CN113512041A - Purine matrix-based zinc ion detection fluorescent probe and preparation method and application thereof - Google Patents
Purine matrix-based zinc ion detection fluorescent probe and preparation method and application thereof Download PDFInfo
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Abstract
The invention discloses a purine matrix-based zinc ion detection fluorescent probe, which has a structural formula shown as the following formula I. The invention also discloses a preparation method of the purine matrix-based zinc ion detection fluorescent probe, which comprises the following steps: purine derivatives and chromone-3-formaldehyde are used as fluorescent groups, and hydrazine hydrate is used as a connecting group. The invention also discloses application of the purine matrix-based zinc ion detection fluorescent probe in detection of zinc ions in a solution. Prepared fluorescent probe is directed to Zn in solution2+The probe shows high sensitivity and high selectivity, and can detect zinc ions in a solid state; the preparation method of the fluorescent probe is simple in steps, raw materials are easy to obtain, and the obtained product is solid powder, is easy to store and has a wide application prospect.
Description
Technical Field
The invention belongs to the technical field of fluorescent probes, and particularly relates to a purine matrix-based zinc ion detection fluorescent probe and a preparation method and application thereof.
Background
Zinc ion (Zn)2+) Has good coordination function, is the second most abundant transition metal ion in human body, and is widely distributed in the nuclear fluid of human body. Zn2+The method has great attention in the field of neurobiology, and plays an important role in life processes such as enzymatic reaction, DNA synthesis and the like in biological systems. However, an excess of Zn2+Can cause nervous system diseases such as epilepsy, Parkinson's disease, ischemic stroke, infantile diarrhea and the like. Therefore, the selective recognition and effective detection of the free zinc ions have important significance for relevant researches in the fields of chemistry, biology, clinical medicine, agriculture and the like.
The zinc ion detection methods commonly used at present comprise Atomic Absorption Spectroscopy (AAS), Atomic Emission Spectroscopy (AES), inductively coupled plasma mass probes, electrochemical methods and the like, but the test methods are expensive, the sample pretreatment is complex, the measurement time is relatively long, and professional operators are required. However, the fluorescent probe has many advantages such as simple design, easy operation, and high sensitivity, and is widely used. So far, there are many reports of zinc ion fluorescent probes, but designing and preparing fluorescent probes with high selectivity and high sensitivity is still a hotspot in environmental and life science research.
Disclosure of Invention
The invention aims to overcome the defects in the prior art and provide a purine matrix-based zinc ion detection fluorescent probe, and the fluorescent probe compound has the advantages of specific recognition of zinc ions, short response time, high sensitivity and the like.
In order to achieve the technical effects, the technical scheme of the invention is as follows: a purine parent based zinc ion detection fluorescent probe has a structural formula shown as the following formula I:
the invention also aims to provide a preparation method of the purine matrix-based zinc ion detection fluorescent probe, which comprises the following steps:
carrying out substitution reaction on S1, 4, 6-dichloro-5-aminopyrimidine and 1-naphthylamine to obtain an intermediate shown in a formula II;
s2: taking the intermediate of the formula II and 1-naphthoic acid as raw materials, and reacting in an organic solvent to obtain an intermediate of a formula III;
s3: dissolving the intermediate in the formula III in an organic solvent to react with hydrazine hydrate to obtain an intermediate in the formula IV;
s4: carrying out condensation reaction on the intermediate shown in the formula IV and chromone-3-formaldehyde to obtain a purine matrix-based fluorescent probe I, namely a purine matrix-based zinc ion detection fluorescent probe;
the reaction route is as follows:
wherein the S1 is: adding 4, 6-dichloro-5-aminopyrimidine and 1-naphthylamine into an organic solvent methanol, adding concentrated hydrochloric acid after dissolving, refluxing and stirring, distilling under reduced pressure to remove the organic solvent after complete reaction, dissolving with NaOH, extracting with ethyl acetate, distilling under reduced pressure to remove ethyl acetate, finally recrystallizing with methanol and water, and drying to obtain the intermediate of the formula II.
Wherein the S2 is: respectively dissolving the intermediate shown in the formula II, 1-naphthoic acid, polyphosphoric acid and dodecyl trimethyl ammonium chloride in phosphorus oxychloride, refluxing and stirring, cooling the reaction liquid to room temperature after the reaction is completed, distilling under reduced pressure to remove the organic solvent, adding an ice water mixture into the reaction system under the condition of ice water bath, purifying and eluting by using MeOH/DCM (v/v, 1/250) through a column chromatography method, and drying to obtain the intermediate shown in the formula III.
Wherein the S3 is: dissolving the intermediate in the formula III in ethanol, adding hydrazine hydrate after the solid is completely dissolved, heating and stirring, cooling the reactant to room temperature after the reaction is completely finished, performing suction filtration, washing the solid with an organic solvent, and drying to obtain the intermediate in the formula IV.
Wherein the S4 is: dissolving the intermediate shown in the formula IV and chromone-3-formaldehyde in organic solvent ethanol, refluxing and stirring the mixed material, cooling the reaction material to room temperature after the reaction is completed, distilling under reduced pressure to remove the solvent, recrystallizing and purifying the crude product, and drying to obtain the fluorescent probe I.
Preferably, the synthetic route of the fluorescent probe of the present invention is shown in the following figure:
wherein the intermediate of the formula II is 6-chloro-N4- (naphthalene-1-yl) pyrimidine-4, 5-diamine, the intermediate of the formula III is 6-chloro-9- (naphthalene-1-yl) -8- (naphthalene ring-1-yl) -9H-purine, the intermediate of the formula IV is 6-hydrazino-9- (naphthalene-1-yl) -8- (naphthalene ring-1-yl) -9H-purine, and the compound of the formula I, namely (E) -3- ((2- (8, 9-di (naphthalene-1-yl) -9H-purin-6-yl) hydrazone) methyl) -4H-chromium-4-ketone, is the fluorescent probe compound for detecting zinc ions.
Further, the preparation process comprises:
s1 preparation of intermediates of formula II
Respectively adding 4, 6-dichloro-5-aminopyrimidine and 1-naphthylamine into organic solvent methanol, adding concentrated hydrochloric acid after dissolving, refluxing and stirring at 65 ℃, removing the organic solvent by reduced pressure distillation after complete reaction, dissolving by 1MNaOH, extracting by ethyl acetate, removing the ethyl acetate by reduced pressure distillation, and recrystallizing by methanol and water to obtain the intermediate of the formula II.
S2 preparation of intermediate of formula III
Dissolving the intermediate shown in the formula II, 1-naphthoic acid, polyphosphoric acid and dodecyl trimethyl ammonium chloride in phosphorus oxychloride, refluxing and stirring at 80 ℃, cooling a reaction solution to room temperature after the reaction is completed, distilling under reduced pressure to remove an organic solvent, adding an ice water mixture into a reaction system at 0-5 ℃ in an ice water bath, eluting with MeOH/DCM (v/v, 1/250), and distilling under reduced pressure to remove the solvent to obtain the intermediate III.
S3 preparation of intermediate of formula IV
Dissolving the intermediate of the formula III in ethanol, adding hydrazine hydrate, heating and stirring at 50 ℃, cooling the reactant to room temperature after the reaction is completed, carrying out suction filtration, and washing the solid with an organic solvent for 3 times to obtain the intermediate of the formula IV.
S4 preparation of purine base-based Zinc ion Probe Compound I
Dissolving the intermediate of formula IV and chromone-3-carbaldehyde in an organic solvent, ethanol, in N2And under protection, refluxing and stirring the reaction system at 80 ℃, cooling the reaction material to room temperature after complete reaction, removing the solvent under reduced pressure, and purifying the crude product by recrystallization to obtain the fluorescent probe compound I.
The invention also aims to provide the application of the purine matrix-based zinc ion detection fluorescent probe in the detection of zinc ions in a solution.
The invention has the advantages and beneficial effects that:
the preparation method takes purine rings and chromone-3-formaldehyde as fluorescent groups and hydrazine hydrate as connecting groups to prepare the purine matrix-based zinc ion detection fluorescent probe, the raw materials of the preparation method are easy to obtain, the method is simple, and the obtained product is solid powder, is easy to store and has good stability;
the purine derivatives are selected as rigid planar structures, and have the advantages of low biotoxicity, strong binding capacity of nitrogen atoms and metals and the like;
the fluorescent probe has specific recognition on zinc ions, short response time, high sensitivity and capability of detecting Zn in solution2+The probe of the invention can detect zinc ions in a solid state, and has good portability and stability.
Drawings
FIG. 1 shows DMSO-H of the fluorescent probe for zinc ion prepared in example 12Pair of zinc ions (Zn) in O (v/v = 9: 1) solution2+) Ultraviolet absorption spectrum of (1);
FIG. 2 shows the DMSO-H fluorescent probe prepared in example 12For different metals in O (v/v = 9: 1) solutionA sub-selective fluorescence spectrum;
FIG. 3 shows the fluorescent probe prepared in example 1 in DMSO-H2For different concentrations of zinc ion (Zn) in O (v/v = 9: 1) solution2+) A fluorescence spectral response map of (a);
FIG. 4 shows the fluorescent probe prepared in example 1 in DMSO-H2Fluorescence response plots for detection of selective interference for different ions in O (v/v = 9: 1) solution;
FIG. 5 shows the fluorescent probe prepared in example 1 in DMSO-H2O (v/v = 9: 1) and zinc ion (Zn)2+) A Job-plot of the complex ratio;
FIG. 6 is a graph showing the test strips prepared by using the fluorescent probe prepared in example 1 and different concentrations of zinc ions;
FIG. 7 is a graph showing response time when the fluorescent probe prepared in example 1 detects zinc ions;
FIG. 8 is a MS spectrum of the fluorescent probe prepared in example 1;
FIG. 9 shows NMR of fluorescent probe prepared in example 11H-NMR spectrum;
FIG. 10 shows NMR of the fluorescent probe obtained in example 113C-NMR spectrum.
Detailed Description
The following further describes embodiments of the present invention with reference to examples. The following examples are only for illustrating the technical solutions of the present invention more clearly, and the protection scope of the present invention is not limited thereby.
The experimental methods used in the present invention are all conventional methods unless otherwise specified. Materials, reagents and the like used in the experiments can be obtained from commercial sources unless otherwise specified. All reagents used in the examples below were either commercially available, analytically pure or chemically pure.
In the embodiment, the ionic solutions of various species are prepared by adding deionized water into chloride chemical reagents with purity of more than 99%, such as anhydrous zinc chloride, anhydrous ferric chloride and the like.
Example 1
The zinc ion fluorescent probe compound based on the purine parent is prepared by the following method:
s1 preparation of intermediate (6-chloro-N4- (naphthalen-1-yl) pyrimidine-4, 5-diamine) of formula II
In a 100 mL round bottom flask, 4, 6-dichloro-5-aminopyrimidine (5.00 g, 30 mmol) and 1-naphthylamine (8.58 g, 60 mmol) were added and dissolved in 50 mL methanol, followed by 5 mL of 12 mol/L HCl. The mixture was stirred at 65 ℃ under reflux for 5 days. After the reaction solution was cooled, the organic solvent was removed by distillation under reduced pressure. The whole crude product obtained is then dissolved in 50 mL of 1M aqueous NaOH and the mixture is extracted 3 times with ethyl acetate which is distilled off under reduced pressure. The organic phase was washed with 1.2M HCl, then dewatered with saturated brine and dried to give the crude product. The crude product is substituted by CH3OH/H2Recrystallization from O (v/v, 1: 5) and drying gave the intermediate of formula II as a pale purple solid powder (5.75 g, 71% yield).
The structural formula of the obtained intermediate of the formula II is as follows:
s2 preparation of intermediate (6-chloro-9- (naphthalen-1-yl) -8- (naphthalen-1-yl) -9H-purine) of formula III
Intermediate of formula II (1.00 g, 3.70 mmol), 1-naphthoic acid (3.18 g, 18.50 mmol) and DTAC (0.10 g, 10% mmol) were dissolved in 25 mL POCl3After the solid matter was dissolved, polyphosphoric acid (5.00 g, 14.80 mmol) was added. The reaction mixture was stirred at 80 ℃ under reflux for 72 hours. After completion of the reaction, the reaction mixture was cooled to room temperature, and the organic solvent was distilled off under reduced pressure to obtain a brown oil. Adding 100 mL of ice-water mixture into the reaction system under the condition of ice-water bath, stirring to separate out a large amount of solid, performing suction filtration to obtain a crude product, purifying by silica gel column chromatography, and using CH3OH/CH2Cl2(v/v, 1/250) and after removal of the solvent by distillation under reduced pressure, it was dried to give the intermediate of formula III as a pale yellow solid (0.56 g, 42% yield).
The structural formula of the intermediate of the formula III is as follows:
s3 preparation of intermediate (6-hydrazino-9- (naphthalen-1-yl) -8- (naphthalen-1-yl) -9H-purine) of formula IV
The intermediate of formula III (0.32 g, 0.80 mmol) was dissolved in 20 mL ethanol and hydrazine hydrate (0.25 g, 4 mmol) was added. The mixture was heated and stirred at 50 ℃ for 3 hours. After completion of the reaction, the mixture was cooled to room temperature, a solid precipitated, filtered with suction, washed three times with ice methanol and dried to give a pale yellow powder (0.23 g, yield 70%).
The structural formula of the intermediate of formula IV is:
s4 preparation of purine-based zinc ion fluorescent probe compound
Intermediate of formula IV (56 mg, 0.14 mmol) and chromone-3-carbaldehyde (37 mg, 0.21 mmol) were dissolved in 2 mL ethanol under N2The mixture was then stirred under reflux at 80 ℃ for 2 hours under protection. After completion of the reaction was followed by dot plate (TLC), the reaction mass was cooled to room temperature and the solvent was distilled off under reduced pressure. And (3) recrystallizing and purifying the crude product by using dichloromethane-methanol, adding a small amount of methanol to dissolve the crude product, adding a proper amount of dichloromethane to turbidity, placing the mixture in a refrigerator for refrigeration until crystals are separated out, performing suction filtration, and drying to obtain the zinc ion fluorescent probe compound I with the probe based on the purine matrix, wherein the zinc ion fluorescent probe compound I is light yellow powder (54.7 mg, 70%).
The structural formula of the obtained fluorescent probe compound is as follows:
the MS spectrogram of the fluorescent probe compound is shown in figure 8;
zinc ion fluorescent probe compound based on purine parent1H-NMR spectrum of (A):1H NMR (400 MHz, DMSO-d 6) δ 12.19 (s, 1H), 8.84 (s, 1H), 8.59 (s, 1H), 8.35 (s, 2H), 8.15 (dd, J = 7.9, 1.7 Hz, 1H), 7.98 (t, J = 7.4 Hz, 2H), 7.93 – 7.82 (m, 3H), 7.74 – 7.65 (m, 2H), 7.58 – 7.47 (m, 6H), 7.41 (dd, J = 4.7, 1.7 Hz, 2H), 7.32 (dd, J= 8.3, 7.2 Hz, 1H), see fig. 9.
Nuclear magnetic resonance 13C-NMR spectrum of purine-based zinc ion fluorescent probe compound:13C NMR (101 MHz, DMSO-d 6) δ 175.44, 156.23, 154.15, 153.32, 150.88, 134.98, 134.00, 133.39, 131.84, 131.50, 130.61, 130.26, 130.10, 129.34, 128.67 (d, J = 6.6 Hz), 127.87 (d, J = 12.1 Hz), 127.43, 127.22 (d, J = 12.6 Hz), 126.86, 126.36 (d, J = 14.7 Hz), 125.74 (d, J= 12.2 Hz), 125.01, 123.85, 122.91, 119.54, 119.16, 118.79, see fig. 10.
Performance testing of zinc ion fluorescent probes
1. Zinc ion fluorescent probe in DMSO-H2Pair of zinc ions (Zn) in O (v/v = 9: 1) solution2+) Ultraviolet absorption of
The zinc ion detection fluorescent probe prepared in example 1 was prepared into a 1mM stock solution of the probe with DMSO, each metal ion was prepared into a 3 mM stock solution of the metal ion with deionized water, and 3 mL of a blank solution DMSO-H was added2Adding 30 mu L of probe stock solution and 50 mu L of metal ion stock solution into O (v/v = 9: 1), and detecting by using a fluorescence spectrometer and an ultraviolet spectrophotometer to obtain that the maximum excitation wavelength of the fluorescence probe is 368 nm and the maximum emission wavelength is 509 nm, wherein the specific test results are as follows:
taking two cuvettes, adding 3 mL of blank solution DMSO-H respectively2O (v/v = 9: 1) neutralized 30 μ L of the probe stock solution, and 50 μ L of the zinc ion stock solution was added to one of the cuvettes, and the other cuvettes were subjected to uv spectroscopy without adding the zinc ion stock solution. The experimental result shows that the fluorescent probe compound has stronger ultraviolet absorption at the wavelength of lambda = 336 nm, when zinc ions are added into the solution, the ultraviolet absorption peak is gradually reduced,in addition, the fluorescent probe has almost no ultraviolet absorption at the wavelength of 368 nm, and the ultraviolet absorption peak is gradually enhanced after the concentration of zinc ions in the solution is increased. The results show that the probe is directed to Zn2+Has high sensitivity, as shown in figure 1.
2. Selective recognition of zinc ions by zinc ion fluorescent probes
To 3 mL of a blank solution DMSO-H2The result of adding 30 μ L of the probe stock solution and 50 μ L of each metal ion stock solution into O (v/v = 9: 1) shows that the fluorescence color of the probe solution changes from colorless to bright yellow when zinc ions are added, the fluorescence intensity of the fluorescence spectrum at 509 nm is obviously enhanced, and the fluorescence does not change when other metal ions are added, namely, the fluorescence probe of the invention has good selectivity for zinc ions, as shown in fig. 2.
3. Influence of zinc ion concentration on fluorescence intensity of zinc ion fluorescent probe
To 3 mL of a blank solution DMSO-H2And adding 30 mu L of probe stock solution and 0-50 mu L (0, 1, 2, 3 … … 40, 45, 50 mu L) of zinc ion solution (3 mM zinc ion stock solution) into O (v/v = 9: 1), wherein the fluorescent probe is colorless in the solution, but the fluorescence is continuously enhanced at 509 nm along with the increase of the concentration of the zinc ion, which shows that the fluorescence intensity is increased along with the increase of the concentration of the zinc ion, and the graph is shown in figure 3.
4. Interference of coexisting ions on zinc ion fluorescent probe
To 3 mL of a blank solution DMSO-H2To O (v/v = 9: 1) were added 30. mu.L of the probe stock solution and 50. mu.L of any other metal ion (Co)2+, Ni2+, Al3+, Cr3+, Mn2+, Mg2+, Pb2+, K+, Ca2+, Cs2+, Na+, Ag+, Cd2+, Pd2+,Fe3+And Cu2+) Stock solution, and finally adding 50 μ L of Zn to the blank solution2+Stock solutions were tested for fluorescence intensity. The results show that Pb2+, Fe3+And Cu2+Has certain quenching effect on the zinc ion fluorescent probe, and the existence of other metal ions can quench the zincThe ionic fluorescent probe compound does not have obvious interference in identifying zinc ions, and is shown in figure 4.
5. Influence of the ratio of Zinc ion to fluorescent Probe substance on fluorescence intensity
Probes and Zn were studied by the Job's plot method2+Binding rate of (2) to 3 mL of a blank solution DMSO-H2Adding a certain volume of probe stock solution and Zn into O (v/v = 9: 1)2+The stock solution (3 mM) was prepared so that the sum of the concentrations of the zinc ion detecting fluorescent probe and zinc ion was 50. mu.M, and the difference between the fluorescence intensity at 509 nm and the combined autofluorescence intensity of the zinc ion fluorescent probe at that concentration was obtained by changing the concentration ratio of the two (the quantitative ratio of the zinc ion detecting fluorescent probe to the zinc ion substance was 1: 9, 2: 8, 3: 7, 4: 6, 5: 5, 6: 4, 7: 3, 8: 2, 9: 1 in this order), and was plotted as the ratio of the ion to the total concentration. When the ratio of zinc ions is 0.5, the ordinate reaches the maximum value, and it can be determined that the fluorescent probe compound and zinc ions are mainly combined in a 1: 1 form to form a stable complex, as shown in FIG. 5.
6. Detection of probe test paper on zinc ions with different concentrations
And (3) soaking the filter paper in the stock solution containing the fluorescent probe for half an hour, taking out the test strip, and drying the test strip in the air to obtain the dry test strip containing the probe. The test strips were soaked in zinc ion concentration solutions of 0 mM, 0.05 mM, 0.1mM, 0.5 mM, and 1mM, respectively, and after soaking for several minutes, air-dried, and a rapidly discolored band was observed under a 365 nm ultraviolet lamp, indicating that the probe of the present invention can detect zinc ions in a solid state, see FIG. 6.
7. Response time of fluorescent probe for detecting zinc ions
To 3 mL of blank buffer DMSO-H2O (v/v = 9: 1) was added 30. mu.L of the probe stock solution and 50. mu.L of Zn2+In the stock solution, the fluorescence intensity of the probe is rapidly increased to the maximum value, and reaches the maximum value in about 5 minutes and the fluorescence intensity of the probe gradually shows a bottom and is stable, which indicates that the probe has the effect on Zn2+The detection is sufficiently stable and fast, see fig. 7.
Compared with the purine parent based zinc ion detection fluorescent probe disclosed in CN112321588A, the zinc ion detection fluorescent probe has the following advantages:
1. structural formula and material properties: the molecular structure of the zinc ion fluorescent probe of CN112321588A contains a thiophene ring, the relative position of the fluorescent probe is a naphthalene ring, and the property of the fluorescent probe is relatively stable;
2. as shown in fig. 7, the fluorescence intensity of the zinc ion fluorescent probe of CN112321588A reaches the highest value in 10 minutes, and decreases to some extent with the time; the fluorescence intensity of the probe reaches the highest value in about 5 minutes, and the fluorescence intensity tends to be stable along with the prolonging of time. The results show that the response time of the fluorescent probe for detecting the zinc ions is shorter, and the detection result is more stable.
The foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, various modifications and decorations can be made without departing from the technical principle of the present invention, and these modifications and decorations should also be regarded as the protection scope of the present invention.
Claims (7)
1. A purine parent based zinc ion detection fluorescent probe has a structural formula shown as the following formula I:
2. the method for preparing the purine precursor-based zinc ion detection fluorescent probe according to claim 1, which is characterized by comprising the following steps:
carrying out substitution reaction on S1, 4, 6-dichloro-5-aminopyrimidine and 1-naphthylamine to obtain an intermediate shown in a formula II;
s2: taking the intermediate of the formula II and 1-naphthoic acid as raw materials, and reacting in an organic solvent to obtain an intermediate of a formula III;
s3: dissolving the intermediate in the formula III in an organic solvent to react with hydrazine hydrate to obtain an intermediate in the formula IV;
s4: carrying out condensation reaction on the intermediate shown in the formula IV and chromone-3-formaldehyde to obtain a purine matrix-based fluorescent probe, namely the purine matrix-based zinc ion detection fluorescent probe shown in the formula I;
the reaction route is as follows:
3. the method according to claim 2, wherein S1 is: adding 4, 6-dichloro-5-aminopyrimidine and 1-naphthylamine into an organic solvent methanol, adding concentrated hydrochloric acid after dissolving, refluxing and stirring, distilling under reduced pressure to remove the organic solvent after complete reaction, dissolving with NaOH, extracting with ethyl acetate, distilling under reduced pressure to remove ethyl acetate, recrystallizing with methanol and water, and drying to obtain the intermediate of the formula II.
4. The method according to claim 2, wherein S2 is: respectively dissolving the intermediate of the formula II, 1-naphthoic acid, polyphosphoric acid and dodecyl trimethyl ammonium chloride in phosphorus oxychloride, refluxing and stirring, cooling the reaction liquid to room temperature after the reaction is completed, distilling under reduced pressure to remove the organic solvent, adding an ice water mixture into the reaction system under the condition of ice water bath, purifying and eluting, and drying to obtain the intermediate of the formula III.
5. The method according to claim 2, wherein S3 is: dissolving the intermediate in the formula III in ethanol, adding hydrazine hydrate after the solid is completely dissolved, heating and stirring, cooling the reactant to room temperature after the reaction is completely finished, carrying out suction filtration, washing the solid with an organic solvent, and drying to obtain the intermediate in the formula IV.
6. The method according to claim 2, wherein S4 is: dissolving the intermediate of the formula IV and chromone-3-formaldehyde in an organic solvent, refluxing and stirring the mixed material, cooling the reaction material to room temperature after the reaction is completed, distilling under reduced pressure to remove the solvent, recrystallizing and purifying the crude product, and drying to obtain the purine matrix-based fluorescent probe.
7. Use of the purine precursor-based zinc ion detection fluorescent probe of claim 1 for detecting zinc ions in a solution.
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| CN114409646A (en) * | 2021-11-25 | 2022-04-29 | 江苏科技大学 | Fluorescent probe for detecting copper ions and preparation method and application thereof |
| CN114773343A (en) * | 2022-03-09 | 2022-07-22 | 江苏科技大学 | Copper and zinc ion dual-detection fluorescent probe and preparation method thereof |
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| CN112321588A (en) * | 2020-11-27 | 2021-02-05 | 江苏科技大学 | Purine matrix-based zinc ion detection fluorescent probe and preparation method and application thereof |
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| CN112321588A (en) * | 2020-11-27 | 2021-02-05 | 江苏科技大学 | Purine matrix-based zinc ion detection fluorescent probe and preparation method and application thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN114409646A (en) * | 2021-11-25 | 2022-04-29 | 江苏科技大学 | Fluorescent probe for detecting copper ions and preparation method and application thereof |
| CN114409646B (en) * | 2021-11-25 | 2022-12-02 | 江苏科技大学 | Fluorescent probe for detecting copper ions and preparation method and application thereof |
| CN114773343A (en) * | 2022-03-09 | 2022-07-22 | 江苏科技大学 | Copper and zinc ion dual-detection fluorescent probe and preparation method thereof |
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