CN114773343A - Copper and zinc ion dual-detection fluorescent probe and preparation method thereof - Google Patents
Copper and zinc ion dual-detection fluorescent probe and preparation method thereof Download PDFInfo
- Publication number
- CN114773343A CN114773343A CN202210231486.4A CN202210231486A CN114773343A CN 114773343 A CN114773343 A CN 114773343A CN 202210231486 A CN202210231486 A CN 202210231486A CN 114773343 A CN114773343 A CN 114773343A
- Authority
- CN
- China
- Prior art keywords
- intermediate compound
- fluorescent probe
- copper
- zinc ions
- reaction
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D473/00—Heterocyclic compounds containing purine ring systems
- C07D473/26—Heterocyclic compounds containing purine ring systems with an oxygen, sulphur, or nitrogen atom directly attached in position 2 or 6, but not in both
- C07D473/32—Nitrogen atom
- C07D473/34—Nitrogen atom attached in position 6, e.g. adenine
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
- C09K11/06—Luminescent, e.g. electroluminescent, chemiluminescent materials containing organic luminescent materials
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
- G01N21/62—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light
- G01N21/63—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light optically excited
- G01N21/64—Fluorescence; Phosphorescence
- G01N21/6428—Measuring fluorescence of fluorescent products of reactions or of fluorochrome labelled reactive substances, e.g. measuring quenching effects, using measuring "optrodes"
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
- C09K2211/10—Non-macromolecular compounds
- C09K2211/1018—Heterocyclic compounds
- C09K2211/1025—Heterocyclic compounds characterised by ligands
- C09K2211/1074—Heterocyclic compounds characterised by ligands containing more than three nitrogen atoms as heteroatoms
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
- C09K2211/10—Non-macromolecular compounds
- C09K2211/1018—Heterocyclic compounds
- C09K2211/1025—Heterocyclic compounds characterised by ligands
- C09K2211/1088—Heterocyclic compounds characterised by ligands containing oxygen as the only heteroatom
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Immunology (AREA)
- Physics & Mathematics (AREA)
- Life Sciences & Earth Sciences (AREA)
- Optics & Photonics (AREA)
- Nuclear Medicine, Radiotherapy & Molecular Imaging (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Analytical Chemistry (AREA)
- Biochemistry (AREA)
- General Health & Medical Sciences (AREA)
- General Physics & Mathematics (AREA)
- Pathology (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Investigating Or Analysing Materials By The Use Of Chemical Reactions (AREA)
Abstract
The invention discloses a dual-detection fluorescent probe for copper and zinc ions and a preparation method thereof, wherein the preparation method comprises the following steps: firstly, carrying out substitution reaction on 4, 6-dichloro-5-aminopyrimidine and 1-naphthylamine to obtain an intermediate compound II; then the intermediate compound II reacts with formic acid in an organic solvent to obtain an intermediate compound III with a purine ring; then the intermediate compound III reacts with a methanol solution of amine to obtain an intermediate compound IV; and finally, carrying out condensation reaction on the intermediate compound IV and chromone-3-formaldehyde to obtain the purine matrix-based fluorescent probe. The fluorescent probe has dual recognition on zinc ions and copper ions, has short response time, and can be used for detecting Zn in solution2+And Cu2+The fluorescent probe shows high sensitivity and high selectivity, and can also detect zinc ions and copper ions in a solid stateThe product has good portability and stability.
Description
Technical Field
The invention relates to a dual-detection fluorescent probe for copper and zinc ions and a preparation method of the dual-detection fluorescent probe.
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 is very interesting in the field of neurobiology, and plays an important role in enzymatic reaction and DNA synthesis in a biological system. However, excess Zn2+Can cause nervous system diseases such as epilepsy, Parkinson disease, ischemic stroke, infantile diarrhea and the like. Therefore, the method has important significance for the selective recognition and effective detection of the free zinc ions in the relevant research in the fields of chemistry, biology, clinical medicine, agriculture and the like.
Copper ion (Cu)2+) Is an indispensable metal element in organisms and plays a crucial role in the biochemistry of organisms, and most of copper ions in human bodies are combined with proteins, which are necessary metal elements for human metabolism. However, an imbalance in copper homeostasis can lead to inherited copper metabolism disorders. Therefore, the method has great significance for selective recognition and effective detection of free copper ions.
Currently, commonly used detection methods for zinc ions and copper ions include Atomic Absorption Spectroscopy (AAS), Atomic Emission Spectroscopy (AES), inductively coupled plasma mass probe, electrochemical methods, and the like, but these test methods are expensive, sample pretreatment is complicated, measurement time is relatively long, and professional operators are required.
Disclosure of Invention
The purpose of the invention is as follows: the invention aims to provide a fluorescent probe with high selectivity and high sensitivity to zinc ions and copper ions, and also aims to provide a preparation method of the fluorescent probe.
The technical scheme is as follows: the invention relates to a dual-detection fluorescent probe for copper and zinc ions, which has the following structural formula:
the preparation method of the dual-detection fluorescent probe for copper ions and zinc ions specifically comprises the following steps: firstly, carrying out substitution reaction on 4, 6-dichloro-5-aminopyrimidine and 1-naphthylamine to obtain an intermediate compound II; then the intermediate compound II and formic acid react in an organic solvent to obtain an intermediate compound III with a purine ring; then the intermediate compound III reacts with a methanol solution of amine to obtain an intermediate compound IV; and finally, carrying out condensation reaction on the intermediate compound IV and chromone-3-formaldehyde to obtain the purine matrix-based fluorescent probe.
Wherein the structural formula of the intermediate compound II is as follows:
the intermediate compound II is prepared by the following method: sequentially adding 4, 6-dichloro-5-aminopyrimidine and 1-naphthylamine into methanol, adding concentrated hydrochloric acid after dissolving, and refluxing and stirring; and after the reaction is completed, distilling under reduced pressure to remove the organic solvent, dissolving with NaOH, extracting with ethyl acetate, distilling under reduced pressure to remove ethyl acetate, recrystallizing with methanol and water, and drying to obtain an intermediate compound II.
Wherein the structural formula of the intermediate compound III is as follows:
the intermediate compound III is prepared by the following method: respectively dissolving the intermediate compound II, acetic acid, polyphosphoric acid and dodecyl trimethyl ammonium chloride in phosphorus oxychloride, and refluxing and stirring; after the reaction is completed, cooling the reaction liquid to room temperature, distilling under reduced pressure to remove the solvent phosphorus oxychloride, adding an ice water mixture into the reaction system under the condition of an ice water bath, purifying and eluting by using MeOH/DCM (v/v,1/250) through a column chromatography method, and drying to obtain an intermediate compound III.
Wherein the structural formula of the intermediate compound IV is as follows:
wherein the intermediate compound IV is prepared by adopting the following method: dissolving the intermediate compound III in a methanol solution of amine, heating and stirring, cooling the reactant to room temperature after the reaction is completed, carrying out suction filtration, washing the solid with an organic solvent, and drying to obtain an intermediate compound IV.
The reaction route of the fluorescent probe of the invention is shown as follows:
when the probe is complexed with different metal ions, the change of fluorescence intensity is different due to different binding sites. When Zn is added2+The increase in conjugation of the complex results in an increase in fluorescence intensity; when Cu is added2+In the process, ions are complexed with an imine structure, and the conjugation of the structure is destroyed, so that the fluorescence intensity is reduced. When other metal ions are added, the fluorescence intensity is not obviously changed from the fluorescence intensity of the probe, so that the fluorescent probe can not detect other metal ions, and the other metal ions basically have no interference on the detection of copper ions and zinc ions by the fluorescent probe.
The intermediate compound II and the intermediate compound III are products containing purine rings synthesized by taking pyrimidine as a basic raw material, and the compounds containing the purine rings take the purine rings as fluorescent luminescent groups, have planar rigid structures and contain rich nitrogen atoms and pi-pi conjugated systems on the one hand, so that the compounds can effectively perform coordination reaction with metal ions; and the purine ring-containing compound (intermediate compound III) reacts with amine to increase the connecting group of the amine, the hydrazone compound is an organic compound formed by condensing an amine compound and an aldehyde compound, the purine ring can be used as one end of the amine compound to condense with the aldehyde compound to form a larger conjugated system, the formed imine structure can increase the binding site with metal ions, and a larger space can be provided for accommodating the metal ions. Therefore, the hydrazone compound formed by taking the purine ring as the parent of the fluorescent probe and taking the Schiff base reaction as the basis can effectively improve the binding capacity of the fluorescent probe compound and metal ions, so that the detection lower limit value of the fluorescent probe compound on the metal ions is low.
Has the advantages that: the fluorescent probe can identify zinc ions with low concentration in the solution and copper ions with low concentration in the solution, and has short response time, thereby showing the effect of the fluorescent probe on Zn in the solution2+And Cu2+The fluorescence probe has high sensitivity and selectivity, and can detect zinc ions and copper ions in a solution in a solid state, so that the fluorescence probe has good portability and stability.
Drawings
FIG. 1 shows the fluorescent probe prepared in example 1 in DMSO-H2Zinc ion (Zn) in O (v/v ═ 9:1) solution2+) And copper ion (Cu)2+) Ultraviolet absorption spectrum of (2);
FIG. 2 shows the fluorescent probe prepared in example 1 in DMSO-H2Fluorescence spectra selective for different metal ions in O (v/v ═ 9:1) solution;
FIG. 3 shows fluorescent probes prepared in example 1 in DMSO-H2For different concentrations of zinc ion (Zn) in O (v/v ═ 9:1) solution2+) And copper ion (Cu)2+) A fluorescence spectral response map of (a);
FIG. 4 shows fluorescent probes prepared in example 1 in DMSO-H2A plot of the fluorescence response to selective interference detection of different ions in O (v/v ═ 9:1) solution;
FIG. 5 shows the fluorescent probe prepared in example 1 in DMSO-H2Neutralization of zinc ion (Zn) in O (v/v ═ 9:1) solution2+) And copper ion (Cu)2+) A Job-plot of the complex ratio;
FIG. 6 is a graph showing the change of fluorescence color when the probe strip prepared from the fluorescent probe prepared in example 1 detects zinc ions and copper ions with different concentrations;
FIG. 7 is a graph showing response times when zinc and copper ions are detected by the fluorescent probe prepared in example 1;
FIG. 8 is a MS spectrum of the fluorescent probe prepared in example 1;
FIG. 9 shows NMR of the fluorescent probe obtained in example 11H-NMR spectrum;
FIG. 10 shows NMR of the fluorescent probe obtained in example 113C-NMR spectrum.
Detailed Description
Example 1
The preparation method of the fluorescent probe for dual detection of copper ions and zinc ions comprises the following steps:
step (1), preparation of intermediate compound II: (6-chloro-N4- (naphthalen-1-yl) pyrimidine-4, 5-diamine)
Adding 50mL of methanol into a 100mL round-bottom flask, adding 4, 6-dichloro-5-aminopyrimidine (5.00g, 30mmol) and 1-naphthylamine (8.58g, 60mmol) into the flask, and adding 5mL of HCl with the concentration of 12mol/L into the flask after the materials are dissolved; the mixture was stirred under reflux at 65 ℃ for 5 days; after the reaction is completed, cooling, and then distilling under reduced pressure to remove the organic solvent methanol; dissolving all the obtained crude products in 50mL of 1M NaOH aqueous solution, extracting the mixture with ethyl acetate for 3 times, and distilling under reduced pressure to remove the ethyl acetate; washing the organic phase with 1.2M HCl, removing water with saturated saline solution, and drying to obtain a crude product; the crude product is substituted by CH3OH/H2Recrystallization from O (v/v, 1: 5) and drying afforded intermediate compound II as a pale purple solid powder (5.75g, 71% yield).
The structural formula of the obtained intermediate compound II is as follows:
intermediate compound II1H NMR(400MHz,DMSO-d6)δ8.92(s,1H),7.99–7.94(m,1H),7.92–7.87(m,1H),7.85–7.81(m,1H),7.63(s,1H),7.58–7.48(m,4H),5.52(s,2H).13C NMR(100MHz,DMSO-d6)δ151.62,145.58,138.88,135.45,134.42,129.88,128.59,126.47,126.33,126.17,126.15,124.96,123.97,123.69.
Step (2), preparation of intermediate compound iii: (6-chloro-9- (naphthalen-1-yl) -8-methyl-9H-purine)
The intermediate compound II (1.00g, 3.70mmol) obtained in step (1), acetic acid (1.11g, 18.50mmol) and DTAC (0.10g,10% mmol) in 25mL of POCl3Adding polyphosphoric acid (5.00g, 14.80mmol) into phosphorus oxychloride after the solid substances are completely dissolved; the reaction mixture was stirred at 80 ℃ under reflux for 72 hours; after the reaction is finished, cooling the reaction liquid to room temperature, and distilling under reduced pressure to remove the organic solvent to obtain brown oily matter; adding 100mL 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 the solvent was distilled off under reduced pressure and then dried to obtain intermediate compound III as a white solid (0.46g, yield 42%).
The structural formula of the obtained intermediate compound III is as follows:
intermediate compound III1H NMR(400MHz,DMSO-d6)1H NMR(400MHz,DMSO-d6)δ8.60(s,1H),8.26(m,J＝8.0,1.1Hz,1H),8.17(d,J＝8.2Hz,1H),7.83–7.73(m,2H),7.68–7.66(m,1H),7.54–7.52(m,1H),7.21(dd,J＝8.5,1.0Hz,1H),2.38(s,3H).13C NMR(101MHz,DMSO-d6)δ156.89,151.31,148.73,145.94,134.27,130.78,130.51,130.10,128.93,128.38,127.41,127.19,126.20,123.55,122.33,14.11.
Step (3), preparation of intermediate compound IV: (6-hydrazino-9- (naphthalen-1-yl) -8-methyl-9H-purine)
Dissolving the intermediate compound III (0.32g, 1.09mmol) obtained in the step (2) in 6mL of an amine in methanol; heating and stirring the mixed material at 65 ℃ for 3 hours; after the reaction is finished, cooling the mixture to room temperature, separating out solids, carrying out suction filtration, washing the solids for three times by using glacial methanol, and drying to obtain white powder (0.21g, yield 70%) which is an intermediate compound IV;
the structural formula of the obtained intermediate compound IV is as follows:
intermediate compound IV1H-NMR (400MHz, DMSO-d 6). delta.9.00 (s,2H), 8.20-8.19 (m,1H), 8.18-8.12 (m,1H),8.07(s,1H), 7.76-7.68 (m,2H), 7.65-7.63 (m,1H), 7.53-7.51 (m,1H), 7.06-7.64 (m,1H),2.24(s,3H).13C NMR(101MHz,DMSO-d6)δ156.86,155.05,151.87，148.05,134.34,131.03,130.98,130.02,129.81,129.02,128.53,127.56,127.44,126.27,122.34,14.11.
Step (4), preparing a fluorescent probe compound:
the intermediate compound IV (56mg, 0.2mmol) obtained in step (3) and chromone-3-carbaldehyde (37mg,0.3mmol) were dissolved in 2mL of ethanol under N2Under the protection, the mixture is refluxed and stirred for 2 hours at the temperature of 80 ℃; after completion of the reaction followed by plate spotting (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 dual fluorescent probe compound based on the purine matrix, wherein the fluorescent probe compound is white powder (60.4mg, 70%).
The structural formula of the obtained fluorescent probe compound is as follows:
fluorescent probe compounds of the invention1H NMR(400MHz,Chloroform-d)δ12.60(d,J＝11.5Hz,1H),8.58(d,J＝11.8Hz,1H),8.50(s,1H),8.10(dd,J＝7.8,1.7Hz,2H),8.01(t,J＝7.2Hz,1H),7.80–7.64(m,1H),7.57–7.44(m,3H),7.19–7.06(m,3H),5.81(d,J＝1.7Hz,1H),2.43(s,3H).
13C NMR(101MHz,Chloroform-d)δ182.72,160.63,156.33,154.70,153.49,152.39,148.07,135.12,134.59,130.66,130.17(d,J＝5.6Hz),128.71(d,J＝5.9Hz),128.05(d,J＝3.0Hz),127.13(d,J＝7.9Hz),126.94,126.31(d,J＝2.2Hz),125.57,122.81,122.30,121.79(d,J＝3.3Hz),120.76,118.62,118.15,108.24,101.75,14.45.
Practice ofMass spectrum MS spectrogram and nuclear magnetic resonance of fluorescent probe prepared in example 11H-NMR spectrum, nuclear magnetic resonance13The C-NMR spectra are shown in FIG. 8, FIG. 9 and FIG. 10, respectively, and illustrate the successful synthesis of the fluorescent probe of the present invention.
Example 2
The fluorescent probe prepared in example 1 was prepared as a 1mM stock solution in DMSO (dimethyl sulfoxide), each metal ion was prepared as a 3mM stock solution in deionized water, and 3mL of a blank DMSO-H solution was added2Adding 30 mu L of probe stock solution and 50 mu L of metal ion stock solution into O (v/v is 9:1), detecting by using a fluorescence spectrometer and an ultraviolet spectrophotometer, and testing to obtain that the maximum excitation wavelength of the fluorescence probe is 388nm and the maximum emission wavelength is 468nm, wherein the specific test results are as follows:
taking two cuvettes, adding 3mL of blank solution DMSO-H into each cuvette2O (v/v ═ 9:1) and 30 μ L of the probe stock solutions, 50 μ L of the zinc ion or copper ion stock solution was added to one of the cuvettes, and the other cuvette was not added with the zinc ion or copper ion stock solution, and the uv spectrum test was performed. As shown in fig. 1, the fluorescent probe compound itself has strong ultraviolet absorption at a wavelength λ of 375nm, and when zinc ions are added to the solution, the ultraviolet absorption peak gradually decreases, and when copper ions are added to the solution, the ultraviolet absorption peak is red-shifted, and thus, strong ultraviolet absorption at a wavelength λ of 446nm occurs. The result shows that the fluorescent probe of the invention is directed to Zn2+And Cu2+All have high sensitivity (probe to Zn)2+Detection limit of (2) was 23nM for Cu2+Has a detection limit of 154 nM).
FIG. 2 is a graph showing fluorescence spectra of fluorescent probes to which various metal ions were added. To 3mL of blank solution DMSO-H2The result of adding 30 mul of probe stock solution and 50 mul of various metal ion stock solution into O (v/v ═ 9:1) shows that the fluorescence color of the probe solution is changed from colorless to light yellow when zinc ions are added, the fluorescence intensity of the fluorescence spectrum at 468nm is obviously enhanced, the fluorescence color of the probe solution is changed from colorless to dark yellow when copper ions are added, and the fluorescence intensity of the fluorescence spectrum at 468nm is obviously enhancedAnd when other metal ions are added, the fluorescence color of the probe solution has no obvious change, which shows that the fluorescent probe has good selectivity on zinc ions and copper ions.
FIG. 3 shows fluorescent probes for different concentrations of Zinc ion (Zn)2+) And copper ion (Cu)2+) Fluorescence spectral response map of (a). To 3mL of blank solution DMSO-H2Adding 30 mu L of probe stock solution and 0-100 mu L of zinc ion or 0-50 mu L of copper ion solution (3mM of zinc or copper ion stock solution) into O (v/v ═ 9:1), wherein the fluorescent probe is colorless in a blank solution, but the fluorescence is continuously enhanced at 468nm along with the increase of the concentration of zinc ions, which shows that the fluorescence intensity is increased along with the increase of the concentration of zinc ions; the fluorescence also decreased continuously at 468nm with increasing copper ion concentration, indicating that the fluorescence intensity decreased with increasing copper ion concentration.
FIG. 4 is a bar graph of fluorescence intensity of fluorescent probes after reaction with zinc ions or copper ions in the presence of different interfering metal ions. To 3mL of 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+And Fe3+) Stock solution, to which 50. mu. LZn was added2+Or Cu2+Stock solutions were tested for fluorescence intensity. The results show that Cr3+、Fe3+And Al3+Has certain influence on the fluorescent probe, and the existence of other metal ions has no obvious interference on the fluorescent probe compound for identifying zinc ions and copper ions.
Probes with Zn were studied by the Job's plot method2+And Cu2+Binding rate of (2), to 3mL of blank solution DMSO-H2Adding a certain volume of probe stock solution and Zn into O (v/v ═ 9:1)2+Or Cu2+Stock solution (3mM) was prepared so that the sum of the concentrations of the fluorescent probe and zinc ion or copper ion was 50. mu.M, by changing the concentration ratio of the fluorescent probe and zinc ion or copper ion species (amount of fluorescent probe and zinc ion or copper ion species)The ratio of the above-mentioned two components is 1: 9, 2: 8, 3: 7, 4: 6, 5: 5, 6: 4, 7: 3, 8: 2, 9:1) in this order, the difference between the fluorescence intensity at 468nm and the fluorescence intensity of the fluorescence probe at that concentration (zinc ion detection) is obtained, and the copper ion detection is carried out by obtaining the difference between the ultraviolet intensity at 446nm and the ultraviolet intensity of the probe at that concentration and plotting the ratio of the ion to the total concentration. From this FIG. 5, it can be seen that when the ratio of zinc ions is 0.7, the ordinate reaches the maximum value, it can be determined that the fluorescent probe compound and zinc ions are mainly combined in a 1: 2 form to form a stable complex, and when the ratio of copper ions is 0.5, the ordinate reaches the maximum value, it can be determined that the fluorescent probe compound and copper ions are mainly combined in a 1: 1 form to form a stable complex.
As shown in fig. 6, the filter paper was immersed in the stock solution containing the fluorescent probe for half an hour, and then the test strip was taken out and dried in the air to obtain a dried test strip containing the probe. The test strips are respectively soaked in zinc ion or copper ion solutions with the concentrations of 0mM, 0.5mM and 1mM, the test strips are soaked for a few minutes and then dried, and quick color change strips shown in figure 6 are observed under a 365nm ultraviolet lamp, which shows that the probe can detect the zinc ions and the copper ions in a solid state.
As shown in FIG. 7, 3mL of blank buffer DMSO-H was added2O (v/v-9: 1) was added with 30. mu.L of the probe stock solution and 50. mu.L of Zn2+Or Cu2+The fluorescence intensity of the probe rapidly increases to the maximum or rapidly decreases to the minimum in the stock solution, and the fluorescence intensity gradually decreases and becomes stable within 10 minutes by adding zinc ions, which indicates that the probe has Zn resistance2+The detection is stable enough and the speed is high; when copper ions were added, the fluorescence intensity decreased and tended to be stable within 1 minute, indicating that the probe was resistant to Cu2+The detection is stable enough and fast.
Claims (8)
1. A dual-detection fluorescent probe for copper and zinc ions is characterized in that the structural formula of the fluorescent probe is as follows:
2. the method for preparing the fluorescent probe for dual detection of copper ions and zinc ions as claimed in claim 1 is characterized by comprising the following steps: firstly, carrying out substitution reaction on 4, 6-dichloro-5-aminopyrimidine and 1-naphthylamine to obtain an intermediate compound II; then the intermediate compound II reacts with formic acid in an organic solvent to obtain an intermediate compound III with a purine ring; then the intermediate compound III reacts with a methanol solution of amine to obtain an intermediate compound IV; and finally, carrying out condensation reaction on the intermediate compound IV and chromone-3-formaldehyde to obtain the purine matrix-based fluorescent probe.
3. The method for preparing the fluorescent probe for dual detection of copper and zinc ions according to claim 2, wherein the structural formula of the intermediate compound II is as follows:
4. the method for preparing the fluorescent probe for dual detection of copper and zinc ions according to claim 3, wherein the intermediate compound II is prepared by the following method: sequentially adding 4, 6-dichloro-5-aminopyrimidine and 1-naphthylamine into methanol, adding concentrated hydrochloric acid after dissolving, and refluxing and stirring; and after the reaction is completed, distilling under reduced pressure to remove the organic solvent, dissolving with NaOH, extracting with ethyl acetate, distilling under reduced pressure to remove ethyl acetate, recrystallizing with methanol and water, and drying to obtain an intermediate compound II.
5. The method for preparing the fluorescent probe for dual detection of copper and zinc ions according to claim 2, wherein the structural formula of the intermediate compound III is as follows:
6. the method for preparing the fluorescent probe for dual detection of copper and zinc ions according to claim 5, wherein the intermediate compound III is prepared by the following method: respectively dissolving an intermediate compound II, acetic acid, polyphosphoric acid and dodecyl trimethyl ammonium chloride in phosphorus oxychloride, and refluxing and stirring; and after the reaction is completed, cooling the reaction liquid to room temperature, carrying out reduced pressure distillation to remove the organic solvent, adding an ice-water mixture into the reaction system under the condition of ice-water bath, purifying, eluting and drying to obtain an intermediate compound III.
7. The method for preparing the fluorescent probe for dual detection of copper and zinc ions according to claim 2, wherein the structural formula of the intermediate compound IV is:
8. the method for preparing the fluorescent probe for dual detection of copper and zinc ions according to claim 7, wherein the intermediate compound IV is prepared by the following method: dissolving the intermediate compound III in a methanol solution of amine, heating and stirring, cooling the reactant to room temperature after the reaction is completed, carrying out suction filtration, washing the solid with an organic solvent, and drying to obtain an intermediate compound IV.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210231486.4A CN114773343A (en) | 2022-03-09 | 2022-03-09 | Copper and zinc ion dual-detection fluorescent probe and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210231486.4A CN114773343A (en) | 2022-03-09 | 2022-03-09 | Copper and zinc ion dual-detection fluorescent probe and preparation method thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN114773343A true CN114773343A (en) | 2022-07-22 |
Family
ID=82423465
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202210231486.4A Pending CN114773343A (en) | 2022-03-09 | 2022-03-09 | Copper and zinc ion dual-detection fluorescent probe and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN114773343A (en) |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| CN113512041A (en) * | 2021-08-13 | 2021-10-19 | 坛墨质检科技股份有限公司 | Purine matrix-based zinc ion detection fluorescent probe and preparation method and application thereof |
-
2022
- 2022-03-09 CN CN202210231486.4A patent/CN114773343A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| CN113512041A (en) * | 2021-08-13 | 2021-10-19 | 坛墨质检科技股份有限公司 | Purine matrix-based zinc ion detection fluorescent probe and preparation method and application thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Zhao et al. | Two ‘turn-off’Schiff base fluorescence sensors based on phenanthro [9, 10-d] imidazole-coumarin derivatives for Fe3+ in aqueous solution | |
| CN109678891B (en) | Palladium ion fluorescent probe compound and preparation method and application thereof | |
| CN109897041B (en) | Near-infrared zinc ion fluorescent probe compound and preparation method and application thereof | |
| CN112321588B (en) | Purine matrix-based zinc ion detection fluorescent probe and preparation method and application thereof | |
| CN113501822B (en) | Purine-vanillin-based palladium and copper ion detection fluorescent probe and preparation method and application thereof | |
| WO2023093399A1 (en) | Benzothiazole-parent-based fluorescent probe for detection of palladium ions, and preparation method therefor and use thereof | |
| CN108640867B (en) | Fluorescent probe compound containing cyano-carbazolyl Schiff base as well as preparation method and application thereof | |
| CN113512041A (en) | Purine matrix-based zinc ion detection fluorescent probe and preparation method and application thereof | |
| CN109206351B (en) | Cyanine structure based near-infrared fluorescent probe for detecting palladium ions, and preparation method and application thereof | |
| CN108484479B (en) | Carbazolyl two-photon fluorescent probe and preparation method and application thereof | |
| CN112094270B (en) | Purine parent-based cadmium ion detection fluorescent probe and preparation method and application thereof | |
| CN110627737B (en) | Water-soluble benzoxazole fluorescent probe for detecting zinc ions as well as preparation method and application thereof | |
| CN111533692A (en) | Fluorescent molecular probe for detecting mercury ions and preparation method and application thereof | |
| CN114736199B (en) | Methylene blue-based near-infrared fluorescent probe and synthetic method and application thereof | |
| CN114773343A (en) | Copper and zinc ion dual-detection fluorescent probe and preparation method thereof | |
| CN113024468B (en) | Fluorescent molecular probe for detecting picric acid and preparation method and application thereof | |
| CN112409261B (en) | Bifunctional fluorescent probe for detecting Pd concentration and pH value and preparation and application thereof | |
| CN111662279B (en) | Naphthalene-substituted carbazole-benzothiazolyl hydrazone compound and preparation method and application thereof | |
| CN113735858A (en) | Purine matrix-based aluminum ion detection fluorescent probe and preparation method and application thereof | |
| CN113861149A (en) | Fluorescent probe based on coumarin and p-bromobenzoyl hydrazine and preparation method thereof | |
| CN114957180A (en) | Fluorescent probe for identifying pH value based on dual-excitation-wavelength fluorescence analysis method and preparation method and application thereof | |
| CN114106018B (en) | Metal ion detection fluorescent probe based on purine parent, and preparation method and application thereof | |
| CN108191760B (en) | Fluorescent probe for detecting Cu (II) and preparation method and application thereof | |
| CN113980023B (en) | Compound PHA, preparation method thereof and application thereof in detection of copper ions | |
| CN114409646B (en) | Fluorescent probe for detecting copper ions and preparation method and application thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination |