CN113896729A - Preparation method and application of fluorescent probe for detecting gamma rays - Google Patents
Preparation method and application of fluorescent probe for detecting gamma rays Download PDFInfo
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- C07D471/00—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, at least one ring being a six-membered ring with one nitrogen atom, not provided for by groups C07D451/00 - C07D463/00
- C07D471/02—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, at least one ring being a six-membered ring with one nitrogen atom, not provided for by groups C07D451/00 - C07D463/00 in which the condensed system contains two hetero rings
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- G01T—MEASUREMENT OF NUCLEAR OR X-RADIATION
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Abstract
The invention discloses a preparation method of a perylene diimide-based fluorescent probe and application of the perylene diimide-based fluorescent probe in quantitative detection of gamma ray intensity. The invention takes perylene tetracarboxylic anhydride, 2-octyldodecylamine, zinc acetate, imidazole and 4-dimethylamino benzylamine as raw materials to prepare the compound with the molecular weight of C53H63N3O4The fluorescent probe molecule of perylene diimide can rapidly detect gamma rays in a solution by utilizing a Photoinduced Electron Transfer (PET) mechanism, and has the advantages of easily modified structure, low cost, light weight, flexibility, easiness in manufacturing into various shapes and the like.
Description
The technical field is as follows: the invention relates to the technical field of fluorescent probe sensing in analytical chemistry, in particular to a preparation method and application of a fluorescent probe for detecting gamma rays.
Background
Gamma rays (Gamma ray) are the third kind of nuclear rays discovered after alpha rays and beta rays, and are widely used in military, biology, medicine, environment, astronomy and other fields. Due to the characteristics of strong penetrating power and high energy, the method for accurately detecting the gamma ray intensity with low dosage has attracted wide attention in recent years.
Conventional gamma ray detection methods include ion chamber detectors, semiconductor detectors, radiographic films, scintillation detectors, and the like, but these methods still have some limitations, such as dependence on large-scale instruments, difficulty in preparing flexible devices from detection materials, difficulty in rapidly obtaining three-dimensional data, and the like. Compared to the above methods, the chemiluminescence sensor manufactured by a solvent-assisted method is receiving attention because of its ease of modification, low cost, thinness, excellent photoelectric properties, and ease of fabrication into various shapes. Although the literature reports experiments of gamma-ray fluorescence detection by applying principles of aggregation-induced emission (AIE), Fluorescence Resonance Energy Transfer (FRET) and Intramolecular Charge Transfer (ICT), as the most widely applied principle of fluorescence sensors at present, the light-induced electron transfer (PET) effect has not been applied to gamma-ray detection, and at present, the reactions of gamma rays detected by fluorescence are all quenching types, and fluorescence enhancement changes can be realized by using the PET mechanism, so that a new fluorescence detection means is developed to effectively detect the intensity of gamma rays.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provides a preparation method and application of a fluorescent probe for detecting gamma rays, and the prepared fluorescent probe is a fluorescent probe for quantitatively detecting the intensity of the gamma rays based on perylene diimide and has the advantages of low cost, light weight, flexibility, low detection limit, wide detection range, simplicity and convenience in operation, strong practicability and the like.
The purpose of the invention is realized by the following technical scheme:
the invention aims to provide a fluorescent probe for detecting gamma rays, which is named PDI-T and has a molecular formula of C53H63N3O4The structural formula is as follows:
the invention also aims to provide a preparation method of the fluorescent probe for detecting gamma rays, which comprises the following steps:
step one, preparing a compound PDI-D: heating, refluxing and stirring a compound perylene tetracarboxylic anhydride, 2-octyldodecylamine, zinc acetate and imidazole to prepare a compound octyldodecyl symmetric imide (PDI-D);
step two, preparing a compound PDI-S: dissolving the compound PDI-D obtained in the step one and potassium hydroxide in tert-butyl alcohol, heating, refluxing and stirring to obtain a compound PDI-S;
step three, preparing a compound PDI-T: heating, refluxing and stirring the compound PDI-S, 4-dimethylaminobenzylamine, zinc acetate and imidazole obtained in the second step until the reaction is complete to obtain the fluorescent probe PDI-T for detecting gamma rays;
the invention also aims to provide the application of the fluorescent probe in gamma ray detection, the fluorescent probe utilizes a PET mechanism, and the chloroform solution is accompanied with obvious fluorescent property change before and after gamma ray irradiation, namely, the fluorescent property of the solution is enhanced along with the increase of the irradiation dose, so that the gamma ray detection is realized.
Compared with the prior art, the invention has the following advantages and effects:
1. the fluorescent probe for detecting the gamma rays, provided by the invention, has the advantages that the detection of the gamma rays by the probe is simple and quick, and the photoinduced electron transfer phenomenon is realized, so that the fluorescent probe has wide application prospects in various fields of national defense, biology, medicine, environment and the like. The detection principle is shown in fig. 2, fluorescence is significantly enhanced (about 43 times enhanced), and a photoinduced electron transfer phenomenon (photoinduced electron transfer is a phenomenon that electrons are transferred intramolecularly or intermolecularly under the induction of light, when incident light irradiates a probe molecule, the donor molecule does not emit or only emits weak fluorescence due to the transfer of electrons from a donor to an excited state fluorophore, when the probe is combined with an analyte, the photoinduced electron transfer is blocked, the fluorophore can recover fluorescence emission), a perylene diimide group at the center of the probe molecule is used as the fluorophore, an aniline group connected with the perylene diimide group is used as the donor, and after gamma-ray irradiation, H generated in a solution is taken as a donor+After the probe is combined with the probe, the photoinduced electron transfer is blocked, the fluorescence emission of the fluorophore is recovered, and the probe is in fluorescent 'off-on' type response, so that the detection sensitivity is high, and the practicability is high.
2. According to the fluorescent probe for detecting the gamma rays, provided by the invention, the chloroform solution of the probe PDI-T is accompanied with obvious fluorescence change before and after gamma ray irradiation, and the larger the gamma ray irradiation dose is, the larger the fluorescence enhancement is, so that the quantitative detection of the gamma rays is realized, the detection limit is low, the detection range is wide, and the using effect is greatly improved.
3. The fluorescent probe for detecting gamma rays provided by the invention has the advantages of simple synthetic route, low cost and good thermal stability, and can be stored and used for a long time.
Drawings
FIG. 1 is a synthesis scheme of a fluorescent probe for detecting gamma-rays provided in example 1 of the present invention;
FIG. 2 is a schematic diagram of luminescence of a fluorescent probe for detecting gamma-rays provided in example 1 of the present invention;
FIG. 3 is a nuclear magnetic hydrogen spectrum diagram of a fluorescent probe for detecting gamma rays provided in example 1 of the present invention;
FIG. 4 is a nuclear magnetic carbon spectrum of a fluorescent probe for detecting gamma rays provided in example 1 of the present invention;
FIG. 5 is a high resolution mass spectrum of a fluorescent probe for detecting gamma rays provided in example 1 of the present invention;
FIG. 6 is a simulated gamma ray fluorescence spectrum of hydrochloric acid titration of different concentrations for the fluorescent probe for detecting gamma ray provided in example 2 of the present invention; wherein, the graph (a) is a fluorescence curve graph in the process of hydrochloric acid titration, and the graph (b) is a graph of the change of the fluorescence intensity of the probe solution at 540nm along with the concentration of hydrochloric acid.
FIG. 7 is a graph of the ultraviolet-visible absorption spectrum of a fluorescent probe for detecting gamma rays according to example 3 of the present invention under direct irradiation with gamma rays at different doses;
FIG. 8 is a graph of different doses of direct gamma-ray fluorescence spectra of the fluorescent probe for detecting gamma-rays provided in example 3 of the present invention; wherein, the graph (a) is a fluorescence curve graph of a gamma ray direct irradiation process, and the graph (b) is a fitting curve graph of fluorescence intensity at 540nm along with the change of irradiation dose.
Detailed Description
The invention is achieved by the following examples, but the conditions and results described in the practice do not limit the content or rights of the invention.
Example 1: fluorescent probe PDI-T
Preparation of fluorescent probe
1. Preparation of Compound PDI-D:
5g of perylenetetracarboxylic anhydride, 25g of imidazole and 100mg of zinc acetate are weighed and added into a 500mL round-bottom flask, 11.5mL of 2-octyldodecylamine is weighed and added, a stirrer is placed into the flask, the flask is placed into an oil bath heating pot, a condensation reflux device is installed and started, the heating temperature is set to 166 ℃, stirring is started, the reaction is stopped after stirring is continued for 3 hours after the temperature reaches 166 ℃, and the solution is reddish black. The solution is kept stirring and cooled to 80 ℃, 180mL of 2mol/L HCl is prepared and added to the solution for stirring and washing, then a large amount of ethanol is added for washing, the filtration is carried out, and a filter cake is washed by ethanol. The synthesized product is subjected to column chromatography separation by adopting a petroleum ether and dichloromethane gradient elution method, rotary evaporation, recrystallization and vacuum drying to obtain 11.258g of purple solid compound with the yield of 90.9%.
2. Preparation of Compound PDI-S:
950mg of the compound PDI-D and 30mg of KOH (one half) were weighed into a 500mL round-bottom three-necked flask, 10mL of t-butanol was added thereto, a stirrer was placed therein, the mixture was placed in an oil bath heating pan, a reflux condenser was installed and turned on, the heating temperature was set to 90 ℃ and stirring was started. Sequentially adding KOH according to a TLC detection result and solution color change, and when a light blue point appears on a point plate and reactants are not reacted completely, continuously adding 15mg of KOH to continue the reaction; when the spot plate generates dark blue and violet byproducts and reactants are not reduced, adding 15mg of KOH into the spot plate; when the reactants are basically completely reacted and the solution is earthy yellow, the reaction is carried out to the end point, and the reaction is stopped. Preparing 20mL of 2mol/L HCL, adding the HCL into the mixture, fully stirring, carrying out suction filtration, and washing a filter cake to be neutral by using water and ethanol. And placing the obtained product into a flask, adding a large amount of ethanol, carrying out oil bath heating reflux stirring, fully dissolving the by-product in the ethanol, carrying out suction filtration, and repeatedly washing with the ethanol until the liquid is light purple. The product is separated by column chromatography by adopting a (petroleum ether/dichloromethane) and (dichloromethane/methanol) gradient elution method, rotary evaporation is carried out, recrystallization is carried out, and then drying is carried out, so that 241.8mg of mauve solid product is obtained, and the yield is 35.9%.
3. Preparation of a probe molecule PDI-T:
300mg of a compound PDI-S, 6g of imidazole, 30mg of zinc acetate and 150mg of 4-dimethyl amino benzylamine are weighed and added into a 500mL round bottom flask, a stirrer is placed into the flask, then the flask is placed into an oil bath heating pot, a condensation reflux device is installed and started, the heating temperature is set to 130 ℃, stirring is started, the reaction progress is detected according to TLC, and after the reaction is completed, the solution is red-black. And (3) keeping stirring and cooling the solution to 90 ℃, then adding a large amount of ethanol, stirring, and carrying out suction filtration to obtain a product. The product is separated by column chromatography by adopting a (petroleum ether/dichloromethane) and (dichloromethane/methanol) gradient elution method, rotary evaporation is carried out, recrystallization is carried out, and then drying is carried out, so that 224.2mg of purple black solid product is obtained, and the yield is 62.2%.
The synthetic route of the probe PDI-T is shown in FIG. 1.
Two, fluorescent probe
1. The prepared fluorescent probe is a perylene diimide-based fluorescent probe for quantitatively detecting gamma rays, is named PDI-T, and has a molecular formula of C53H63N3O4The structural formula is as follows:
2. the light emitting principle of the probe molecule PDI-T is shown in figure 2, and is accompanied with photoinduced electron transfer phenomenon, wherein a perylene diimide group at the center of the probe molecule is used as a fluorophore, an aniline group connected with the perylene diimide group is used as a donor, and H generated in a solution after gamma ray irradiation+Upon binding to the probe, the photoinduced electron transfer is blocked and the fluorophore resumes fluorescent emission, and the probe is a fluorescent "off-on" type response.
3. The nuclear magnetic hydrogen spectrum of the probe molecule PDI-T is shown in FIG. 3, the nuclear magnetic carbon spectrum of the probe molecule PDI-T is shown in FIG. 4, and the high resolution mass spectrum (measured by a Fourier transform high resolution mass spectrometer) of the probe molecule PDI-T is shown in FIG. 5.
Example 2: fluorescence spectrum change of different concentration hydrochloric acid titration of probe PDI-T
Dissolving the probe PDI-T prepared in example 1 in chloroform (with pure chromatogram and 5% of 1-pentene added as a stabilizer) to prepare 5mL of 1mmol/L probe mother solution, measuring 0.1mL of 1mmol/L solution by using a pipette, adding the solution into a 10mL sample bottle, and adding 9.9mL of chloroform solution into the sample bottle to dilute the solution to obtain 10mL of 10 mu mol/L solution; using chloroform as a solvent to prepare a 2.4mmol/L HCl chloroform solution (diluting with 4 mol/L1, 4 dioxane solution of hydrochloric acid and chloroform); 3mL of prepared probe mother liquor is added into a cuvette for testing the fluorescence spectrum of a blank sample solution, after the probe mother liquor is taken out, 2.4mmol/L hydrochloric acid with a certain volume (5 muL, 10 muL, 50 muL, 100 muL, the times are different, till 400 muL) is added into the cuvette containing the solution to be tested one by one for titration, and after the probe mother liquor is uniformly mixed, the fluorescence spectrum test is carried out on the sample solution after each titration.
FIG. 6 is a graph showing the change of fluorescence spectrum of the probe PDI-T after reacting with HCl of different concentrations, and it can be seen that the emission intensity at 540nm is gradually increased with the increase of the HCl concentration, and the maximum enhancement factor can reach 43 times. And taking the peak values of different hydrochloric acid concentrations at 540nm as a scatter diagram, and enhancing the fluorescence intensity to an extreme value when the hydrochloric acid concentration reaches 115 mu mol/L. The judgment is that the combination of PDI-T molecules and HCl molecules inhibits the effect of intramolecular PET, the higher the HCl concentration is, the more PDI-T molecules can be combined, the stronger the inhibition capacity of the formed PET is, the more obvious the fluorescence intensity is enhanced, when the HCl concentration is increased to a certain value, the inhibition capacity of the formed PET is maximized, and at the moment, the fluorescence is not enhanced any more. The hydrochloric acid titration experiment can be used for simulating the change trend of gamma ray irradiation.
Example 3: ultraviolet spectrum and fluorescence spectrum changes of probe PDI-T under different doses of gamma ray irradiation
The probe PDI-T prepared in example 1 was dissolved in chloroform (for chromatographic purification, 5% 1-pentene was added as a stabilizer) to prepare 5mL of a 1mmol/L probe solution, 1mL of the 1mmol/L probe solution was measured by a pipette and added to a clean, water-tight 100mL volumetric flask, the chloroform solution was added to the volumetric flask and diluted to obtain 100mL of a 10. mu. mol/L probe solution, and 70mL of the 10. mu. mol/L probe solution was takenDividing the probe solution into 14 parts by mol/L, adding the parts into 5mL sample bottles, marking corresponding irradiation dose labels (0-380Gy), and carrying out gamma ray irradiation on the packaged probe solution at corresponding doses. In an Elekta Synergy linac 6MV photon beam (TPR)20,100.685) radiation field, and performing an irradiation experiment on the sample solution by using a self-made three-dimensional water tank measuring and transferring system. The experimental conditions of the photon beam water absorbent dose irradiation are as follows: the nominal energy of the ray is 6MV, the SSD is 100cm, and the dose rate is about 2Gy/min at the water depth of 10 cm. And after the irradiation is finished, carrying out ultraviolet spectrum test and fluorescence spectrum test on the sample.
FIG. 7 is a graph of the ultraviolet absorption spectrum of the probe PDI-T after being irradiated by different doses of gamma rays, and it can be seen that the absorption peak is unchanged, which indicates that the structure of the chromophore is not changed; fig. 8 is a fluorescence spectrum of the probe PDI-T irradiated with different doses of gamma rays, and it can be seen that the emission intensity at 540nm gradually increases with the increase of the dose of gamma rays, and the peak value of the different doses at 540nm is taken as a scattergram, and the fitting equation is fitted to obtain y ═ 426.99+29353.55/(1+10^ ((30.59-x) × 0.046)). The enhancement factor calculated from the minimum and maximum fluorescence values was about 43 times. When the gamma ray dose reaches 130Gy, the fluorescence intensity is enhanced to an extreme value, the irradiation dose corresponding to the error value of the initial fluorescence value excluding three times is taken as the detection limit, the irradiation dose corresponding to the fluorescence enhancement to 95% of the maximum value is taken as the maximum detection range, and the detection range is 0.186-72.665Gy calculated by a fitting curve. In addition, the chromophore structure is not changed, but fluorescence is changed at the same time, which shows that the emission is influenced by N-containing substituents on the periphery, rather than the PDI parent nucleus. Therefore, the quantitative detection of the gamma rays by the PDI-T is realized by fitting the relation between the irradiation dose of the gamma rays and the fluorescence intensity, and the method has the advantages of low detection limit, wide detection range, easy modification of the structure, low cost, light weight, sensitivity, easy manufacture into various shapes and the like.
Finally, it should be noted that: the above examples are only intended to illustrate the technical solution of the present invention, but not to limit it; although the present invention has been described in detail with reference to the foregoing embodiments, it will be understood by those of ordinary skill in the art that: the technical solutions described in the foregoing embodiments may still be modified, or some technical features may be equivalently replaced; and such modifications or substitutions do not depart from the spirit and scope of the corresponding technical solutions of the embodiments of the present invention.
Claims (7)
1. A fluorescent probe for detecting gamma rays by a Photoinduced Electron Transfer (PET) mechanism, characterized in that: the molecular formula is C53H63N3O4The structural formula is as follows:
2. a method for preparing a fluorescent probe for detecting gamma rays by a PET mechanism according to claim 1, comprising: the preparation method comprises the following steps:
step one, preparing a compound PDI-D: heating, refluxing and stirring a compound perylene tetracarboxylic anhydride, 2-octyldodecylamine, zinc acetate and imidazole to prepare a compound octyldodecyl symmetric imide (PDI-D);
step two, preparing a compound PDI-S: dissolving the compound PDI-D obtained in the step one and potassium hydroxide in tert-butyl alcohol, heating, refluxing and stirring to obtain a compound PDI-S;
step three, preparing a compound PDI-T: and (3) heating, refluxing and stirring the compound PDI-S, 4-dimethylaminobenzylamine, zinc acetate and imidazole obtained in the second step until the reaction is complete, thus obtaining the fluorescent probe PDI-T for detecting gamma rays.
3. The method for preparing a fluorescent probe for detecting gamma rays by a PET mechanism according to claim 2, wherein: in the first step, the consumption of the perylene tetracarboxylic anhydride is 2-8g, the consumption of the 2-octyldodecylamine is 8-15mL, the consumption of the imidazole is 15-35g, the consumption of the zinc acetate is 50-150mg, the heating temperature is 100-200 ℃, the stirring is carried out for 2-6h, and the reaction is finished; and (3) keeping stirring, cooling the reaction to 50-90 ℃, adding hydrochloric acid to wash the product, then adding a large amount of ethanol to wash, performing suction filtration, performing vacuum drying, and performing column chromatography separation to obtain a mauve solid compound PDI-D.
4. The method for preparing a fluorescent probe for detecting gamma rays by a PET mechanism according to claim 2, wherein: in the second step, the PDI-D is 0.5-1.5g, the tert-butyl alcohol is 5-20mL, the KOH is 20-80mg, the PDI-D, the tert-butyl alcohol and the KOH are sequentially added in batches according to the TLC monitoring result and the color change of the solution, the heating temperature is 50-120 ℃, the stirring is carried out for 1-4 hours, and the reaction is finished; adding hydrochloric acid into the mixture, stirring, carrying out suction filtration, sequentially adding water and ethanol, washing until the product is free of acid, carrying out suction filtration, heating and stirring the product obtained after the suction filtration by using a large amount of ethanol, carrying out suction filtration to remove violet byproducts, and carrying out column chromatography separation on the residual product to obtain a red solid PDI-S.
5. The method for preparing a fluorescent probe for detecting gamma rays by a PET mechanism according to claim 2, wherein: in the third step, the dosage of PDI-S is 200-500mg, the dosage of 4-dimethylamino benzylamine is 60-160mg, the dosage of imidazole is 5-25g, the dosage of zinc acetate is 5-50mg, the heating temperature is 100-200 ℃, the stirring is carried out for 1-5h, and the reaction is finished; and cooling to 50-100 ℃, adding a large amount of ethanol, stirring, carrying out suction filtration, and carrying out column chromatography separation to obtain a purple black solid, namely the fluorescent probe PDI-T.
6. Use of a fluorescent probe according to claim 1 for detecting gamma radiation, characterized in that: by utilizing a PET mechanism, after aromatic amine is introduced into PDI molecules, lone pair electrons on N atoms in amino groups have a PET effect on perylene diimide groups to inhibit the fluorescence of the molecules, and at the moment, the PDI-T molecules have weak fluorescence intensity and emit weak fluorescence; after a certain dose of gamma ray irradiation, H, Cl and other free radicals can be generated in the PDI-T chloroform solution and then rapidly combined into molecules such as HCl, the HCl molecules are combined with N atoms on the amino group, the lone pair electrons are blocked to the PET effect of the perylene group, the fluorescence of the molecules is released, and a strong fluorescence phenomenon is shown.
7. Use of a fluorescent probe according to claim 1 for detecting gamma radiation, characterized in that: with the increase of the irradiation dose of the gamma rays, the fluorescence property of the solution is enhanced, and the fluorescence enhancement multiple can reach about 43 times; by fitting the relation between the gamma ray irradiation dose and the fluorescence intensity, the detection limit can reach 0.186Gy after three times of errors are eliminated; setting a maximum detection range by using the irradiation dose corresponding to the fluorescence value at the position of the fluorescence enhancement maximum value of 95%, wherein the range of the gamma rays detected by the PDI-T is 0.186-72.665 Gy; the fluorescent probe realizes the quantitative detection of gamma rays, and has the advantages of easy structure modification, low cost, light weight, sensitivity, easy manufacture into various shapes and the like.
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