CN114349753B - Fluorescent probe for detecting zinc ions and preparation method and application thereof - Google Patents
Fluorescent probe for detecting zinc ions and preparation method and application thereof Download PDFInfo
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- CN114349753B CN114349753B CN202111535418.9A CN202111535418A CN114349753B CN 114349753 B CN114349753 B CN 114349753B CN 202111535418 A CN202111535418 A CN 202111535418A CN 114349753 B CN114349753 B CN 114349753B
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- PTFCDOFLOPIGGS-UHFFFAOYSA-N Zinc dication Chemical compound [Zn+2] PTFCDOFLOPIGGS-UHFFFAOYSA-N 0.000 title claims abstract description 46
- 239000007850 fluorescent dye Substances 0.000 title claims abstract description 32
- 238000002360 preparation method Methods 0.000 title claims abstract description 9
- RGHHSNMVTDWUBI-UHFFFAOYSA-N 4-hydroxybenzaldehyde Chemical compound OC1=CC=C(C=O)C=C1 RGHHSNMVTDWUBI-UHFFFAOYSA-N 0.000 claims abstract description 14
- 238000001514 detection method Methods 0.000 claims abstract description 8
- 238000000034 method Methods 0.000 claims abstract description 7
- QOCWEEWOIWWTPH-UHFFFAOYSA-N B(O)(O)O.C1(=CC=CC=C1)C(=C(C1=CC=CC=C1)C1=CC=CC=C1)C1=CC=CC=C1 Chemical compound B(O)(O)O.C1(=CC=CC=C1)C(=C(C1=CC=CC=C1)C1=CC=CC=C1)C1=CC=CC=C1 QOCWEEWOIWWTPH-UHFFFAOYSA-N 0.000 claims abstract description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 10
- 239000000243 solution Substances 0.000 claims description 10
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 9
- 238000006243 chemical reaction Methods 0.000 claims description 8
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 6
- 230000005284 excitation Effects 0.000 claims description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 6
- USFZMSVCRYTOJT-UHFFFAOYSA-N Ammonium acetate Chemical compound N.CC(O)=O USFZMSVCRYTOJT-UHFFFAOYSA-N 0.000 claims description 5
- 239000005695 Ammonium acetate Substances 0.000 claims description 5
- 229940043376 ammonium acetate Drugs 0.000 claims description 5
- 235000019257 ammonium acetate Nutrition 0.000 claims description 5
- 229960000583 acetic acid Drugs 0.000 claims description 3
- 239000003054 catalyst Substances 0.000 claims description 3
- 239000012043 crude product Substances 0.000 claims description 3
- 238000010790 dilution Methods 0.000 claims description 3
- 239000012895 dilution Substances 0.000 claims description 3
- 238000001914 filtration Methods 0.000 claims description 3
- 239000012362 glacial acetic acid Substances 0.000 claims description 3
- 230000007935 neutral effect Effects 0.000 claims description 3
- NFHFRUOZVGFOOS-UHFFFAOYSA-N palladium;triphenylphosphane Chemical compound [Pd].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 NFHFRUOZVGFOOS-UHFFFAOYSA-N 0.000 claims description 3
- 239000000047 product Substances 0.000 claims description 3
- 239000002904 solvent Substances 0.000 claims description 3
- UGNPVAGAVUVKII-UHFFFAOYSA-N 2-hydroxy-4,4,5,5-tetraphenyl-1,3,2-dioxaborolane Chemical compound B1(OC(C(O1)(C2=CC=CC=C2)C3=CC=CC=C3)(C4=CC=CC=C4)C5=CC=CC=C5)O UGNPVAGAVUVKII-UHFFFAOYSA-N 0.000 claims description 2
- 238000001816 cooling Methods 0.000 claims description 2
- 239000011261 inert gas Substances 0.000 claims description 2
- 239000011259 mixed solution Substances 0.000 claims description 2
- 238000000967 suction filtration Methods 0.000 claims description 2
- 239000013067 intermediate product Substances 0.000 claims 3
- 150000001875 compounds Chemical class 0.000 abstract description 8
- 229940125904 compound 1 Drugs 0.000 abstract description 7
- 230000035945 sensitivity Effects 0.000 abstract description 5
- 238000001917 fluorescence detection Methods 0.000 abstract description 2
- 238000012360 testing method Methods 0.000 description 6
- 229910021645 metal ion Inorganic materials 0.000 description 4
- 230000008569 process Effects 0.000 description 3
- 239000011701 zinc Substances 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- -1 Cesium ions Chemical class 0.000 description 2
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- 238000003917 TEM image Methods 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- WLZRMCYVCSSEQC-UHFFFAOYSA-N cadmium(2+) Chemical compound [Cd+2] WLZRMCYVCSSEQC-UHFFFAOYSA-N 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- IDGUHHHQCWSQLU-UHFFFAOYSA-N ethanol;hydrate Chemical compound O.CCO IDGUHHHQCWSQLU-UHFFFAOYSA-N 0.000 description 2
- AICOOMRHRUFYCM-ZRRPKQBOSA-N oxazine, 1 Chemical compound C([C@@H]1[C@H](C(C[C@]2(C)[C@@H]([C@H](C)N(C)C)[C@H](O)C[C@]21C)=O)CC1=CC2)C[C@H]1[C@@]1(C)[C@H]2N=C(C(C)C)OC1 AICOOMRHRUFYCM-ZRRPKQBOSA-N 0.000 description 2
- 239000000523 sample Substances 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 238000004448 titration Methods 0.000 description 2
- 208000024827 Alzheimer disease Diseases 0.000 description 1
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- BHPQYMZQTOCNFJ-UHFFFAOYSA-N Calcium cation Chemical compound [Ca+2] BHPQYMZQTOCNFJ-UHFFFAOYSA-N 0.000 description 1
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 description 1
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 description 1
- VTLYFUHAOXGGBS-UHFFFAOYSA-N Fe3+ Chemical compound [Fe+3] VTLYFUHAOXGGBS-UHFFFAOYSA-N 0.000 description 1
- 208000032382 Ischaemic stroke Diseases 0.000 description 1
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 1
- JLVVSXFLKOJNIY-UHFFFAOYSA-N Magnesium ion Chemical compound [Mg+2] JLVVSXFLKOJNIY-UHFFFAOYSA-N 0.000 description 1
- WAEMQWOKJMHJLA-UHFFFAOYSA-N Manganese(2+) Chemical compound [Mn+2] WAEMQWOKJMHJLA-UHFFFAOYSA-N 0.000 description 1
- 206010034010 Parkinsonism Diseases 0.000 description 1
- NPYPAHLBTDXSSS-UHFFFAOYSA-N Potassium ion Chemical compound [K+] NPYPAHLBTDXSSS-UHFFFAOYSA-N 0.000 description 1
- 206010060862 Prostate cancer Diseases 0.000 description 1
- 208000000236 Prostatic Neoplasms Diseases 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- 235000011114 ammonium hydroxide Nutrition 0.000 description 1
- 206010002026 amyotrophic lateral sclerosis Diseases 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 229910001422 barium ion Inorganic materials 0.000 description 1
- 229910052792 caesium Inorganic materials 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 229910001424 calcium ion Inorganic materials 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000013522 chelant Substances 0.000 description 1
- 238000001311 chemical methods and process Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- 229910001430 chromium ion Inorganic materials 0.000 description 1
- 229910001429 cobalt ion Inorganic materials 0.000 description 1
- XLJKHNWPARRRJB-UHFFFAOYSA-N cobalt(2+) Chemical compound [Co+2] XLJKHNWPARRRJB-UHFFFAOYSA-N 0.000 description 1
- 239000011365 complex material Substances 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 229910001431 copper ion Inorganic materials 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 206010012601 diabetes mellitus Diseases 0.000 description 1
- 206010015037 epilepsy Diseases 0.000 description 1
- 229910001447 ferric ion Inorganic materials 0.000 description 1
- 229910001448 ferrous ion Inorganic materials 0.000 description 1
- 238000002189 fluorescence spectrum Methods 0.000 description 1
- 238000001727 in vivo Methods 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229910001416 lithium ion Inorganic materials 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 229910001425 magnesium ion Inorganic materials 0.000 description 1
- 239000011572 manganese Substances 0.000 description 1
- 229910001437 manganese ion Inorganic materials 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 229910001453 nickel ion Inorganic materials 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- KDLHZDBZIXYQEI-UHFFFAOYSA-N palladium Substances [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 1
- 230000036285 pathological change Effects 0.000 description 1
- 231100000915 pathological change Toxicity 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229910001414 potassium ion Inorganic materials 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000011540 sensing material Substances 0.000 description 1
- 239000000741 silica gel Substances 0.000 description 1
- 229910002027 silica gel Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910001415 sodium ion Inorganic materials 0.000 description 1
- 239000012086 standard solution Substances 0.000 description 1
- 239000012085 test solution Substances 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- 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
- C07D471/12—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 three hetero rings
- C07D471/14—Ortho-condensed systems
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D519/00—Heterocyclic compounds containing more than one system of two or more relevant hetero rings condensed among themselves or condensed with a common carbocyclic ring system not provided for in groups C07D453/00 or C07D455/00
-
- 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
-
- 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"
- G01N2021/6439—Measuring fluorescence of fluorescent products of reactions or of fluorochrome labelled reactive substances, e.g. measuring quenching effects, using measuring "optrodes" with indicators, stains, dyes, tags, labels, marks
Abstract
The invention belongs to the technical field of fluorescent probes, and particularly relates to a fluorescent probe for detecting zinc ions, and a preparation method and application thereof. The method comprises the following steps: 1) 3,8 dibromo-10-phenanthroline-5, 6-diketone reacts with p-hydroxybenzaldehyde to obtain a compound 1; 2) And (3) reacting the compound 1 obtained in the step (1) with tetraphenyl ethylene borate to obtain a fluorescent probe compound P for detecting zinc ions. The fluorescent probe provided by the invention realizes fluorescence detection of zinc ions by fluorescence enhancement and blue shift, and has the advantages of high selectivity, high sensitivity, wide detection concentration range, good biological safety, low cost, simplicity in operation and the like.
Description
Technical Field
The invention belongs to the technical field of fluorescent probes, and particularly relates to a fluorescent probe for detecting zinc ions, and a preparation method and application thereof.
Background
The fluorescence identification method has the advantages of high sensitivity, good selectivity, simple and convenient operation, low cost, high sensitivity, capability of realizing in-vivo rapid in-situ on-line detection and the like.
Zinc is a transition metal element with the second content in human bodies, and related researches show that zinc ions participate in and actively regulate a plurality of physiological and chemical processes. Meanwhile, zinc ions are also closely related to the pathological change process of many organisms, and ischemic stroke, alzheimer's disease, amyotrophic lateral sclerosis, parkinson's syndrome, epilepsy, diabetes, prostate cancer and the like. Therefore, the development of the simple and sensitive fluorescent sensing material has practical significance and important application value for qualitative identification and quantitative detection of zinc ions.
Many probes capable of detecting zinc ions have been reported, but few are fluorescence-enhanced probes capable of detecting in aqueous solutions and free from interference by other metal ions, particularly cadmium ions.
Disclosure of Invention
In order to solve the defects in the prior art, the invention provides a fluorescent probe for detecting zinc ions, and a preparation method and application thereof.
The technical scheme provided by the invention is as follows:
a fluorescent probe for detecting zinc ions has the following structural formula:
wherein n is 2-10.
The fluorescent probe provided by the invention realizes fluorescence detection of zinc ions by fluorescence enhancement and blue shift, and has the advantages of high selectivity, high sensitivity, wide detection concentration range, good biological safety, low cost, simplicity in operation and the like.
The fluorescent probe designed by the technical scheme of the invention can realize the identification of zinc ions in a single system and the selective identification of zinc ions in a complex metal ion system.
The invention also provides a preparation scheme of the fluorescent probe for detecting zinc ions, which comprises the following steps:
1) 3,8 dibromo-10-phenanthroline-5, 6-diketone reacts with p-hydroxybenzaldehyde to obtain a compound 1, and the structural formula is as follows:
2) And (3) reacting the compound 1 obtained in the step (1) with tetraphenyl ethylene borate to obtain a fluorescent probe compound P for detecting zinc ions.
The step 1) comprises the following steps: dissolving 3,8 dibromo-10-phenanthroline-5, 6-diketone, ammonium acetate and p-hydroxybenzaldehyde in glacial acetic acid, keeping the temperature of 70-90 ℃ for 2-4 hours, then raising the temperature to 115-130 ℃ for 2-4 hours, stopping the reaction, adding water for dilution, adjusting the pH value to be neutral, filtering, and separating and purifying the obtained crude product by using a column to obtain the compound 1.
Specifically, in the step 1):
the molar usage ratio of the 3,8 dibromo-10-phenanthroline-5, 6-diketone to the ammonium acetate is as follows: 1 (25-35);
the molar usage ratio of the 3,8 dibromo-10-phenanthroline-5, 6-diketone to the p-hydroxybenzaldehyde is as follows: 1: (0.8-1.5).
The step of the step 2) comprises the following steps: dissolving the compound 1 and tetraphenyl ethylene borate prepared in the step 1) in DMF, and sequentially adding a catalyst Pd [ P (C) 6 H 5 ) 3 ] 4 、K 2 CO 3 And (3) keeping the temperature of the solution at 120-140 ℃ under the protection of inert gas, reacting for 18-36h, cooling to room temperature after the reaction is finished, adding acetonitrile into the solution, and carrying out suction filtration to obtain the fluorescent probe compound P for detecting zinc ions.
Specifically, in the step 2), the molar ratio of the compound 1 to the tetraphenylethylene borate is as follows: 1: (1-1.2).
A specific synthetic route of the invention is as follows:
the invention also provides application of the fluorescent probe for detecting zinc ions, which is used as a zinc ion fluorescent probe.
Specific:
the solvent of the detection system is a mixed solution of water and ethanol;
the excitation wavelength is 310nm;
excitation light slit 10nm;
an emission light slit of 10nm;
the concentration of the fluorescent probe for detecting zinc ions is not lower than 1 mu M;
the detection limit of zinc ions is 2.3X10 -8 mol/L。
The fluorescent probe provided by the technical scheme of the invention has the advantages of good stability, low cost, no need of complex synthesis process and expensive instrument, and effectively solves the problems of high cost, low stability and complex material synthesis process in the prior art.
Drawings
FIG. 1 is a diagram of the addition of Compound PFluorescence change curves of different metal ions, excitation wavelength: 310nm, slit: (10 nm/10 nm); solvent: v (V) (Water) /V (ethanol) ＝1/1。
FIG. 2 is a graph showing the fluorescence concentration titration of a compound P with respect to zinc ions, wherein the concentration of the fluorescent probe P is 1. Mu.M, the concentration of zinc ions is 0-10. Mu.M in sequence, the excitation wavelength is 310nm, the slit width is 10nm/10nm, the abscissa is the wavelength, and the ordinate is the relative fluorescence intensity.
FIG. 3 is a diagram of P and P-Zn 2+ Wherein the left side is a TEM image of P and the right side is P-Zn 2+ Is a TEM image of (1).
Detailed Description
The principles and features of the present invention are described below with examples only to illustrate the present invention and not to limit the scope of the present invention.
Example 1
A preparation method of a fluorescent probe for detecting zinc ions comprises the following steps:
(1) 3,8 dibromo-10-phenanthroline-5, 6-dione (0.75 g,2.0475 mmol), ammonium acetate (2.3625 g,60 mmol) and p-hydroxybenzaldehyde (0.2497 g,2.0475 mmol) are taken and dissolved in glacial acetic acid (26.25 ml), the reaction is carried out for two hours at 90 ℃, then the temperature is increased to 120 ℃, water (200 ml) is added for dilution after the reaction is stopped, the pH is regulated to be neutral by using strong ammonia water, and then filtration is carried out, and the obtained crude product is purified by a silica gel chromatographic column (the developing agent is ethanol: dimethyl sulfoxide=40:1) to obtain the compound 1.
(2) Dissolving compound 1 (0.1753 g,0.3 mmol) and tetraphenyl ethylene borate (0.1410 g,0.3 mmol) prepared in step (1) in DMF (10 ml), and sequentially adding catalyst tetra (triphenylphosphine) palladium (4 mg), 2M K 2 CO 3 (2 ml) solution, the temperature was kept at 120℃under nitrogen protection, and the reaction was continued for 36h. After the reaction, the mixture was cooled to room temperature, poured into acetonitrile (200 mL), and filtered to obtain the target product P.
Example 2
Ion selectivity of the target product was tested as shown in figure 1. P and metal ions are respectively added into water-ethanol solution (1:1, v/v), and the concentration of P in the liquid to be detected is 1 multiplied by 10 -6 mol/L, 5 times equivalent of sodium ion (Na + ) Magnesium ions (Mg) 2 + ) Calcium ion (Ca) 2+ ) Cadmium ion (Cd) 2+ ) Chromium ion (Cr) 2+ ) Lithium ion (Li) + ) Barium ion (Ba) 2+ ) Manganese ion (Mn) 2+ ) Potassium ion (K) + ) Ferrous ions (Fe) 2+ ) Ferric ion (Fe) 3+ ) Cobalt ion (Co) 2+ ) Nickel ion (Ni) 2+ ) Copper ion (Cu) 2+ ) Cesium ions (Sr) 2+ ) Aluminum ion (Al) 2+ ). It can be seen from the figure that the emission peak of the system is not substantially changed except for zinc ions, and that the fluorescence intensity is significantly enhanced (about 15 times) with significant blue shift after zinc ions are added. The fluorescent probe P has better fluorescence selective recognition capability on zinc ions.
Example 3
Fluorescence titration of zinc ions by the target compound as shown in FIG. 2. P is dissolved in ethanol to a concentration of 1X 10 -6 And (3) a mol/L standard solution, then dropwise adding a zinc ion solution with the mol ratio of 0-10eq, and testing the fluorescence spectrum at room temperature. From the test results, it was found that the fluorescence emission peak was significantly enhanced and blue shifted after the addition of 0.001 times equivalent of zinc ion. And the fluorescence emission intensity is also enhanced along with the increase of the concentration of zinc ions in the test system. This indicates that the fluorescent probe P has higher sensitivity to recognition of zinc ions.
Example 4
TEM contrast of the target compound and zinc ion added to the target compound is shown in FIG. 3. P was added to a water-ethanol solution (1:1, v/v) to give a concentration of P in the test solution of 1X 10 -6 TEM testing was performed on mol/L. Then 10eq of zinc ion solution was added to the solution to be tested and then subjected to TEM testing. The test results show that polymer P is a complete agglomerate that is uniformly dispersed into approximately spherical nanoparticles after the addition of zinc ions. This demonstrates that the fluorescent probe P can quickly form a chelate with zinc ions after the addition.
The foregoing description of the preferred embodiments of the invention is not intended to limit the invention to the precise form disclosed, and any such modifications, equivalents, and alternatives falling within the spirit and scope of the invention are intended to be included within the scope of the invention.
Claims (6)
1. The preparation method of the fluorescent probe for detecting zinc ions is characterized by comprising the following steps of:
the step 1) comprises the following steps: dissolving 3,8 dibromo-10-phenanthroline-5, 6-diketone, ammonium acetate and p-hydroxybenzaldehyde in glacial acetic acid, keeping the temperature of 70-90 ℃ for 2-4 hours, then raising the temperature to 115-130 ℃ for 2-4 hours, stopping the reaction, adding water for dilution, adjusting the pH value to be neutral, filtering, and separating and purifying the obtained crude product by using a column to obtain an intermediate product;
the step of the step 2) comprises the following steps: dissolving the intermediate product prepared in the step 1) and tetraphenyl ethylene borate in DMF, and sequentially adding catalysts of tetrakis (triphenylphosphine) palladium and K 2 CO 3 And (3) keeping the temperature of the solution at 120-140 ℃ under the protection of inert gas, reacting for 18-36h, cooling to room temperature after the reaction is finished, adding acetonitrile into the solution, and carrying out suction filtration to obtain a fluorescent probe product for detecting zinc ions.
2. The method for preparing a fluorescent probe for detecting zinc ions according to claim 1, wherein in the step 1):
the molar usage ratio of the 3,8 dibromo-10-phenanthroline-5, 6-diketone to the ammonium acetate is as follows: 1 (25-35);
the molar usage ratio of the 3,8 dibromo-10-phenanthroline-5, 6-diketone to the p-hydroxybenzaldehyde is as follows: 1: (0.8-1.5).
3. The method for preparing a fluorescent probe for detecting zinc ions according to claim 1, wherein in the step 2), the molar ratio of the intermediate product to the tetraphenylethylene borate is as follows: 1: (0.9-1.1).
4. A fluorescent probe for detecting zinc ions prepared by the preparation method according to any one of claims 1 to 3.
5. Use of a fluorescent probe for detecting zinc ions according to claim 4, characterized in that: as a zinc ion fluorescent probe.
6. The use according to claim 5, characterized in that:
the solvent of the detection system is a mixed solution of water and ethanol;
the excitation wavelength is 310nm;
excitation light slit 10nm;
an emission light slit of 10nm;
the concentration of the fluorescent probe for detecting zinc ions is not lower than 1 mu M;
the detection limit of zinc ions is 2.3X10 -8 mol/L。
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202111535418.9A CN114349753B (en) | 2021-12-15 | 2021-12-15 | Fluorescent probe for detecting zinc ions and preparation method and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202111535418.9A CN114349753B (en) | 2021-12-15 | 2021-12-15 | Fluorescent probe for detecting zinc ions and preparation method and application thereof |
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