A probe for measuring beta and gamma radiation dose based on fluorescence response and a method for preparing the same

Abstract

The application discloses a probe for measuring beta and gamma radiation dose based on fluorescence response and a preparation method thereof. Under beta and gamma irradiation, the characteristic reaction of the charged particle beam and the halogen-containing copolymer high polymer material releases acidic substances as intermediates. The special solution with a pH-sensitive fluorescence response mechanism is matched to realize instant response to beta and gamma irradiation, generate fluorescence signals carrying incident ray information, and match conventional fluorescence detection means to realize quantitative detection of beta and gamma radiation dose. The probe has the characteristics of novel mechanism, timely response, small volume, low cost, maintenance-free, wide application prospect and good market value.

Description

Technical Field

[0001] This invention belongs to the field of fluorescence detection probe technology, specifically relating to a fluorescence-based probe for measuring β and γ radiation doses and its preparation method. Background Technology

[0002] X-rays are a type of high-energy radiation, including alpha particles, beta particles, and gamma rays. Under the irradiation of X-rays, matter will undergo ionization or reflect light. In order to quantitatively detect the intensity of X-rays, commonly used detection instruments mainly include equipment composed of ionizable gases or solids, photomultiplier tubes, and electronic instruments.

[0003] Research on detector materials is also an important part of probe research. Currently, scintillator materials, gas detectors, and semiconductor materials are widely used in radiation measurement and are constantly being optimized and improved. Beta particles are high-speed charged particles, and gamma rays are electromagnetic waves. They interact with detector materials, producing ionization effects or energy deposition. By measuring the characteristics and quantity of the charge or light signal generated by the detector, the magnitude of the radiation dose can be deduced.

[0004] In existing technologies, due to the different response characteristics of different detector materials to β and γ radiation, the probes still have limitations in terms of measurement range and energy response, and cannot meet the wide range of radiation measurement needs. Summary of the Invention

[0005] 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.

[0006] In view of the problems existing in the above and / or prior art, the present invention is proposed.

[0007] Therefore, the purpose of this invention is to overcome the shortcomings of the prior art and provide a fluorescence-based probe for detecting β and γ radiation doses.

[0008] To solve the above-mentioned technical problems, the present invention provides the following technical solution: the probe has a multi-stage structure, including,

[0009] Photochemical zone 100 is used to convert radiation signals into chemical signals;

[0010] The chromogenic region 200 is used to convert chemical signals into fluorescent signals;

[0011] The shielding layer 300 is used to wrap the photochemical region 100 and hold the color development region 200 solution;

[0012] The photochemical region 100 is made of vinylidene chloride methyl acrylate polymer, and the solution of the colorimetric region (200) is a 3-7 μM CNER-pH solution. The solvent of the CNER-pH solution includes one of acetonitrile, ethanol, dimethyl sulfoxide, and phosphate buffer solution. The structural formula of the CNER-pH is shown in formula (A).

[0013]

[0014] The material in the photochemical region 100 is composed of a polymer material that can release water-soluble acidic substances under irradiation. The photochemical reaction mechanism of producing acidic substances under β and γ irradiation is clear, and the product is singular and has good water solubility.

[0015] The material in the color development region 200 is composed of a solution with a pH-sensitive fluorescence response mechanism. The acidic substances generated by the photochemical region material under irradiation ionize in the solution and change the pH environment of the solution. By utilizing the pH sensitivity of the fluorescent substances in the color development region solution, the chemical signal carrying the energy-carrying ray information is converted into a fluorescence signal.

[0016] As a preferred embodiment of the fluorescence-responsive probe for β and γ radiation dose measurement described in this invention, the number of the photochemical region 100 and the shielding layer 300 are both set to two.

[0017] As a preferred embodiment of the fluorescence-responsive probe for β and γ radiation dose measurement according to the present invention, wherein: the colorimetric region 200 is disposed between the two photochemical regions 100, the outer sides of the two photochemical regions 100 are respectively attached to the inner sides of the two shielding layers 300, and the outer diameter of the shielding layer 300 is larger than the outer diameter of the photochemical region 100.

[0018] As a preferred embodiment of the fluorescence-responsive probe for β and γ radiation dose measurement described in this invention, the shielding layer 300 is made of a material resistant to acidic substance penetration, including polyethylene material with α-alumina sputtered on its surface.

[0019] The shielding layer is made of a material with good resistance to the penetration of acidic substances, so as to ensure that almost all the acidic intermediates generated in the photochemical zone enter the color development zone. The shielding layer material should also have good waterproof performance and a certain structural strength, and be used as a container to hold the solution in the color development zone.

[0020] As a preferred embodiment of the fluorescence-responsive probe for β and γ radiation dose measurement described in this invention, the material of the colorimetric region 200 does not chemically react or permeate with the material of the photochemical region 100 and the material of the shielding layer 300.

[0021] As a preferred embodiment of the fluorescence-responsive probe for β and γ radiation dose measurement described in this invention, the total thickness of the photochemical region 100 is ≤2mm, and the peel force between the shielding layer 300 and the photochemical region 100 is ≥50N / 15mm.

[0022] As a preferred embodiment of the fluorescence-responsive probe for β and γ radiation dose measurement described in this invention, the probe has an operating temperature range of -20℃ to 45℃ and an ultraviolet lamp wavelength of 365nm.

[0023] As a preferred embodiment of the fluorescence-responsive probe for β and γ radiation dose measurement described in this invention, the probe achieves quantitative detection of β and γ radiation dose through a pH-sensitive fluorescence response to β and γ radiation.

[0024] Another object of the present invention is to provide a method for preparing a fluorescence-responsive probe for detecting β and γ radiation doses, comprising using a vinylidene chloride methyl acrylate copolymer film as the photochemical region 100 material, using a polyethylene material with α-alumina sputtered on its surface as the shielding layer 300 material, and using a CNER-pH solution as the colorimetric region 200 material.

[0025] The material of the shielding layer 300 is cut to a shape that matches the material of the photochemical region 100, and the size of the material of the shielding layer 300 is greater than the size of the material of the photochemical region 100. The material of the photochemical region 100 is then attached to the material of the shielding layer 300 and slowly immersed in the solution of the color development region 200 until the internal space is filled. The material of the shielding layer 300 is then encapsulated using a high-frequency hot air blower to obtain the probe.

[0026] The probe of this invention can perform photoelectric conversion using common fluorescence detection methods. Therefore, the photoelectric region of the probe does not require special design. According to its function, it can be divided into two parts: one is the ultraviolet lamp band that provides the fluorescence detection background for the β and γ radiation dose detector, and the other is the signal processing part that analyzes the fluorescence band.

[0027] Another object of the present invention is to provide a detector for detecting β and γ radiation doses.

[0028] Beneficial effects of this invention:

[0029] This invention utilizes the characteristic reaction between an energetic particle beam and a halogen-containing copolymer polymer material under β and γ irradiation to release acidic substances as intermediates. Combined with a special solution exhibiting a pH-sensitive fluorescence response mechanism, it achieves an immediate response to β and γ irradiation and generates a fluorescence signal carrying incident radiation information. This is then combined with conventional fluorescence detection methods to achieve quantitative detection of β and γ radiation dose. This detector probe features a novel mechanism, timely response, small size, low cost, and maintenance-free operation, demonstrating broad application prospects and significant market value. Attached Figure Description

[0030] To more clearly illustrate the technical solutions of the embodiments of the present invention, the 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:

[0031] Figure 1 This is a schematic diagram of the probe structure in Embodiment 1 of the present invention.

[0032] Figure 2 This is a graph showing the fluorescence response of the probe in Embodiment 1 of the present invention under a UV background. Detailed Implementation

[0033] 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.

[0034] 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.

[0035] 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.

[0036] The synthetic route of the CNER-pH solution used in this invention is shown in formula (B):

[0037]

[0038] Compound 1 (473.3 mg, 1 mmol) and Boc-N-aminoethylpiperazine (229.3 mg, 1 mmol) were dissolved in 5 mL of ethylene glycol dimethyl ether. The mixture was stirred at 120 °C for 4 h under a nitrogen atmosphere. After the reaction solution was allowed to stand at room temperature, an equal volume of distilled water was added to the reaction flask. The solvent was removed by filtration to obtain a solid. The solid was purified to obtain orange-yellow compound 2 (503.6 mg, 81.0%).

[0039] Compound 2 (310.9 mg, 0.5 mmol) was dissolved in 25 mL of DCM, and 5 mL of TFA dilution (TFA:DCM = 2:3, v / v) was slowly added dropwise to the reaction system and stirred at 25 °C for 3 h. The solvent was then removed and the obtained solid compound was purified to obtain a light yellow solid CNER-1 (216.5 mg, 83.0%).

[0040] Compound CNER-1 (104.3 mg, 0.2 mmol), 7-hydroxycoumarin-3-carboxylic acid (41.2 mg, 0.2 mmol), HOBT (13.5 mg, 0.1 mmol), and EDC (76.7 mg, 0.4 mmol) were dissolved in 5 mL of LDM and stirred at room temperature. After 10 min, 200 μL of DIEA was added and stirring continued for 5 h. After completion, the solvent was removed, and the obtained solid product was purified to obtain the yellow compound CNER-pH (68.1 mg, 48.0%).

[0041] Unless otherwise specified, all other raw materials used in this invention can be obtained by those skilled in the art through conventional means.

[0042] Example 1

[0043] Reference Figure 1 This embodiment provides a fluorescence-responsive probe for measuring β and γ radiation doses and its fabrication method, specifically as follows:

[0044] A vinylidene chloride methyl acrylate copolymer (VdCl2MA) film was used as the photochemical zone 100 material; a polyethylene material with α-alumina sputtered on its surface was used as the shielding layer 300 material; and a CNER-pH solution was used as the color development zone 200 material. The CNER-pH solution was CNER-pH dissolved in acetonitrile with a concentration of 5 μM.

[0045] The material of the shielding layer 300 is cut to a shape consistent with that of the photochemical region 100, and the size of the shielding layer 300 is greater than that of the photochemical region 100. The photochemical region 100 is then attached to the shielding layer 300 and placed therein. The color development region 200 solution is then slowly immersed in the solution until the internal space is filled. The shielding layer 300 is then encapsulated using a high-frequency hot air blower to obtain the probe.

[0046] The total thickness of the photochemical region 100 of the probe obtained by this invention is ≤2mm, and the peel force between the shielding layer 300 and the photochemical region 200 is ≥50N / 15mm; the operating temperature range is -20℃~45℃; the ultraviolet lamp wavelength is 365nm.

[0047] Reference Figure 2 The image shows the effect of the detector probe of the present invention under ultraviolet background fluorescence response. Under alkaline conditions, the probe generally shows strong blue fluorescence, and under weakly acidic conditions, it shows strong green fluorescence. Moreover, the fluorescence color change of CNER-pH solution under 365nm irradiation due to pH change is significant, which is consistent with the response mechanism.

[0048] This invention uses the vinylidene chloride methyl acrylate copolymer VdCl2MA as the photochemical region material. Under irradiation conditions such as β and γ, it can release acidic substances. The CNER-pH solution undergoes significant changes in fluorescence color due to pH changes under 365nm ultraviolet light irradiation. Using the acidic substances produced by the vinylidene chloride methyl acrylate copolymer VdCl2MA under irradiation as intermediates, the irradiation signal is converted into a chemical signal. Then, the pH response sensitivity of the CNER-pH solution is used to convert the chemical signal into a fluorescence signal. Using common fluorescence signal analysis techniques, it can be converted into an electrical signal, thereby realizing the quantitative detection of irradiation intensity. The detector probe used for radiation detection has the characteristics of timely response, small size, low cost, and maintenance-free operation.

[0049] Example 2

[0050] The difference between this embodiment and Embodiment 1 is that the solvent of the CNER-pH solution is adjusted to ethanol, while the other materials and structures are the same as in Embodiment 1, resulting in the detection probe of this embodiment.

[0051] Example 3

[0052] The difference between this embodiment and Example 1 is that the solvent of the CNER-pH solution is adjusted to dimethyl sulfoxide, while the other materials and structures are the same as in Example 1, resulting in the detection probe of this embodiment.

[0053] Example 4

[0054] The difference between this embodiment and Embodiment 1 is that the solvent of the CNER-pH solution is adjusted to a phosphate buffer solution, while the other materials and structures are the same as in Embodiment 1, resulting in the detection probe of this embodiment.

[0055] The effectiveness of the probes in Examples 1 to 4 of this invention in measuring β and γ radiation doses was tested. It was found that all the probes had significant response effects, but the probe in Example 1 had the fastest response time, while the probe in Example 4 had the lowest responsiveness. The analysis suggests that acetonitrile may interact more readily with acidic substances in the copolymer than other solvents, promoting their release and generating a response. On the other hand, the phosphate buffer solution may stabilize the pH of the solution to some extent, leading to a decrease in the responsiveness of CNER-pH.

[0056] Example 5

[0057] The difference between this embodiment and Example 1 is that the concentration of the CNER-pH solution is adjusted to 3 μM, while the other materials and structures are the same as in Example 1, resulting in the detection probe of this embodiment.

[0058] Example 6

[0059] The difference between this embodiment and Example 1 is that the concentration of the CNER-pH solution is adjusted to 7 μM, while the other materials and structures are the same as in Example 1, resulting in the detection probe of this embodiment.

[0060] The effectiveness of the probes in Examples 5 and 6 of this invention in measuring β and γ radiation doses was tested and compared with that in Example 1. It was found that all the probes had significant response effects, while the probe in Example 1 had the fastest response time.

[0061] Generally, the higher the concentration of the CNER-pH solution, the more pronounced its response. High-concentration CNER-pH solutions contain more pH-sensitive molecules, which undergo more pH changes upon exposure to ultraviolet light, resulting in more significant changes in fluorescence color. Therefore, the detection effect of radiation dose is better. However, increasing the solution concentration does not necessarily mean that the response will increase linearly. CNER-pH solutions exceeding a certain concentration may lead to increased intermolecular interactions, thus affecting the solution's response performance.

[0062] Comparative Example 1

[0063] This comparative example provides a radiation dosimeter for detecting radiation dose in the prior art, specifically:

[0064] The radiation dosimeter consists of a first functional layer, a second functional layer, and a third functional layer.

[0065] The first functional layer is polytetrafluoroethylene or polyvinylidene chloride;

[0066] The second functional layer is composed of polypropylene nonwoven fabric material, and the polypropylene nonwoven fabric material is coated with dye leuco-diarylmethane dye.

[0067] The third functional layer is an impermeable material – polyethylene with α-alumina sputtered on its surface;

[0068] The radiation dosimeter in this scheme utilizes the characteristic that its first functional layer generates hydrogen fluoride or hydrogen chloride when stimulated in β and γ irradiation environments. The hydrogen fluoride and hydrogen chloride are collected and reacted with the leuco dye, thereby causing the leuco dye to form an alpha structure, which in turn changes the color of the leuco dye, thus enabling timely measurement of the environmental concentration of β and γ in the environment.

[0069] Compared with the detector in Embodiment 1 of this invention, this scheme requires the dye to undergo a chemical reaction to form an activating structure before it can change color, resulting in a slower response speed. The acidic substances generated in the photochemical region of this invention can convert the chemical signal into a fluorescent signal through a pH-sensitive CNER-pH solution, resulting in a faster response speed and providing more accurate and precise quantitative detection of radiation intensity.

[0070] In summary, this invention utilizes the characteristic reaction between an energetic particle beam and a halogen-containing copolymer polymer material under β and γ irradiation to release acidic substances as intermediates. Combined with a special solution exhibiting a pH-sensitive fluorescence response mechanism, it achieves an immediate response to β and γ irradiation and generates a fluorescence signal carrying incident radiation information. This is then combined with conventional fluorescence detection methods to achieve quantitative detection of β and γ radiation dose. This detector probe features a novel mechanism, timely response, small size, low cost, and maintenance-free operation, demonstrating broad application prospects and significant market value.

[0071] 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 fluorescence-response-based probe for measuring β and γ radiation dose, characterized in that: The probe has a multi-stage structure. include, The photochemical region (100) is used to convert radiation signals into chemical signals; The chromogenic region (200) is used to convert chemical signals into fluorescent signals; A shielding layer (300) is used to enclose the photochemical region (100) and hold the colorimetric region (200) solution; The photochemical region (100) is made of vinylidene chloride methyl acrylate polymer, and the colorimetric region (200) is a 3-7 μM CNER-pH solution. The solvent of the CNER-pH solution includes one of acetonitrile, ethanol, dimethyl sulfoxide, and phosphate buffer solution. The structural formula of the CNER-pH is shown in formula (A). ； Formula (A); The number of photochemical zones (100) and shielding layers (300) is set to two; The color development area (200) is disposed between the two photochemical areas (100), the outer sides of the two photochemical areas (100) are respectively attached to the inner sides of the two shielding layers (300), and the outer diameter of the shielding layer (300) is larger than the outer diameter of the photochemical area (100).

2. The fluorescence-response-based probe for measuring β and γ radiation dose as described in claim 1, characterized in that: The material of the shielding layer (300) is a material that prevents the penetration of acidic substances, including polyethylene material with α-alumina sputtered on its surface.

3. The fluorescence-responsive probe for measuring β and γ radiation dose as described in claim 1, characterized in that: The material of the color development zone (200) does not chemically react or permeate with the material of the photochemical zone (100) and the material of the shielding layer (300).

4. The fluorescence-response-based probe for measuring β and γ radiation dose as described in claim 1, characterized in that: The total thickness of the photochemical zone (100) is ≤2mm, and the peel force between the shielding layer (300) and the photochemical zone (100) is ≥50N / 15mm.

5. The fluorescence-responsive probe for measuring β and γ radiation dose as described in claim 1, characterized in that: The probe has an operating temperature range of -20℃ to 45℃ and an ultraviolet lamp wavelength of 365nm.

6. The fluorescence-responsive probe for measuring β and γ radiation dose as described in claim 5, characterized in that: The probe achieves quantitative detection of β and γ radiation doses through a pH-sensitive fluorescence response to β and γ radiation.

7. The method for fabricating a fluorescence-responsive probe for measuring β and γ radiation dose as described in claim 6, characterized in that: include, A polyvinylidene chloride methyl acrylate copolymer film was used as the photochemical zone (100) material, a polyethylene material with α-alumina sputtered on the surface was used as the shielding layer (300) material, and a CNER-pH solution was used as the color development zone (200) material. The shielding layer (300) material is cut to a shape consistent with the photochemical region (100) material, and the size of the shielding layer (300) material is greater than the size of the photochemical region (100) material. The photochemical region (100) material is attached to the shielding layer (300) material and placed therein. The color development region (200) solution is slowly soaked in the solution until the internal space is filled. The shielding layer (300) material is then encapsulated by a high-frequency hot air blower to obtain the probe.

8. A detector for detecting β and γ radiation doses, characterized in that: The probe described in any one of claims 1 to 6 is used.

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