, these films have broad application prospects. In existing technologies, fluorescent quinoline dyes, which change from blue to red fluorescence upon contact with acid, are used to create films with PVC, exhibiting radiation-responsive properties. However, their sensitivity and linearity range are not high, and the commonly used film-forming methods have significant limitations, making it difficult to achieve lightweight and flexible designs. With the increasing demand for flexible dosimeters, some polymer films prepared by solution methods are too rigid, leading to a growing trend of manufacturing thin-film dosimeters using polymer fibers. Conventional spinning techniques cannot produce ultrafine fibers; dry spinning and wet spinning processes typically yield fibers with diameters between 5 μm and 50 μm. Electrospinning, however, is a technology capable of producing uniform nanofibers. Fibers produced by electrospinning offer advantages such as good flexibility, uniform diameter, high specific surface area, and high porosity. Producing flexible fluorescent nanofiber membranes by mixing polymers and fluorescent dyes and employing electrospinning technology is an effective approach for preparing ionizing radiation dosimeters. The novel dosimeter, which combines electrospinning technology with fluorescent quinoline dyes, offers multiple advantages such as better flexibility, response sensitivity, and linear response range, demonstrating significant superiority over existing technologies. Summary of the Invention

[0004] The purpose of this invention is to overcome the shortcomings of existing technologies and provide a fluorescent flexible fiber membrane dosimeter, its preparation method, and its applications. The fluorescent fiber membrane dosimeter exhibits a linear response within the range of 0-350 Gy. Furthermore, this dosimeter possesses advantages such as high sensitivity, stable performance, good flexibility, and skin-adherence, making it suitable for use in radiomedicine, scientific research, and the radiation industry.

[0005] To achieve the objectives of this invention, the present invention will be implemented using the technical solutions described below.

[0006] A fluorescent flexible fiber membrane dosimeter is prepared by comprising 10-15 parts by weight of polyvinyl chloride, 0.01-0.02 parts by weight of fluorescent quinoline dye, and 100 parts by weight of organic solvent; wherein:

[0007] The structural formula of the fluorescent quinoline dye is:

[0008]

[0009] The fiber diameter of the fluorescent flexible fiber membrane dosimeter is 100 nm to 900 nm;

[0010] The dose linear response range of the fluorescent flexible fiber membrane dosimeter is 0–350 Gy;

[0011] The organic solvent is a mixture of tetrahydrofuran and N,N-dimethylformamide in a ratio of 5-7:3-5.

[0012] A method for preparing a fluorescent flexible fiber membrane dosimeter includes the following steps:

[0013] S21. Add 0.01-0.02 parts of fluorescent quinoline dye to 100 parts of organic solvent, stir and dissolve at room temperature. After complete dissolution, add 10-15 parts of polyvinyl chloride powder, stir at 50°C for 2 hours, and after complete dissolution, let stand at room temperature to remove air bubbles and obtain a uniform spinning solution; wherein, the organic solvent is a mixture of tetrahydrofuran and N,N-dimethylformamide in a mixing ratio of 5-7:3-5.

[0014] S22. Using electrospinning technology, prepare an electrospun flexible fiber membrane from the spinning solution obtained in step S21, and completely evaporate the solvent at room temperature; wherein, the electrospinning parameters are: voltage 10-18kV, spinning distance 13-15cm, spinning solution flow rate 3.5-5.5ml / h, and temperature 20-40℃.

[0015] S23. Peel the dried electrospun flexible fiber membrane off the aluminum foil to obtain a fluorescent flexible fiber membrane dosimeter, wherein the fiber diameter of the fluorescent flexible fiber membrane dosimeter is 100nm~900nm and the dose linear response range is 0~350Gy.

[0016] An application of a fluorescent flexible fiber membrane dosimeter in measuring ionizing radiation, wherein the fluorescent flexible fiber membrane dosimeter is prepared by means of 10-15 parts by weight of polyvinyl chloride, 0.01-0.02 parts by weight of fluorescent quinoline dye, and 100 parts by weight of organic solvent; wherein:

[0017] The structural formula of the fluorescent quinoline dye is:

[0018]

[0019] The fiber diameter of the fluorescent flexible fiber membrane dosimeter is 100 nm to 900 nm;

[0020] The dose linear response range of the fluorescent flexible fiber membrane dosimeter is 0–350 Gy;

[0021] The organic solvent is a mixture of tetrahydrofuran and N,N-dimethylformamide in a ratio of 5-7:3-5.

[0022] As a preferred embodiment of the present invention, the fluorescent flexible fiber membrane dosimeter exhibits a red fluorescence color after being irradiated, and a gradient color difference appears with the irradiation dose, with obvious color changes, making it easy to observe.

[0023] As a preferred embodiment of the present invention, the radiation source of the ionizing radiation is an X-ray tube.

[0024] As a preferred embodiment of the present invention, the dose rate of the ionizing radiation is 0.4 Gy / min-4.98 Gy / min.

[0025] As a preferred embodiment of the present invention, the fluorescent flexible fiber membrane dosimeter is used in radiomedicine.

[0026] As a preferred embodiment of the present invention, the fluorescent flexible fiber membrane dosimeter is used in scientific experiments.

[0027] As a preferred embodiment of the present invention, the fluorescent flexible fiber membrane dosimeter is used in the radiation industry.

[0028] As a preferred embodiment of the present invention, the fluorescent flexible fiber membrane dosimeter can be sewn into gloves and wearable devices for personal dose monitoring in hazardous environments such as radiation interventional therapy and high-risk radiochemical operations.

[0029] Beneficial effects

[0030] 1. The fluorescent fiber membrane dosimeter produced by this invention adopts electrospinning technology. The fiber membrane has good flexibility and can fit the skin. It has broad application prospects in radiotherapy and wearable dosimeters. It has the advantages of low weight, high sensitivity, easy preparation and stable performance, and easy measurement.

[0031] 2. The fluorescent fiber membrane dosimeter fabricated in this invention exhibits a dual emission spectrum with blue and red peaks in its steady-state emission spectrum after irradiation. A linear relationship is established between the fluorescence intensity ratio of these two peaks and the radiation dose, resulting in a dose response linear range of 0-350 Gy. Compared to the evaporation film-forming method, the fluorescent fiber dosimeter prepared by spinning has a wider linear response range. Furthermore, due to the larger surface area of ​​the fiber membrane, its contact area with air increases, allowing air to penetrate the material more effectively compared to non-fiber membranes. Since oxygen can participate in and accelerate the radiation-induced degradation of polymers under radiation, the fiber membrane can produce more acid at the same radiation dose, resulting in a stronger acid-responsive fluorescent molecule response; correspondingly, finer fiber membranes produce more acid. The introduction of electrospinning achieves multiple benefits—increasing response sensitivity and linear range—while simultaneously achieving flexibility, which is a significant advantage of this invention compared to other fluorescent radiation dosimeters.

[0032] 3. Due to the improved response performance, compared with other reported fiber membrane fluorescence dosimeters that show changes in fluorescence brightness after irradiation, the fluorescent fiber membrane produced in this invention exhibits strong blue fluorescence under 365nm excitation light when unirradiated, and turns red after irradiation. Moreover, it shows a gradient color difference with the irradiation dose, and the color change is obvious, making it easy to observe. It can even be quickly read by taking pictures with portable devices such as mobile phones. Attached Figure Description

[0033] Figure 1 The bimodal (red region emission peak and blue region emission peak) fluorescence intensity ratio of the flexible fiber film with different fiber thicknesses in this invention is compared with the response of the radiation dose to solvent evaporation film-forming materials.

[0034] Figure 2 These are photographs of the fluorescent flexible fiber membrane in this invention after being irradiated with different doses;

[0035] Figure 3 This is the invention Figure 2 The color values ​​(i.e., RGB values) of photographs taken after irradiation with different doses of fluorescent flexible fiber membrane, and the relationship between the B / R value and the radiation dose;

[0036] Figure 4 These are photographs of a fluorescent flexible fiber membrane of a certain formulation in this invention after being irradiated with lead plates covered with holes of different shapes, in order to distinguish between irradiated and unirradiated areas. The blue area is the unirradiated area, and the red area is the irradiated area.

[0037] Figure 5 This is a schematic diagram illustrating the visual sensing of protons generated by X-ray irradiation of PVC by fluorescent quinoline groups. Detailed Implementation

[0038] The embodiments of the present invention will now be described in detail with reference to the accompanying drawings. These embodiments are implemented based on the technical solutions of the present invention, providing detailed implementation methods and specific operating procedures. However, the scope of protection of the present invention is not limited to the following embodiments. All other embodiments obtained by those skilled in the art based on the embodiments of the present invention without creative effort are within the scope of protection of the present invention.

[0039] As an embodiment of the present invention, a fluorescent flexible fiber membrane dosimeter is prepared by comprising 15 parts by weight of polyvinyl chloride, 0.015 parts by weight of fluorescent quinoline dye, 50 parts by weight of tetrahydrofuran, and 50 parts by weight of N,N-dimethylformamide; wherein:

[0040] The structural formula of the fluorescent quinoline dye is:

[0041]

[0042] The fluorescent flexible fiber membrane dosimeter has a fiber diameter of 864 nm;

[0043] The dose linear response range of the fluorescent flexible fiber membrane dosimeter is 0–350 Gy.

[0044] As an embodiment of the present invention, such as Figures 1 to 3 As shown, a method for preparing a fluorescent flexible fiber membrane dosimeter includes the following steps:

[0045] First, 0.015 parts of quinoline fluorescent dye were added to a mixed solvent of 50 parts tetrahydrofuran and 50 parts N,N-dimethylformamide and stirred at room temperature for 30 minutes. Then, 15 parts of polyvinyl chloride powder were added and stirred at 50°C for 2 hours. After complete dissolution, the mixture was allowed to stand at room temperature to remove air bubbles, finally obtaining a uniform spinning solution.

[0046] The spinning solution was loaded into a 10ml syringe and fixed to a syringe pump. The voltage was 10kV, the spinning distance was 15cm, the spinning solution flow rate was 5.5ml / h, and the temperature was 25℃. A reciprocating pump was used to make the needle move back and forth at a uniform speed, thus obtaining a nanofiber dosimeter with uniform thickness. After winding, the fiber membrane was evaporated overnight at room temperature to ensure complete solvent evaporation. The dried fiber membrane was then peeled off from the aluminum foil to obtain the fluorescent flexible fiber membrane dosimeter.

[0047] After the fiber membrane dosimeter was placed in X-ray irradiation, the fluorescence spectrum changes were obtained using an ELISA reader. The ratio of the fluorescence intensity of the two peaks (the emission peak in the red region and the emission peak in the blue region) was linearly fitted to the radiation dose. The linear response relationship between the fluorescence ratio intensity and the X-ray dose is as follows: Figure 1 As shown. The color of the thin film under 365nm ultraviolet light excitation changes with radiation dose as follows. Figure 2 As shown, the relationship between the B / R value and the radiation dose is as follows: Figure 3 As shown in the image. Lead plates with different shaped holes were placed over the surface of a fiber membrane dosimeter and then placed in an X-ray radiation field. The resulting images are shown in the image. Figure 4 As shown, the blue area represents the unirradiated area, and the red area represents the irradiated area.

[0048] As an embodiment of the present invention, a fluorescent flexible fiber membrane dosimeter contains, by weight, 10 parts of polyvinyl chloride powder, 0.01 parts of fluorescent quinoline dye, 60 parts of tetrahydrofuran, and 40 parts of N,N-dimethylformamide. Wherein:

[0049] The structural formula of the fluorescent quinoline dye is:

[0050]

[0051] The fluorescent flexible fiber membrane dosimeter has a fiber diameter of 123 nm;

[0052] The dose linear response range of the fluorescent flexible fiber membrane dosimeter is 0–350 Gy.

[0053] As an embodiment of the present invention, such as Figures 1 to 3 As shown, a method for preparing a fluorescent flexible fiber membrane dosimeter includes the following steps:

[0054] First, 0.01 parts of quinoline fluorescent dye were added to a mixed solvent of 60 parts tetrahydrofuran and 40 parts N,N-dimethylformamide and stirred at room temperature for 30 minutes. Then, 10 parts of polyvinyl chloride powder were added and stirred at 50°C for 2 hours. After complete dissolution, the mixture was allowed to stand at room temperature to remove air bubbles, finally obtaining a uniform spinning solution.

[0055] The spinning solution was loaded into a 10ml syringe and fixed to a syringe pump. The voltage was 15kV, the spinning distance was 13.5cm, the spinning solution flow rate was 4ml / h, and the temperature was 25℃. A reciprocating pump was used to make the needle move back and forth at a uniform speed, thus obtaining a nanofiber dosimeter with uniform thickness. After winding, the fiber membrane was evaporated overnight at room temperature to ensure complete solvent evaporation. The dried fiber membrane was then peeled off from the aluminum foil to obtain the fluorescent flexible fiber membrane dosimeter.

[0056] After the fiber membrane dosimeter was placed in X-ray irradiation, the fluorescence spectrum changes were obtained using an ELISA reader. The ratio of the fluorescence intensity of the two peaks (the emission peak in the red region and the emission peak in the blue region) was linearly fitted to the radiation dose. The linear response relationship between the fluorescence ratio intensity and the X-ray dose is as follows: Figure 1 As shown.

[0057] As an embodiment of the present invention, a fluorescent flexible fiber membrane dosimeter contains, by weight, 15 parts of polyvinyl chloride powder, 0.015 parts of fluorescent quinoline dye, 70 parts of tetrahydrofuran, and 30 parts of N,N-dimethylformamide. Wherein:

[0058] The structural formula of the fluorescent quinoline dye is:

[0059]

[0060] The fluorescent flexible fiber membrane dosimeter has a fiber diameter of 540 nm;

[0061] The dose linear response range of the fluorescent flexible fiber membrane dosimeter is 0–350 Gy.

[0062] As an embodiment of the present invention, a method for preparing a fluorescent flexible fiber membrane dosimeter includes the following steps:

[0063] First, 0.015 parts of quinoline fluorescent dye were added to a mixed solvent of 70 parts tetrahydrofuran and 30 parts N,N-dimethylformamide and stirred at room temperature for 30 minutes. Then, 15 parts of polyvinyl chloride powder were added and stirred at 50°C for 2 hours. After complete dissolution, the mixture was allowed to stand at room temperature to remove air bubbles, finally obtaining a uniform spinning solution.

[0064] The spinning solution was loaded into a 10ml syringe and fixed to a syringe pump. The voltage was 15kV, the spinning distance was 14cm, the spinning solution flow rate was 5.5ml / h, and the temperature was 25℃. A reciprocating pump was used to make the needle move back and forth at a uniform speed, thus obtaining a nanofiber dosimeter with uniform thickness. After winding, the fiber membrane was evaporated overnight at room temperature to ensure complete solvent evaporation. The dried fiber membrane was then peeled off from the aluminum foil to obtain the fluorescent flexible fiber membrane dosimeter.

[0065] After the fiber membrane dosimeter was placed in X-ray irradiation, the fluorescence spectrum changes were obtained using an ELISA reader. The ratio of the fluorescence intensity of the two peaks (the emission peak in the red region and the emission peak in the blue region) was linearly fitted to the radiation dose. The linear response relationship between the fluorescence ratio intensity and the X-ray dose is as follows: Figure 1 As shown.

[0066] As an embodiment of the present invention, a fluorescent flexible fiber membrane dosimeter contains, by weight, 12 parts of polyvinyl chloride powder, 0.024 parts of fluorescent quinoline dye, 50 parts of tetrahydrofuran, and 50 parts of N,N-dimethylformamide. Wherein:

[0067] The structural formula of the fluorescent quinoline dye is:

[0068]

[0069] The fluorescent flexible fiber membrane dosimeter has a fiber diameter of 400 nm;

[0070] The dose linear response range of the fluorescent flexible fiber membrane dosimeter is 0–350 Gy.

[0071] As an embodiment of the present invention, such as Figures 1 to 3 As shown, a method for preparing a fluorescent flexible fiber membrane dosimeter includes the following steps:

[0072] First, 0.024 parts of quinoline fluorescent dye were added to a mixed solvent of 50 parts tetrahydrofuran and 50 parts N,N-dimethylformamide and stirred at room temperature for 30 minutes. Then, 12 parts of polyvinyl chloride powder were added and stirred at 50°C for 2 hours. After complete dissolution, the mixture was allowed to stand at room temperature to remove air bubbles, finally obtaining a uniform spinning solution.

[0073] The spinning solution was loaded into a 10ml syringe and fixed to a syringe pump. The voltage was 18kV, the spinning distance was 14cm, the spinning solution flow rate was 5.5ml / h, and the temperature was 25℃. A reciprocating pump was used to make the needle move back and forth at a uniform speed, thus obtaining a nanofiber dosimeter with uniform thickness. After winding, the fiber membrane was evaporated overnight at room temperature to ensure complete solvent evaporation. The dried fiber membrane was then peeled off from the aluminum foil to obtain the fluorescent flexible fiber membrane dosimeter.

[0074] As an embodiment of the present invention, an application of a fluorescent flexible fiber membrane dosimeter in measuring ionizing radiation is provided. The fluorescent flexible fiber membrane dosimeter is composed of 10-15 parts by weight of polyvinyl chloride, 0.01-0.02 parts by weight of fluorescent quinoline dye, and 100 parts by weight of organic solvent; wherein:

[0075] The structural formula of the fluorescent quinoline dye is:

[0076]

[0077] The dose linear response range of the fluorescent flexible fiber membrane dosimeter is 0–350 Gy, such as Figure 2 As shown.

[0078] As an embodiment of the present invention, such as Figure 2 and Figure 3 As shown, after ionizing radiation, the fluorescence color and emission wavelength of the fluorescent flexible fiber membrane dosimeter change.

[0079] As an embodiment of the present invention, the radiation source of the ionizing radiation is an X-ray tube.

[0080] As an embodiment of the present invention, the dose rate of the ionizing radiation is 0.4 Gy / min-4.98 Gy / min.

[0081] As an embodiment of the present invention, such as Figure 4 As shown, the fluorescent flexible fiber membrane dosimeter can be used in radiotherapy, scientific research, and the radiation industry.

[0082] As an embodiment of the present invention, the fluorescent flexible fiber membrane dosimeter can be sewn into wearable devices such as gloves for personal dose monitoring in hazardous environments such as interventional radiation therapy and high-risk radiochemical operations.

[0083] Figure 5 This is a visual sensing diagram of the fluorescent quinoline group on the protons generated by X-ray irradiation of PVC, showing that in the existing technology, the fluorescent quinoline dye has the characteristic of changing from blue to red fluorescence when it encounters acid.

[0084] The preferred embodiments of the present application have been described above with reference to the accompanying drawings, but this does not limit the scope of the claims of the present application. Any modifications, equivalent substitutions, and improvements made by those skilled in the art without departing from the scope and substance of the embodiments of the present application shall be within the scope of the claims of the present application.

Claims

1. A method for preparing a fluorescent flexible fiber membrane dosimeter, characterized in that: Includes the following steps: S21. Add 0.01-0.02 parts of fluorescent quinoline dye to 100 parts of organic solvent, stir and dissolve at room temperature. After complete dissolution, add 10-15 parts of polyvinyl chloride powder, stir at 50°C for 2 hours, and after complete dissolution, let stand at room temperature to remove air bubbles and obtain a uniform spinning solution; wherein, the organic solvent is a mixture of tetrahydrofuran and N,N-dimethylformamide in a mixing ratio of 5-7:3-5. S22. Using electrospinning technology, prepare an electrospun flexible fiber membrane from the spinning solution obtained in step S21, and completely evaporate the solvent at room temperature; wherein, the electrospinning parameters are: voltage 10-18kV, spinning distance 13-15cm, spinning solution flow rate 3.5-5.5ml / h, and temperature 20-40℃. S23. Peel the dried electrospun flexible fiber membrane off the aluminum foil to obtain a fluorescent flexible fiber membrane dosimeter, wherein the fiber diameter of the fluorescent flexible fiber membrane dosimeter is 100nm~900nm and the dose linear response range is 0~350Gy.

2. The fluorescent flexible fiber membrane dosimeter prepared according to the preparation method of claim 1, characterized in that: The fluorescent flexible fiber membrane dosimeter is prepared by comprising 10-15 parts by weight of polyvinyl chloride, 0.01-0.02 parts by weight of fluorescent quinoline dye, and 100 parts by weight of organic solvent; wherein: The structural formula of the fluorescent quinoline dye is: The fiber diameter of the fluorescent flexible fiber membrane dosimeter is 100 nm to 900 nm; The dose linear response range of the fluorescent flexible fiber membrane dosimeter is 0–350 Gy; The organic solvent is a mixture of tetrahydrofuran and N,N-dimethylformamide in a ratio of 5-7:3-5.

3. The application of the fluorescent flexible fiber membrane dosimeter according to claim 2 in the measurement of ionizing radiation, characterized in that: The fluorescent flexible fiber membrane dosimeter is prepared by comprising 10-15 parts by weight of polyvinyl chloride, 0.01-0.02 parts by weight of fluorescent quinoline dye, and 100 parts by weight of organic solvent; wherein: The structural formula of the fluorescent quinoline dye is: The fiber diameter of the fluorescent flexible fiber membrane dosimeter is 100 nm to 900 nm; The dose linear response range of the fluorescent flexible fiber membrane dosimeter is 0–350 Gy; The organic solvent is a mixture of tetrahydrofuran and N,N-dimethylformamide in a ratio of 5-7:3-5.

4. The application according to claim 3, characterized in that: The fluorescent flexible fiber membrane dosimeter glows red after being irradiated, and exhibits a gradient color difference with varying irradiation doses, making the color change obvious and easy to observe.

5. The application according to claim 4, characterized in that: The source of the ionizing radiation is an X-ray tube.

6. The application according to claim 5, characterized in that: The dose rate of the ionizing radiation is 0.4 Gy / min to 4.98 Gy / min.

7. The application according to claim 6, characterized in that: Application of the fluorescent flexible fiber membrane dosimeter in radiomedicine.

8. The application according to claim 6, characterized in that: Application of the fluorescent flexible fiber membrane dosimeter in scientific experiments.

9. The application according to claim 6, characterized in that: Application of the fluorescent flexible fiber membrane dosimeter in the radiation industry.

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