CN111892534A - pH-sensitive fluorescent probe, and preparation method and application thereof - Google Patents

pH-sensitive fluorescent probe, and preparation method and application thereof Download PDF

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CN111892534A
CN111892534A CN202010772134.0A CN202010772134A CN111892534A CN 111892534 A CN111892534 A CN 111892534A CN 202010772134 A CN202010772134 A CN 202010772134A CN 111892534 A CN111892534 A CN 111892534A
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张国庆
裴斌
陈彪
黄文环
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University of Science and Technology of China USTC
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Abstract

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.

Description

pH-sensitive fluorescent probe, and preparation method and application thereof
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;
Figure BDA0002617039050000011
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);
Figure BDA0002617039050000031
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;
Figure BDA0002617039050000061
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),
Figure BDA0002617039050000062
Figure BDA0002617039050000071
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);
Figure BDA0002617039050000072
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.
Example 1
Reacting a compound shown as a formula (III 1) with p-toluenesulfonamide in toluene at a molar ratio of 1:1.1 at 110 ℃ for 0.5h, then adding a compound shown as a formula (II 1) with the same equivalent into a reaction system, reacting for 120h, and recrystallizing in ethanol to obtain a molecule 1 shown in a figure 1; FIGS. 15 and 16 show the molecular 1 in DMSO-d, respectively6Hydrogen and carbon spectra in (1), FIG. 17 is an ESI mass spectrum of molecule 1;
Figure BDA0002617039050000091
example 2
Reacting a compound shown as a formula (III 1) with p-toluenesulfonamide in toluene at a molar ratio of 1:1.1 at 110 ℃ for 0.5h, then adding a compound shown as a formula (II 2) with the same equivalent into a reaction system, reacting for 120h, and recrystallizing in ethanol to obtain a molecule 2 shown as a figure 1; FIGS. 18 and 19 show the presence of molecule 2 in DMSO-d, respectively6Hydrogen and carbon spectra in (1), FIG. 20 is an ESI mass spectrum of molecule 2;
Figure BDA0002617039050000092
example 3
Reacting a compound shown as a formula (III 2) with p-toluenesulfonamide in toluene at a molar ratio of 1:1.1 at 110 ℃ for 0.5h, then adding a compound shown as a formula (II 2) with the same equivalent into a reaction system, reacting for 120h, and recrystallizing in ethanol to obtain a molecule 3 shown in a figure 1; FIGS. 21 and 22 show the presence of molecule 3 in DMSO-d, respectively6Hydrogen and carbon spectra in (1), FIG. 23 is an ESI mass spectrum of molecule 3;
Figure BDA0002617039050000101
example 4
Reacting a compound shown as a formula (III 3) with p-toluenesulfonamide in toluene at a molar ratio of 1:1.1 at 110 ℃ for 0.5h, then adding a compound shown as a formula (II 2) with the same equivalent into a reaction system, reacting for 120h, and recrystallizing in ethanol to obtain a molecule 4 shown in a figure 1; FIGS. 24 and 25 show the presence of molecule 4 in DMSO-d, respectively6Hydrogen and carbon spectra in (1), FIG. 26 is an ESI mass spectrum of molecule 4;
Figure BDA0002617039050000102
example 5
Reacting a compound shown as a formula (III 4) with p-toluenesulfonamide in toluene at a molar ratio of 1:1.1 at 110 ℃ for 0.5h, then adding a compound shown as a formula (II 2) with the same equivalent into a reaction system, reacting for 120h, and recrystallizing in ethanol to obtain a molecule 5 shown in a figure 1; FIGS. 27 and 28 show molecular 5 in DMSO-d, respectively6Hydrogen and carbon spectra in (1), FIG. 29 is an ESI mass spectrum of molecule 5;
Figure BDA0002617039050000103
example 6
Reacting a compound shown as a formula (III 4) with p-toluenesulfonamide in toluene at a molar ratio of 1:1.1 at 110 ℃ for 0.5h, then adding a compound shown as a formula (II 1) with the same equivalent into a reaction system, reacting for 120h, and recrystallizing in ethanol to obtain a molecule 6 shown in a figure 1; FIGS. 30 and 31 are the DMSO-d of formula 6, respectively6Hydrogen and carbon spectra in (1), FIG. 32 is an ESI mass spectrum of molecule 6;
Figure BDA0002617039050000111
example 7
Dissolving PMMA or PVC by adopting an organic solvent dichloromethane to prepare a solution with the concentration of 80g/100 ml;
respectively dissolving pure organic fluorescent molecules 1-6 by using an organic solvent methanol to prepare a solution with the concentration of 3 mg/ml;
the two solutions prepared were mixed at 37.5: 1, so that the mass concentration of the pure organic fluorescent molecules in the final solution is one thousandth of the mass concentration of the macromolecular matrix;
and (3) taking the final solution, spin-coating the final solution on a glass plate, putting the final solution into an oven for drying for 24 hours after the solvent is volatilized, and thus obtaining the polymer film doped with the fluorescent molecules.
Irradiating the polymer thin film with gamma rays of different radiation doses (4.06KGy, 0.34KGy, 0.12KGy) to obtain results as shown in fig. 2 to 9;
in FIG. 2
Figure BDA0002617039050000117
The curve is the photoluminescence spectrum of the molecules 1 without gamma irradiation of the PMMA thin film doped with the molecules 1,
Figure BDA0002617039050000112
the curve is the photoluminescence spectrum of the molecule 1 after the PMMA film doped with the molecule 1 is irradiated by 0.12KGy gamma ray,
Figure BDA0002617039050000113
the curve is the photoluminescence spectrum of the molecule 1 after the PMMA film doped with the molecule 1 is irradiated by 0.34KGy gamma ray,
Figure BDA0002617039050000114
the curve is the photoluminescence spectrum of the molecule 1 after the PMMA film doped with the molecule 1 is irradiated by 4.06KGy gamma rays,
Figure BDA0002617039050000115
the curve is that after the PMMA film doped with the molecule 1 is irradiated by 4.06KGy gamma ray, the PMMA film is dissolved by methylene dichloride, then a trace amount of triethylamine is added, the photoluminescence spectrum of the molecule 1 after the film is prepared again,
Figure BDA0002617039050000116
the curve is that in the preparation process of the PMMA film doped with the molecule 1, a trace amount of acetic acid is added, the photoluminescence spectrum of the molecule 1 of the film not subjected to gamma ray irradiation is shown in figure 2, as can be seen from figure 2, the fluorescence spectrum of the molecule 1 is also red-shifted and basically consistent with the system irradiated by the high-dose gamma ray, and after the system irradiated by the gamma ray is added with triethylamine, the fluorescence spectrum of the molecule 1 is blue-shifted and basically consistent with the spectrum of the system not irradiated. It can thus be demonstrated that fluorescent molecule 1 is essentially a fluorescent probe sensitive to pH;
in FIG. 3
Figure BDA00026170390500001214
The curve is the photoluminescence spectrum of molecules 2 without gamma irradiation of the PMMA thin film doped with molecules 2,
Figure BDA0002617039050000121
the curve is the photoluminescence spectrum of the molecule 2 after the PMMA film doped with the molecule 2 is irradiated by 0.12KGy gamma ray,
Figure BDA0002617039050000122
the curve is the photoluminescence spectrum of the molecule 2 after the PMMA film doped with the molecule 2 is irradiated by 0.34KGy gamma ray,
Figure BDA0002617039050000123
the curve is the photoluminescence spectrum of the molecule 2 after the PMMA film doped with the molecule 2 is irradiated by 4.06KGy gamma rays,
Figure BDA0002617039050000124
the curve is that after the PMMA film doped with molecule 2 is irradiated by 4.06KGy gamma ray, the PMMA film is dissolved by methylene dichloride, then a trace amount of triethylamine is added, the photoluminescence spectrum of molecule 2 after the film is prepared again,
Figure BDA0002617039050000125
the curve is that in the preparation process of the PMMA film doped with the molecules 2, trace acetic acid is added, the photoluminescence spectrum of the molecules 2 of the film is not irradiated by gamma rays, as can be seen from figure 3, the fluorescence spectrum of the molecules 2 is also red-shifted when the acetic acid is added into the system, and is basically consistent with the system irradiated by high-dose gamma rays, and the fluorescence spectrum of the molecules 2 is blue-shifted after the triethylamine is added into the system irradiated by gamma rays, and is basically consistent with the spectrum of the system not irradiated. It can be shown that the fluorescent molecule 2 provided in this application is also essentially a pH sensitive fluorescent probe.
In FIG. 4
Figure BDA0002617039050000126
The curve is the photoluminescence spectrum of molecule 1 without gamma irradiation of the PVC film doped with molecule 1,
Figure BDA0002617039050000127
the curve is the photoluminescence spectrum of the molecule 1 after the PVC film doped with the molecule 1 is irradiated by 0.12KGy gamma ray,
Figure BDA0002617039050000128
the curve is the photoluminescence spectrum of the molecule 1 after the PVC film doped with the molecule 1 is irradiated by 0.34KGy gamma ray,
Figure BDA0002617039050000129
the curve is the photoluminescence spectrum of the molecule 1 after the PVC film doped with the molecule 1 is irradiated by 4.06KGy gamma rays;
in FIG. 5
Figure BDA00026170390500001210
The curve is the photoluminescence spectrum of molecules 2 without gamma irradiation of the PVC film doped with molecules 2,
Figure BDA00026170390500001211
the curve is the photoluminescence spectrum of the molecule 2 after the PVC film doped with the molecule 2 is irradiated by 0.12KGy gamma ray,
Figure BDA00026170390500001212
the curve is the photoluminescence spectrum of the molecule 2 after the PVC film doped with the molecule 2 is irradiated by 0.34KGy gamma ray,
Figure BDA00026170390500001213
the curve is the photoluminescence spectrum of the molecule 2 after the PVC film doped with the molecule 2 is irradiated by 4.06KGy gamma rays;
in FIG. 6
Figure BDA0002617039050000131
The curve is the photoluminescence spectrum of molecules 3 without gamma irradiation of the PMMA thin film doped with molecules 3,
Figure BDA0002617039050000132
the curve is the photoluminescence of the molecule 3 after the PMMA film doped with the molecule 3 is irradiated by 0.12KGy gamma rayThe spectrum of the light beam is measured,
Figure BDA0002617039050000133
the curve is the photoluminescence spectrum of the molecule 3 after the PMMA film doped with the molecule 3 is irradiated by 0.34KGy gamma ray,
Figure BDA0002617039050000134
the curve is the photoluminescence spectrum of the molecule 3 after the PMMA film doped with the molecule 3 is irradiated by 4.06KGy gamma rays;
in FIG. 7
Figure BDA0002617039050000135
The curve is the photoluminescence spectrum of molecules 4 without gamma irradiation of the PMMA thin film doped with molecules 4,
Figure BDA0002617039050000136
the curve is the photoluminescence spectrum of the molecule 4 after the PMMA film doped with the molecule 4 is irradiated by 0.12KGy gamma ray,
Figure BDA0002617039050000137
the curve is the photoluminescence spectrum of the molecule 4 after the PMMA film doped with the molecule 4 is irradiated by 0.34KGy gamma ray,
Figure BDA0002617039050000138
the curve is the photoluminescence spectrum of the molecule 4 after the PMMA film doped with the molecule 4 is irradiated by 4.06KGy gamma rays;
in FIG. 8
Figure BDA0002617039050000139
The curve is the photoluminescence spectrum of molecules 5 without gamma irradiation of the PMMA thin film doped with molecules 5,
Figure BDA00026170390500001310
the curve is the photoluminescence spectrum of the molecules 5 after the PMMA film doped with the molecules 5 is irradiated by 0.12KGy gamma rays,
Figure BDA00026170390500001311
PMMA film with curve of doped molecule 5The photoluminescence spectrum of molecule 5 after irradiation with 0.34KGy gamma ray,
Figure BDA00026170390500001312
the curve is the photoluminescence spectrum of the molecules 6 after the PMMA film doped with the molecules 6 is irradiated by 4.06KGy gamma rays;
in FIG. 9
Figure BDA00026170390500001313
The curve is the photoluminescence spectrum of molecules 6 without gamma irradiation of the PMMA thin film doped with molecules 6,
Figure BDA00026170390500001314
the curve is the photoluminescence spectrum of the molecule 6 after the PMMA film doped with the molecule 6 is irradiated by 0.12KGy gamma ray,
Figure BDA00026170390500001315
the curve is the photoluminescence spectrum of the molecule 6 after the PMMA film doped with the molecule 6 is irradiated by 0.34KGy gamma ray,
Figure BDA00026170390500001316
the curve is the photoluminescence spectrum of the molecules 6 after the PMMA film doped with the molecules 6 is irradiated by 4.06KGy gamma rays;
like molecules 1 and 2, molecules 3, 4, 5 and 6 are fluorescent probes sensitive to pH, and as can be seen from fig. 6 to 9, molecules 3, 4, 5 and 6 doped into a specific polymer matrix (PMMA, PVC) can also be used for detecting gamma ray radiation dose. Theoretically, the fluorescent probe sensitive to pH provided by the application can be used for detecting the radiation dose of gamma rays in a specific polymer matrix;
FIG. 10 shows the irradiation dose of gamma rays corresponding to different sites, and FIG. 11 shows the photoluminescence spectra of molecules 2 in the 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 exposure of molecules 2 to gamma radiation at different sites.
As can be seen from FIGS. 2 to 14, the emission spectrum of the pure organic fluorescent molecules in the specific polymer matrix (PMMA, PVC) changes under different gamma radiation doses. As the radiation dose increases, a new emission peak appears at 600nm, and the ratio of the emission peak at 600nm to the original emission peak increases with the radiation dose.
The above description of the embodiments is only intended to facilitate the understanding of the method of the invention and its core idea. It should be noted that, for those skilled in the art, it is possible to make various improvements and modifications to the present invention without departing from the principle of the present invention, and those improvements and modifications also fall within the scope of the claims of the present invention.
The previous description of the disclosed embodiments is provided to enable any person skilled in the art to make or use the present invention. Various modifications to these embodiments will be readily apparent to those skilled in the art, and the generic principles defined herein may be applied to other embodiments without departing from the spirit or scope of the invention. Thus, the present invention is not intended to be limited to the embodiments shown herein but is to be accorded the widest scope consistent with the principles and novel features disclosed herein.

Claims (10)

1. A pH sensitive fluorescent probe comprises a pure organic fluorescent material shown as a formula (I) and a high molecular substrate;
Figure FDA0002617039040000011
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);
Figure FDA0002617039040000021
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.
CN202010772134.0A 2020-08-04 2020-08-04 pH-sensitive fluorescent probe, and preparation method and application thereof Pending CN111892534A (en)

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