阅读说明：本技术 一种pH敏感的荧光探针、其制备方法及其应用 (pH-sensitive fluorescent probe, and preparation method and application thereof ) 是由 张国庆 裴斌 陈彪 黄文环 于 2020-08-04 设计创作，主要内容包括：本发明提供了一种可用于伽马射线辐射剂量检测的荧光探针,其包括纯有机荧光材料和高分子基质,该荧光探针中的高分子基质受伽马射线辐照后产生质子,而纯有机荧光材料中具有较大的共振结构,该结构对pH极其敏感,与高分子基质中生成的质子结合后,荧光光谱发生较大位移,进而根据光谱实现伽马射线辐射剂量的检测。(The invention provides a fluorescent probe for gamma ray radiation dose detection, which comprises a pure organic fluorescent material and a high molecular substrate, wherein the high molecular substrate in the fluorescent probe generates protons after being irradiated by gamma rays, the pure organic fluorescent material has a larger resonance structure which is extremely sensitive to pH, and after the structure is combined with the protons generated in the high molecular substrate, a fluorescence spectrum generates larger displacement, so that the gamma ray radiation dose detection is realized according to the spectrum.)

1. A pH sensitive fluorescent probe comprises a pure organic fluorescent material shown as a formula (I) and a high molecular substrate;

wherein R is₁、R₂Is a purely organic electron donating group;

when X is N, R₈Is absent;

when X is C, R₈Selected from hydrogen, halogen, cyano, amino, hydroxyl, carboxyl, cyano, sulfydryl, amido, substituted alkyl of C1-C6, unsubstituted alkyl of C1-C6, and substituted cycloalkyl of C1-C6Unsubstituted C1-C6 cycloalkyl, substituted C1-C6 alkoxy, unsubstituted C1-C6 alkoxy, substituted C6-C30 arylamine, unsubstituted C6-C30 arylamine, substituted C6-C30 aryl or unsubstituted C6-C30 aryl;

R₃、R₄、R₅、R₆and R₇Independently selected from hydrogen, halogen, cyano, amino, hydroxyl, carboxyl, cyano, sulfydryl, amido, substituted alkyl of C1-C6, unsubstituted alkyl of C1-C6, substituted cycloalkyl of C1-C6, unsubstituted cycloalkyl of C1-C6, substituted alkoxy of C1-C6, unsubstituted alkoxy of C1-C6, substituted arylamine of C6-C30, unsubstituted arylamine of C6-C30, substituted aryl of C6-C30 or unsubstituted aryl of C6-C30.

2. The fluorescent probe of claim 1, wherein R is the number of atoms when X is C₃、R₄、R₅、R₆、R₇And R₈Independently selected from hydrogen, halogen, substituted C1-C3 alkyl, unsubstituted C1-C3 alkyl, substituted C1-C3 alkoxy or unsubstituted C1-C3 alkoxy; when X is N, R₃、R₄、R₅、R₆And R₇Independently selected from hydrogen, halogen, substituted C1-C3 alkyl, unsubstituted C1-C3 alkyl, substituted C1-C3 alkoxy or unsubstituted C1-C3 alkoxy.

3. The fluorescent probe of claim 1, wherein R is₁、R₂Independently selected from hydroxyethyl or methyl, R is R when X is C₃、R₄、R₅、R₆、R₇And R₈Independently selected from H, alkoxy, Cl, Br and F; when X is N, R₃、R₄、R₅、R₆And R₇Independently selected from H, alkoxy, Cl, Br and F.

4. The fluorescent probe of claim 1, wherein the polymeric matrix is PMMA or PVC.

5. The fluorescent probe of claim 1, wherein the doping amount of the pure organic fluorescent material in the polymer matrix is one thousandth to one hundredth of the mass of the polymer matrix.

6. The fluorescent probe according to claim 1, wherein the preparation method of the pure organic fluorescent material specifically comprises the following steps:

reacting a compound with a structure shown in a formula (II) with a mixture with a structure shown in a formula (III) in a solvent, and separating to obtain a pure organic fluorescent material with a structure shown in a formula (I);

wherein R is₁、R₂Is a purely organic electron donating group;

when X is N, R₈Is absent;

when X is C, R₈Selected from hydrogen, halogen, cyano, amino, hydroxyl, carboxyl, cyano, sulfydryl, amido, substituted alkyl of C1-C6, unsubstituted alkyl of C1-C6, substituted cycloalkyl of C1-C6, unsubstituted cycloalkyl of C1-C6, substituted alkoxy of C1-C6, unsubstituted alkoxy of C1-C6, substituted arylamine of C6-C30, unsubstituted arylamine of C6-C30, substituted aryl of C6-C30 or unsubstituted aryl of C6-C30;

R₃、R₄、R₅、R₆and R₇Independently selected from hydrogen, halogen, cyano, amino, hydroxyl, carboxyl, cyano, sulfydryl, amido, substituted alkyl of C1-C6, unsubstituted alkyl of C1-C6, substituted cycloalkyl of C1-C6, unsubstituted cycloalkyl of C1-C6, substituted alkoxy of C1-C6, unsubstituted alkoxy of C1-C6, substituted arylamine of C6-C30, unsubstituted arylamine of C6-C30, substituted aryl of C6-C30 or unsubstituted C6-C30Aryl group of (1).

7. The fluorescent probe of claim 6, wherein the molar ratio of the compound having the structure of formula (II) to the compound having the structure of formula (III) is 1: (0.8 to 1.2).

8. The method for preparing the fluorescent probe according to claim 1, comprising the steps of:

dissolving a polymer matrix by adopting an organic solvent to obtain a solution of the polymer matrix;

dissolving a pure organic fluorescent material shown in a formula (I) by adopting an organic solvent to obtain a solution of the pure organic fluorescent material;

mixing the solution of the polymer matrix and the solution of the pure organic fluorescent material.

9. The method according to claim 8, wherein the organic solvent in the solution for obtaining the polymer matrix is selected from dichloromethane or tetrahydrofuran, and the organic solvent in the solution for obtaining the pure organic fluorescent material is selected from methanol, ethanol or tetrahydrofuran.

10. Use of the fluorescent probe according to any one of claims 1 to 7 or the fluorescent probe prepared by the preparation method according to any one of claims 8 to 9 in gamma ray radiation dose detection.

Technical Field

The invention relates to the technical field of organic materials, in particular to a pH-sensitive fluorescent probe, a preparation method and application thereof.

Background

To date, essentially all methods of gamma ray characterization are based on their ionization effect, i.e., the photon energy of a gamma ray is converted into the kinetic energy of an electron, which is then captured, amplified and analyzed. Detectors and spectrometers for detecting gamma rays using atomic or molecular gases (e.g., Ar) (p.t. eisenberger, w.reed, phys.rev.a 1972,5,2085.) and semiconductors (e.g., high purity germanium or HPG) (z.he, nuclear.instruments.methods phys.res., sect.a 2001,463, 250-. The detection of gamma rays based on inorganic (e.g., NaI) and organic scintillators (e.g., anthracene) is based on essentially the same principle.

However, this technique has not been reported in the case of a pure organic fluorescent material, in which the variation of the fluorescence spectrum reflects the dose of gamma radiation. Compared with the traditional detection method, the method has the advantages of low cost, strong processability, almost no place limitation, approximate estimation of radiation dose by observing color change, and huge potential application in the fields of high-energy physics, aerospace, nuclear power stations and the like.

Disclosure of Invention

The invention aims to provide a pH-sensitive fluorescent probe which can realize the detection of gamma ray radiation dose in a specific polymer matrix.

In view of the above, the present application provides a pH-sensitive fluorescent probe, which includes a pure organic fluorescent material represented by formula (i) and a polymer matrix;

wherein R is₁、R₂Is a purely organic electron donating group;

when X is N, R₈Is absent;

when X is C, R₈Selected from hydrogen, halogen, cyano, amino, hydroxyl, carboxyl, cyano, sulfydryl, amido, substituted alkyl of C1-C6, unsubstituted alkyl of C1-C6, substituted cycloalkyl of C1-C6, unsubstituted cycloalkyl of C1-C6, substituted alkoxy of C1-C6, unsubstituted alkoxy of C1-C6, substituted arylamine of C6-C30, unsubstituted arylamine of C6-C30, substituted alkoxy of C1-C6The aryl of C6-C30 or unsubstituted aryl of C6-C30;

R₃、R₄、R₅、R₆and R₇Independently selected from hydrogen, halogen, cyano, amino, hydroxyl, carboxyl, cyano, sulfydryl, amido, substituted alkyl of C1-C6, unsubstituted alkyl of C1-C6, substituted cycloalkyl of C1-C6, unsubstituted cycloalkyl of C1-C6, substituted alkoxy of C1-C6, unsubstituted alkoxy of C1-C6, substituted arylamine of C6-C30, unsubstituted arylamine of C6-C30, substituted aryl of C6-C30 or unsubstituted aryl of C6-C30.

Preferably, R is C when X is₃、R₄、R₅、R₆、R₇And R₈Independently selected from hydrogen, halogen, substituted C1-C3 alkyl, unsubstituted C1-C3 alkyl, substituted C1-C3 alkoxy or unsubstituted C1-C3 alkoxy; when X is N, R₃、R₄、R₅、R₆And R₇Independently selected from hydrogen, halogen, substituted C1-C3 alkyl, unsubstituted C1-C3 alkyl, substituted C1-C3 alkoxy or unsubstituted C1-C3 alkoxy.

Preferably, said R is₁、R₂Independently selected from hydroxyethyl or methyl, R is R when X is C₃、R₄、R₅、R₆、R₇And R₈Independently selected from H, alkoxy, Cl, Br and F; when X is N, R₃、R₄、R₅、R₆And R₇Independently selected from H, alkoxy, Cl, Br and F.

Preferably, the polymer matrix is PMMA or PVC.

Preferably, the doping amount of the pure organic fluorescent material in the polymer matrix is one thousandth to one hundredth of the mass of the polymer matrix.

Preferably, the preparation method of the pure organic fluorescent material specifically comprises the following steps:

reacting a compound with a structure shown in a formula (II) with a mixture with a structure shown in a formula (III) in a solvent, and separating to obtain a pure organic fluorescent material with a structure shown in a formula (I);

wherein R is₁、R₂Is a purely organic electron donating group;

when X is N, R₈Is absent;

when X is C, R₈Selected from hydrogen, halogen, cyano, amino, hydroxyl, carboxyl, cyano, sulfydryl, amido, substituted alkyl of C1-C6, unsubstituted alkyl of C1-C6, substituted cycloalkyl of C1-C6, unsubstituted cycloalkyl of C1-C6, substituted alkoxy of C1-C6, unsubstituted alkoxy of C1-C6, substituted arylamine of C6-C30, unsubstituted arylamine of C6-C30, substituted aryl of C6-C30 or unsubstituted aryl of C6-C30;

R₃、R₄、R₅、R₆and R₇Independently selected from hydrogen, halogen, cyano, amino, hydroxyl, carboxyl, cyano, sulfydryl, amido, substituted alkyl of C1-C6, unsubstituted alkyl of C1-C6, substituted cycloalkyl of C1-C6, unsubstituted cycloalkyl of C1-C6, substituted alkoxy of C1-C6, unsubstituted alkoxy of C1-C6, substituted arylamine of C6-C30, unsubstituted arylamine of C6-C30, substituted aryl of C6-C30 or unsubstituted aryl of C6-C30.

Preferably, the molar ratio of the compound having the structure of formula (ii) to the compound having the structure of formula (iii) is 1: (0.8 to 1.2).

The application also provides a preparation method of the fluorescent probe, which comprises the following steps:

dissolving a polymer matrix by adopting an organic solvent to obtain a solution of the polymer matrix;

dissolving a pure organic fluorescent material shown in a formula (I) by adopting an organic solvent to obtain a solution of the pure organic fluorescent material;

mixing the solution of the polymer matrix and the solution of the pure organic fluorescent material.

Preferably, in the solution for obtaining the polymer matrix, the organic solvent is selected from dichloromethane or tetrahydrofuran, and in the solution for obtaining the pure organic fluorescent material, the organic solvent is selected from methanol, ethanol or tetrahydrofuran.

The application also provides the application of the fluorescent probe or the fluorescent probe prepared by the preparation method in gamma ray radiation dose detection.

The application provides a pH sensitive fluorescent probe, and the polymer matrix in the fluorescent probe generates protons after being irradiated by gamma rays, and the pure organic fluorescent material has a larger resonance structure, and the structure is extremely sensitive to the protons generated by the polymer matrix, and after being combined with the protons, the fluorescence spectrum generates larger displacement, so that the detection of gamma ray radiation dose is realized according to the spectrum.

Drawings

FIG. 1 is a structural formula of a pure organic fluorescent molecule according to the present invention;

FIG. 2 shows the photoluminescence spectra of molecule 1 after different doses of gamma radiation in a PMMA matrix;

FIG. 3 is a photoluminescence spectrum of molecule 1 after being subjected to different doses of gamma radiation in a PVC matrix;

FIG. 4 is a photoluminescence spectrum of molecules 2 in a PMMA matrix after being subjected to different radiation doses of gamma rays;

FIG. 5 is a photoluminescence spectrum of molecule 2 in a PVC matrix after different doses of gamma radiation;

FIG. 6 is a photoluminescence spectrum of molecules 3 in a PMMA matrix after being subjected to different radiation doses of gamma rays;

FIG. 7 is a photoluminescence spectrum of molecules 4 in a PMMA matrix after being subjected to different radiation doses of gamma rays;

FIG. 8 is a photoluminescence spectrum of molecules 5 in a PMMA matrix after being subjected to different doses of gamma radiation;

FIG. 9 is a photoluminescence spectrum of molecules 6 in a PMMA matrix after being subjected to different doses of gamma radiation;

FIG. 10 shows the radiation dose of gamma rays corresponding to different sites;

FIG. 11 shows the photoluminescence spectra of molecules 2 in a PMMA matrix after being irradiated by gamma rays at different sites;

FIG. 12 is a graph of the change in the fluorescence peak of molecule 2 as a function of the dose of gamma radiation;

FIG. 13 is a photograph of a PMMA matrix with molecules 2 irradiated with gamma rays at different sites under natural light;

FIG. 14 is a photograph of the PMMA matrix at 365nm of ultraviolet light after molecules 2 are irradiated by gamma rays at different sites;

FIG. 15 is a hydrogen spectrum of molecule 1 prepared in example 1;

FIG. 16 is a carbon spectrum of molecule 1 prepared in example 1;

FIG. 17 is an ESI mass spectrum of molecule 1 prepared in example 1;

FIG. 18 is a hydrogen spectrum of molecule 2 prepared in example 1;

FIG. 19 is a carbon spectrum of molecule 2 prepared in example 1;

FIG. 20 is an ESI mass spectrum of molecule 2 prepared in example 1;

FIG. 21 is a hydrogen spectrum of molecule 3 prepared in example 1;

FIG. 22 is a carbon spectrum of molecule 3 prepared in example 1;

FIG. 23 is an ESI mass spectrum of molecule 3 prepared in example 1;

FIG. 24 is a hydrogen spectrum of molecule 4 prepared in example 1;

FIG. 25 is a carbon spectrum of molecule 4 prepared in example 1;

FIG. 26 is an ESI mass spectrum of molecule 4 prepared in example 1;

FIG. 27 is a hydrogen spectrum of molecule 5 prepared in example 1;

FIG. 28 is a carbon spectrum of molecule 5 prepared in example 1;

FIG. 29 is an ESI mass spectrum of molecule 5 prepared in example 1;

FIG. 30 is a hydrogen spectrum of molecule 6 prepared in example 1;

FIG. 31 is a carbon spectrum of molecule 6 prepared in example 1;

FIG. 32 is an ESI mass spectrum of molecule 6 prepared in example 1.

Detailed Description

For a further understanding of the invention, reference will now be made to the preferred embodiments of the invention by way of example, and it is to be understood that the description is intended to further illustrate features and advantages of the invention, and not to limit the scope of the claims.

The embodiment of the invention discloses a pH sensitive fluorescent probe, wherein a pure organic fluorescent material in the fluorescent probe is a quinoline derivative, the structure of the pure organic fluorescent material is provided with sites capable of combining H protons, the pure organic fluorescent material is essentially a pH sensitive fluorescent probe, a high molecular substrate generates protons after being irradiated by gamma rays, the pure organic fluorescent material has a larger resonance structure and is extremely sensitive to the protons, the fluorescence spectrum generates larger displacement after being combined with the protons, and the detection of the irradiation dose of the gamma rays can be realized according to the change of the displacement. Specifically, the pH-sensitive fluorescent probe provided by the application comprises a pure organic fluorescent material shown as a formula (I) and a polymer matrix;

wherein R is₁、R₂Is a purely organic electron donating group;

when X is N, R₈Is absent;

when X is C, R₈Selected from hydrogen, halogen, cyano, amino, hydroxyl, carboxyl, cyano, sulfydryl, amido, substituted alkyl of C1-C6, unsubstituted alkyl of C1-C6, substituted cycloalkyl of C1-C6, unsubstituted cycloalkyl of C1-C6, substituted alkoxy of C1-C6, unsubstituted alkoxy of C1-C6, substituted arylamine of C6-C30, unsubstituted arylamine of C6-C30, substituted aryl of C6-C30 or unsubstituted aryl of C6-C30;

R₃、R₄、R₅、R₆and R₇Independently selected from hydrogen, halogen, cyano, amino, hydroxyl, carboxyl, cyano, sulfydryl, amido, substituted C1-C6 alkyl, unsubstituted C1-C6 alkyl and substituted C1-C6 cycloalkyl, unsubstituted C1-C6 cycloalkyl, substituted C1-C6 alkoxy, unsubstituted C1-C6 alkoxy, substituted C6-C30 arylamine, unsubstituted C6-C30 arylamine, substituted C6-C30 aryl or unsubstituted C6-C30 aryl.

According to different choices of X, the structural formula of the pure organic fluorescent material can be specifically selected from structures shown as a formula (I1) or a formula (I2),

more specifically, R₃、R₄、R₅、R₆、R₇And R₈Independently selected from hydrogen, halogen, substituted C1-C3 alkyl, unsubstituted C1-C3 alkyl, substituted C1-C3 alkoxy or unsubstituted C1-C3 alkoxy; when X is N, R₃、R₄、R₅、R₆And R₇Independently selected from hydrogen, halogen, substituted C1-C3 alkyl, unsubstituted C1-C3 alkyl, substituted C1-C3 alkoxy or unsubstituted C1-C3 alkoxy; in a specific embodiment, R when X is C₃、R₄、R₅、R₆、R₇And R8 is independently selected from H, alkoxy, Cl, Br, and F; when X is N, R₃、R₄、R₅、R₆And R₇Independently selected from H, alkoxy, Cl, Br and F.

The R is₁And R₂Is a purely organic electron donating group, which is a group well known to those skilled in the art, more specifically, R₁、R₂Independently selected from hydroxyethyl or methyl.

The preparation method of the pure organic fluorescent material comprises the following steps:

reacting a compound with a structure shown in a formula (II) with a mixture with a structure shown in a formula (III) in a solvent, and separating to obtain a pure organic fluorescent material with a structure shown in a formula (I);

wherein R is₁、R₂Is a purely organic electron donating group;

when X is N, R₈Is absent;

when X is C, R₈Selected from hydrogen, halogen, cyano, amino, hydroxyl, carboxyl, cyano, sulfydryl, amido, substituted alkyl of C1-C6, unsubstituted alkyl of C1-C6, substituted cycloalkyl of C1-C6, unsubstituted cycloalkyl of C1-C6, substituted alkoxy of C1-C6, unsubstituted alkoxy of C1-C6, substituted arylamine of C6-C30, unsubstituted arylamine of C6-C30, substituted aryl of C6-C30 or unsubstituted aryl of C6-C30;

R₃、R₄、R₅、R₆and R₇Independently selected from hydrogen, halogen, cyano, amino, hydroxyl, carboxyl, cyano, sulfydryl, amido, substituted alkyl of C1-C6, unsubstituted alkyl of C1-C6, substituted cycloalkyl of C1-C6, unsubstituted cycloalkyl of C1-C6, substituted alkoxy of C1-C6, unsubstituted alkoxy of C1-C6, substituted arylamine of C6-C30, unsubstituted arylamine of C6-C30, substituted aryl of C6-C30 or unsubstituted aryl of C6-C30.

In the preparation process, the molar ratio of the compound with the structure of the formula (II) to the compound with the structure of the formula (III) is 1: (0.8 to 1.2); the solvent is toluene.

In the present application, the polymer matrix can generate protons under gamma ray irradiation, that is, the polymer matrix can generate protons under gamma ray irradiation, and in a specific embodiment, the polymer matrix is selected from PMMA or PVC. The doping amount of the pure organic fluorescent material in the high molecular matrix is one thousandth to one hundredth of the mass of the high molecular matrix.

The application also provides a preparation method of the fluorescent probe, which comprises the following steps:

dissolving a polymer matrix by adopting an organic solvent to obtain a solution of the polymer matrix;

dissolving a pure organic fluorescent material shown in a formula (I) by adopting an organic solvent to obtain a solution of the pure organic fluorescent material;

mixing the solution of the polymer matrix and the solution of the pure organic fluorescent material.

In the preparation process of the pure organic fluorescent material composition, the organic solvent in the solution for obtaining the polymer matrix is selected from dichloromethane or tetrahydrofuran, and the organic solvent in the solution for obtaining the pure organic fluorescent material is selected from methanol, ethanol or tetrahydrofuran.

In order to facilitate the composition to be used for detecting the gamma ray dose, the obtained solution is further spin-coated on a substrate, and the polymer film doped with fluorescent molecules is obtained after the solvent is volatilized and dried.

The invention discloses a series of pH-sensitive fluorescent probes based on quinoline derivatives, wherein a pure organic fluorescent material is characterized in that molecules have a larger resonance structure and are extremely sensitive to protons, and after the molecules are combined with the protons, a fluorescence spectrum can generate larger displacement, so that the fluorescent probes provided by the application can be used for detecting gamma ray radiation dose. The pure organic fluorescent material provided by the application has the advantages of simplicity and convenience in synthesis, low cost, easiness in chemical modification, low toxicity, environmental friendliness and the like.

For further understanding of the present invention, the pH fluorescent probe, the preparation method thereof and the application thereof provided by the present invention will be described in detail with reference to the following examples, and the scope of the present invention is not limited by the following examples.