CN108440441B - AIE fluorescent probe molecule and method for detecting p-nitroaniline and fluorine ions - Google Patents
AIE fluorescent probe molecule and method for detecting p-nitroaniline and fluorine ions Download PDFInfo
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- 239000007850 fluorescent dye Substances 0.000 title claims abstract description 76
- TYMLOMAKGOJONV-UHFFFAOYSA-N 4-nitroaniline Chemical compound NC1=CC=C([N+]([O-])=O)C=C1 TYMLOMAKGOJONV-UHFFFAOYSA-N 0.000 title claims abstract description 38
- -1 fluorine ions Chemical class 0.000 title claims abstract description 22
- 238000000034 method Methods 0.000 title claims abstract description 21
- 229910052731 fluorine Inorganic materials 0.000 title claims abstract description 17
- 239000011737 fluorine Substances 0.000 title claims abstract description 17
- 230000000694 effects Effects 0.000 claims abstract description 16
- 239000000243 solution Substances 0.000 claims description 41
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 40
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 38
- NROKBHXJSPEDAR-UHFFFAOYSA-M potassium fluoride Chemical compound [F-].[K+] NROKBHXJSPEDAR-UHFFFAOYSA-M 0.000 claims description 36
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 28
- 239000007864 aqueous solution Substances 0.000 claims description 20
- 235000003270 potassium fluoride Nutrition 0.000 claims description 18
- 239000011698 potassium fluoride Substances 0.000 claims description 18
- 230000005284 excitation Effects 0.000 claims description 17
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 14
- 239000011259 mixed solution Substances 0.000 claims description 13
- 238000002189 fluorescence spectrum Methods 0.000 claims description 10
- 239000000523 sample Substances 0.000 claims description 10
- 230000008859 change Effects 0.000 claims description 9
- 150000001875 compounds Chemical class 0.000 claims description 6
- 238000002156 mixing Methods 0.000 claims description 6
- 229910001414 potassium ion Inorganic materials 0.000 claims description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 3
- 229910001415 sodium ion Inorganic materials 0.000 claims description 3
- 238000001228 spectrum Methods 0.000 claims description 3
- 125000003172 aldehyde group Chemical group 0.000 claims description 2
- LQNUZADURLCDLV-UHFFFAOYSA-N nitrobenzene Chemical compound [O-][N+](=O)C1=CC=CC=C1 LQNUZADURLCDLV-UHFFFAOYSA-N 0.000 claims description 2
- 230000002776 aggregation Effects 0.000 abstract description 9
- 238000004220 aggregation Methods 0.000 abstract description 9
- 230000000171 quenching effect Effects 0.000 abstract description 6
- 238000010791 quenching Methods 0.000 abstract description 5
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 abstract description 4
- KIWUVOGUEXMXSV-UHFFFAOYSA-N rhodanine Chemical compound O=C1CSC(=S)N1 KIWUVOGUEXMXSV-UHFFFAOYSA-N 0.000 abstract description 4
- OHUWRYQKKWKGKG-UHFFFAOYSA-N formaldehyde;pyrene Chemical compound O=C.C1=CC=C2C=CC3=CC=CC4=CC=C1C2=C43 OHUWRYQKKWKGKG-UHFFFAOYSA-N 0.000 abstract description 2
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 abstract description 2
- 239000002994 raw material Substances 0.000 abstract description 2
- 239000003054 catalyst Substances 0.000 abstract 1
- 238000001308 synthesis method Methods 0.000 abstract 1
- 239000012488 sample solution Substances 0.000 description 10
- 238000001514 detection method Methods 0.000 description 8
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 6
- 239000012046 mixed solvent Substances 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 4
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical class [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 description 4
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 description 4
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 4
- 238000004020 luminiscence type Methods 0.000 description 4
- 238000011160 research Methods 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 230000007246 mechanism Effects 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- 238000005160 1H NMR spectroscopy Methods 0.000 description 2
- MVVGSPCXHRFDDR-UHFFFAOYSA-N 2-(1,3-benzothiazol-2-yl)phenol Chemical class OC1=CC=CC=C1C1=NC2=CC=CC=C2S1 MVVGSPCXHRFDDR-UHFFFAOYSA-N 0.000 description 2
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 2
- 239000012496 blank sample Substances 0.000 description 2
- 238000012790 confirmation Methods 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 125000002485 formyl group Chemical group [H]C(*)=O 0.000 description 2
- 239000003208 petroleum Substances 0.000 description 2
- 239000001103 potassium chloride Substances 0.000 description 2
- 235000011164 potassium chloride Nutrition 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 238000010992 reflux Methods 0.000 description 2
- SMQUZDBALVYZAC-UHFFFAOYSA-N salicylaldehyde Chemical compound OC1=CC=CC=C1C=O SMQUZDBALVYZAC-UHFFFAOYSA-N 0.000 description 2
- 235000017550 sodium carbonate Nutrition 0.000 description 2
- 229910000029 sodium carbonate Inorganic materials 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- NWZSZGALRFJKBT-KNIFDHDWSA-N (2s)-2,6-diaminohexanoic acid;(2s)-2-hydroxybutanedioic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O.NCCCC[C@H](N)C(O)=O NWZSZGALRFJKBT-KNIFDHDWSA-N 0.000 description 1
- STOVYWBRBMYHPC-KAVGSWPWSA-N 2-[(E)-[(E)-(2-hydroxyphenyl)methylidenehydrazinylidene]methyl]phenol Chemical compound OC1=CC=CC=C1\C=N\N=C\C1=CC=CC=C1O STOVYWBRBMYHPC-KAVGSWPWSA-N 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 208000035967 Long Term Adverse Effects Diseases 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 230000002159 abnormal effect Effects 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 150000001299 aldehydes Chemical class 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- XJHABGPPCLHLLV-UHFFFAOYSA-N benzo[de]isoquinoline-1,3-dione Chemical class C1=CC(C(=O)NC2=O)=C3C2=CC=CC3=C1 XJHABGPPCLHLLV-UHFFFAOYSA-N 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- QKIUAMUSENSFQQ-UHFFFAOYSA-N dimethylazanide Chemical compound C[N-]C QKIUAMUSENSFQQ-UHFFFAOYSA-N 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 238000004043 dyeing Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 230000037406 food intake Effects 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 231100000086 high toxicity Toxicity 0.000 description 1
- IKDUDTNKRLTJSI-UHFFFAOYSA-N hydrazine monohydrate Substances O.NN IKDUDTNKRLTJSI-UHFFFAOYSA-N 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 239000005457 ice water Substances 0.000 description 1
- 230000005764 inhibitory process Effects 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012544 monitoring process Methods 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- OVARTBFNCCXQKS-UHFFFAOYSA-N propan-2-one;hydrate Chemical compound O.CC(C)=O OVARTBFNCCXQKS-UHFFFAOYSA-N 0.000 description 1
- 230000035945 sensitivity Effects 0.000 description 1
- 239000000741 silica gel Substances 0.000 description 1
- 229910002027 silica gel Inorganic materials 0.000 description 1
- 238000010898 silica gel chromatography Methods 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 238000012795 verification Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D277/00—Heterocyclic compounds containing 1,3-thiazole or hydrogenated 1,3-thiazole rings
- C07D277/02—Heterocyclic compounds containing 1,3-thiazole or hydrogenated 1,3-thiazole rings not condensed with other rings
- C07D277/20—Heterocyclic compounds containing 1,3-thiazole or hydrogenated 1,3-thiazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
- C07D277/32—Heterocyclic compounds containing 1,3-thiazole or hydrogenated 1,3-thiazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
- C07D277/36—Sulfur atoms
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- 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
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- 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"
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- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
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- C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
- C09K2211/10—Non-macromolecular compounds
- C09K2211/1003—Carbocyclic compounds
- C09K2211/1011—Condensed systems
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- 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
- C09K2211/1029—Heterocyclic compounds characterised by ligands containing one nitrogen atom as the heteroatom
- C09K2211/1037—Heterocyclic compounds characterised by ligands containing one nitrogen atom as the heteroatom with sulfur
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- 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"
- G01N2021/6432—Quenching
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Abstract
The invention relates to an AIE fluorescent probe molecule and a method for detecting p-nitroaniline and fluorine ions, which solves the technical problems of poor fluorescent probe identification capability and serious fluorescence quenching in the prior art. The invention obtains the 5-pyrenemethylene rhodanine by taking pyrene formaldehyde and rhodanine as raw materials and pyridine as a catalyst through a simple synthesis method. The molecule shows good aggregation-induced emission effect, and is a high-sensitivity fluorescent probe molecule for detecting p-nitroaniline and fluorine ions.
Description
Technical Field
The invention relates to the field of aggregation-induced emission effect and fluorescent probes, in particular to an AIE fluorescent probe molecule and a method for detecting p-nitroaniline and fluorine ions.
Background
Aggregation-induced emission (AIE) was first discovered in the subject group of Thanksgurni academy in 2001, and compared with the traditional fluorescent chromophore, which has the phenomenon that the fluorescence is reduced or even does not emit light at high concentration, the polymer greatly enhances the luminescence in an aggregated state or under a solid film, and the luminescence enhancement effect caused by aggregation is called aggregation-induced emission effect. Based on the recognition and research of the AIE phenomenon, a series of AIE substances are synthesized and made into high-efficiency light-emitting devices and chemical biosensors. As such, research into the mechanisms of the AIE phenomenon has also been extensively and extensively conducted, with the AIE mechanisms currently proposed including intramolecular rotational confinement (RIR), intramolecular coplanarity, inhibition of photochemical or photophysical processes, and the like. The abnormal light-emitting behavior arouses great interest of vast researchers at home and abroad, the research on the mechanism and the application of the AIE is more and more deep, and the light-emitting material with the AIE effect has wide application prospect in the fields of organic electroluminescent devices, chemical sensors, biological fluorescent probes and the like.
Para-nitroaniline is widely used in the dye industry for artificially synthesizing chemicals, is an intermediate of various printing and dyeing and pharmaceutical chemicals, and can also be used in analytical reagents. However, paranitroaniline has high toxicity, is toxic to inhalation, skin contact and ingestion, has an accumulative effect, is harmful to aquatic organisms, and may have long-term adverse effects on the water environment. Therefore, designing and preparing a suitable fluorescent probe is currently the most important research. However, p-nitroaniline has an obvious quenching effect on the fluorescent probe molecule in the invention, and the molecule in the invention is an effective fluorescent probe for detecting the p-nitroaniline.
In recent years, a molecular structure of a fluorine ion fluorescent probe is proposed to be various, for example: CN104449677A proposes a 2- (2-hydroxyphenyl) benzothiazole derivative, CN104610955A prepared ratio type fluorescent probe taking the 2- (2-hydroxyphenyl) benzothiazole derivative as a parent structure, and CN105985291A naphthalimide compounds which can be used as fluorine ion colorimetric fluorescent probe for detecting fluorine ions and CN106632450A prepared salicylaldehyde as a raw material, form salicylaldehyde azine with hydrazine hydrate, and then form the fluorine ion fluorescent probe through silicon protection. However, no fluorine ion fluorescent probe molecule with 5-pyrene methylene rhodanine as a matrix structure is found so far.
Disclosure of Invention
The invention aims to provide an AIE fluorescent probe molecule and a method for detecting p-nitroaniline and fluorine ions.
The technical purpose of the invention is realized by the following technical scheme:
an AIE fluorescent probe molecule characterized by: the structural formula of the compound is
Preferably, R is selected from hydrogen or an aldehyde group.
A method for detecting paranitroaniline by using AIE fluorescent probe molecules is characterized by comprising the following steps: the method comprises the following steps:
dissolving fluorescent probe molecules in water and acetone or water and tetrahydrofuran solution to obtain fluorescent probe molecule solution with AIE effect, mixing the fluorescent probe molecule solution with p-nitroaniline aqueous solution to be detected to obtain mixed solution, and detecting the concentration of p-nitrobenzene in the aqueous solution to be detected through the change of the fluorescence spectrum intensity of the probe molecules in the mixed solution, wherein the excitation wavelength is 300 nm.
Preferably, the volume ratio of water to acetone or water to tetrahydrofuran in the fluorescent probe molecular solution is 90: 10-60: 40; the concentration of the fluorescent probe molecules in the fluorescent probe molecule solution is 10-4mol/L。
Preferably, the volume ratio of water to acetone or water to tetrahydrofuran in the fluorescent probe molecule solution is 80: 20.
Preferably, the concentration of the paranitroaniline aqueous solution is 0.003 g/L-15 g/L.
A method for detecting fluorine ions by AIE fluorescent probe molecules is characterized in that: the method comprises the following steps:
dissolving fluorescent probe molecules in water and acetone or water and tetrahydrofuran solution to obtain fluorescent probe molecule solution with AIE effect, mixing the fluorescent probe molecule solution with potassium fluoride aqueous solution to be detected to obtain mixed solution, and detecting the concentration of potassium fluoride in the aqueous solution to be detected through the change of fluorescent spectrum intensity of the probe molecules in the mixed solution, wherein the excitation wavelength is 300 nm.
Preferably, the concentration of the fluorine ions in the potassium fluoride aqueous solution is 0.01 g/L-10 g/L.
Preferably, the concentrations of potassium ions, sodium ions and chloride ions in the potassium fluoride aqueous solution are respectively 0.11g/L to 10 g/L.
The invention has the beneficial effects that:
the invention introduces aggregation-induced emission effect (AIE) into the fluorescent probe, solves the limitation that the conventional fluorescent probe molecule needs good water solubility, has strong light stability, small influence of fluorescence on the environment, higher sensitivity and selectivity on p-nitroaniline and fluorine ions, simple and easy preparation method and good application prospect in environmental monitoring and biological systems.
Drawings
FIG. 1 shows the compound solution (10) of the fluorescent probe molecule of the present invention in the mixed solvent of water and acetone with different volume ratios-4M) a fluorescence spectrum (left) and a corresponding fluorescence intensity change curve (right) (the fluorescence excitation wavelength is 300 nm);
FIG. 2 shows the compound solution (10) of the fluorescent probe molecule of the present invention in the mixed solvent of water and acetone with different volume ratios-4M) a real object graph;
FIG. 3 shows the water/acetone mixed solvent compound solution (10) with different volume ratios under the excitation of 365nm ultraviolet lamp for fluorescent probe molecules of the present invention-4M) a real object graph;
FIG. 4 shows fluorescent probe molecules of the present invention against p-nitroaniline sample solutions (10) of different concentrations-4M) and the corresponding fluorescence intensity bar chart (right) (with 300nm as the fluorescence excitation wavelength);
FIG. 5 shows the p-nitroaniline sample solutions (10) with different concentrations of the fluorescent probe molecule of the invention under 365nm ultraviolet lamp-4M) a real object diagram;
FIG. 6 shows the fluorescent probe molecules of the present invention against different concentrations of potassium fluoride sample solutions (10)-4M) and the corresponding fluorescence intensity bar chart (right) (with 300nm as the fluorescence excitation wavelength);
FIG. 7 shows potassium fluoride sample solutions (10) of different concentrations of fluorescent probe molecules of the present invention under 365nm UV excitation-4M) excitation pattern under 365nm UV lamp;
FIG. 8 shows the fluorescent probe molecules of the present invention against potassium chloride sample solutions (10) of different concentrations-4M) and the corresponding fluorescence intensity bar chart (right) (with 300nm as the fluorescence excitation wavelength);
FIG. 9 shows the solution of the fluorescent probe molecule of the present invention in water/tetrahydrofuran mixed solvent compound (10) with different volume ratios- 4M) a fluorescence spectrum (left) and a corresponding fluorescence intensity change curve (right) (fluorescence excitation wavelength is 390 nm);
FIG. 10 shows fluorescent probe molecules of the present invention against p-nitroaniline samples of different concentrationsSolution (10)-4M) and the corresponding fluorescence intensity bar chart (right) (with 390nm as the fluorescence excitation wavelength);
FIG. 11 is the structural formula of the AIE fluorescent probe molecule capable of detecting p-nitroaniline and fluorine ions.
Detailed Description
The invention provides an AIE fluorescent probe molecule and a detection method for p-nitroaniline and fluorine ions;
the first embodiment is as follows:
1. the preparation method of the fluorescent probe molecule 5-pyrenemethylenerhodanine (R ═ H) comprises the following steps:
(1) adding 0.046g (0.2mmol) of pyrene formaldehyde, 0.0483g (0.3mmol) of rhodanine and 3 drops of acetic acid into a 50mL three-necked flask, and dissolving with 8mL of absolute ethanol;
(2) adding 3 drops of pyridine for catalysis, and carrying out reflux reaction at 80 ℃ for 3 hours;
(3) after cooling, TLC detection reaction is complete, the solution is orange, and orange-red crystals are separated out at the bottom after long-time placement;
(4) removing the solvent by reduced pressure distillation, and separating with silica gel column by using petroleum ether, dichloromethane and methanol at a ratio of 3:7:0.5 as mobile phase to obtain target product 5-pyrenemethylene rhodanine as orange red powder with a yield of about 76.2%.
The data for structural confirmation of the target product as an orange-red powder are as follows: 1H NMR (500MHz, CDCl3) delta 8.55-8.39 (m,1H), 8.35-7.94 (m,7H),7.26(s,2H), 4.39-4.19 (m,2H),1.25(s, 3H); the following molecular structural formula is as follows:
2. and (3) verifying the aggregation-induced emission (AIE) effect of the fluorescent probe molecules:
(1) the fluorescent probe molecule 5-pyrene methylene rhodanine is researched by the fluorescence of the 5-pyrene methylene rhodanine in different volume ratios of water and acetone, and the 5-pyrene methylene rhodanine is added by 10-4The concentration of M was dispersed in 10 groups of mixed solvents of water and acetone (volume ratio 0/100-90/10) and fluorescence excitation wavelength was 300nm, to obtain the fluorescence spectrum shown in FIG. 1(ii) a As can be seen from FIG. 1, the fluorescence spectrum shows a clear and regular change, and as the water is increased, the maximum absorption peak is gradually increased without moving, and reaches the maximum at a water-acetone ratio of 80/20. The fluorescence intensity of the sample increased from 17.64a.u (0%) to 878.9a.u (80%), and the luminescence intensity increased 49-fold.
(2) The sample solution of fluorescent probe molecule 5-pyrenemethylenerhodanine in water and acetone at the ratio of 10/90, 30/70, 60/40 and 80/20 is shown in FIG. 2; under the irradiation of a 365nm ultraviolet lamp, a sample solution with the water and acetone ratios of 20/80, 40/60, 80/20 and 90/10 is shown in figure 3, as is obvious from figure 2, the solution is from transparent light yellow to deepened color and finally to turbid solution, the molecular aggregation phenomenon occurs, the phenomenon in figure 3 is matched with a fluorescence spectrogram, the fluorescence is strongest at 80/20, and the fluorescent probe molecule is verified to have an AIE effect.
3. Fluorescent probe molecule for detecting p-nitroaniline
(1) Dissolving fluorescent probe molecules in water and acetone or water and tetrahydrofuran solution to obtain fluorescent probe molecule solution with AIE effect, mixing the fluorescent probe molecule solution with p-nitroaniline aqueous solution to be detected to obtain mixed solution, and detecting the concentration of the p-nitroaniline in the aqueous solution to be detected through the change of the fluorescence spectrum intensity of the probe molecules in the mixed solution, wherein the excitation wavelength is 300 nm; the concentration of the fluorescent probe molecule solution is 10-4mol/L, wherein the volume ratio of water to acetone or water to tetrahydrofuran is 80: 20; nine groups of p-nitroaniline aqueous solutions with different concentrations (the concentrations are respectively 0.03g/L, 0.05g/L, 0.1g/L, 0.5g/L, 1g/L, 1.5g/L, 2g/L, 3g/L and 15g/L) are prepared for reference comparison, as shown in FIG. 4, the results show that: as the concentration of paranitroaniline increased, the fluorescence intensity of the sample decreased dramatically, from 6223a.u (0g/L) to 51.29a.u., by a factor of 121. Therefore, the fluorescent molecule has good detection performance on paranitroaniline.
(2) When the blank sample solution with the concentrations of 0.5g/L, 5g/L and 10g/L and without adding p-nitroaniline is subjected to ultraviolet lamp irradiation, as shown in FIG. 5, it is obvious that: the sample solution added with the paranitroaniline almost becomes clear, the nano particles are reduced, the fluorescence intensity is sharply reduced, the obvious quenching phenomenon of the paranitroaniline on the fluorescent probe molecules is verified, and the method is well applied to the detection of the paranitroaniline.
4. Detection of fluorine ions by fluorescent probe molecules
(1) Dissolving fluorescent probe molecules in water and acetone or water and tetrahydrofuran solution to obtain fluorescent probe molecule solution with AIE effect, mixing the fluorescent probe molecule solution with potassium fluoride aqueous solution to be detected to obtain mixed solution, and detecting the concentration of potassium fluoride in the aqueous solution to be detected through the change of fluorescent spectrum intensity of the probe molecules in the mixed solution, wherein the excitation wavelength is 300 nm; the concentration of the fluorescent probe molecule solution is 10-4mol/L, wherein the volume ratio of water to acetone or water to tetrahydrofuran is 80: 20; seven groups of p-nitroaniline aqueous solutions with different concentrations (the concentrations are respectively 0.03g/L, 0.05g/L, 0.1g/L, 0.5g/L, 1g/L, 5g/L and 10g/L) are prepared for reference comparison, as shown in FIG. 6, the results show that: as the concentration of the sample solution to which potassium fluoride is added increases, the luminescence intensity decreases, and a fluorescence quenching phenomenon occurs.
(2) When potassium fluoride of 1g/L, 5g/L and 10g/L and a blank sample solution without potassium fluoride are subjected to ultraviolet lamp irradiation, as shown in FIG. 7, it can be seen that the sample solution with potassium fluoride added has a decrease in luminous intensity with an increase in concentration, which is theoretically consistent with data on a fluorescence spectrum.
(3) In order to verify that the ions causing the fluorescence quenching of the sample in the potassium fluoride are not potassium ions but fluorine ions, potassium chloride was added at concentrations of 0.1g/L, 1g/L and 10g/L, and the fluorescence intensity was measured by a fluorescence photometer using an excitation wavelength of 300nm, as shown in FIG. 8, which indicates that: potassium ions have little influence on the fluorescence intensity of the sample and have no obvious fluorescence quenching phenomenon; the concentrations of potassium ions, sodium ions and chloride ions in the potassium fluoride aqueous solution are respectively 0.11 g/L-10 g/L.
Example two
When R is replaced by amino or aldehyde, the rest conditions are the same as those in example 1, and the AIE fluorescent probe molecule capable of detecting fluorine ions can be prepared, and the result is similar to that in example 1.
EXAMPLE III
1. The preparation method of the fluorescent probe molecule (R ═ CHO) comprises the following steps:
(1) 1.4728g (4mmol) of 5-pyrenemethylenerhodanine and 6.2411g (85mmol) of N, N-dimethylamide from example 1 were added to a 100mL three-necked flask, and 3.2mL of OCl were slowly added dropwise over half an hour in an ice bath at 0 deg.C3Keeping the temperature at 0 ℃ for ice bath reaction for 1h, and then heating to 90-100 ℃ for reflux reaction for about 24 h;
(2) after the reaction solution is cooled, the TLC detection reaction is complete, and the solution is black;
(3) adding 3mL of ice water for hydrolysis; cooling to room temperature again, adjusting the pH value to 5-6 by using a concentrated Na2CO3 solution, extracting by using 3X 30mL of toluene, and taking a lower layer solution;
(4) washing with concentrated Na2CO3 solution and deionized water, distilling under reduced pressure to remove solvent, and separating by silica gel column chromatography with 3:2 petroleum ether and dichloromethane as mobile phase to obtain the target product with yield of about 65%.
The structure confirmation data of the target product are as follows: 1H NMR (500MHz, CDCl 3). delta.8.96 (s,1H), 8.64-7.86 (m,7H),7.26(s,2H), 4.54-3.28 (m,2H), 1.40-1.27 (m, 3H).
2. Verification of aggregation-induced emission (AIE) effect and p-nitroaniline detection by fluorescent probe molecule (R ═ CHO):
the method is the same as that of points 2 and 3 in example one, except that in a mixed solution of water and tetrahydrofuran, the fluorescence spectrum excitation wavelength is 390nm, and the fluorescence spectrum shown in FIG. 9 and the p-nitroaniline detection shown in FIG. 10 are respectively obtained. Conclusions were drawn on similar properties to the molecule of example one.
The present embodiment is only for explaining the present invention, and it is not limited to the present invention, and those skilled in the art can make modifications of the present embodiment without inventive contribution as needed after reading the present specification, but all of them are protected by patent law within the scope of the claims of the present invention.
Claims (8)
1. An AIE fluorescent probe molecule characterized by: the structural formula of the compound isAnd R is selected from aldehyde group.
2. A method for detecting paranitroaniline using the AIE fluorescent probe molecule of claim 1, characterized in that: the method comprises the following steps:
dissolving fluorescent probe molecules in water and acetone or water and tetrahydrofuran solution to obtain fluorescent probe molecule solution with AIE effect, mixing the fluorescent probe molecule solution with p-nitroaniline aqueous solution to be detected to obtain mixed solution, and detecting the concentration of p-nitrobenzene in the aqueous solution to be detected through the change of the fluorescence spectrum intensity of the probe molecules in the mixed solution, wherein the excitation wavelength is 300 nm.
3. The method for detecting p-nitroaniline according to claim 2, wherein: the volume ratio of water to acetone or water to tetrahydrofuran in the fluorescent probe molecular solution is 90: 10-60: 40; the concentration of the fluorescent probe molecules in the fluorescent probe molecule solution is 10-4mol/L。
4. The method for detecting p-nitroaniline according to claim 3, characterized in that: the volume ratio of water to acetone or water to tetrahydrofuran in the fluorescent probe molecular solution is 80: 20.
5. The method for detecting p-nitroaniline according to claim 2, wherein: the concentration of the paranitroaniline aqueous solution is 0.003 g/L-15 g/L.
6. A method for detecting fluoride ions using the AIE fluorescent probe molecule of claim 1, characterized in that: the method comprises the following steps:
dissolving fluorescent probe molecules in water and acetone or water and tetrahydrofuran solution to obtain fluorescent probe molecule solution with AIE effect, mixing the fluorescent probe molecule solution with potassium fluoride aqueous solution to be detected to obtain mixed solution, and detecting the concentration of potassium fluoride in the aqueous solution to be detected through the change of fluorescent spectrum intensity of the probe molecules in the mixed solution, wherein the excitation wavelength is 300 nm.
7. The method for detecting fluorine ions according to claim 6, wherein: the concentration of the fluorinion in the potassium fluoride water solution is 0.01 g/L-10 g/L.
8. The method for detecting fluorine ions according to claim 6, wherein: the concentrations of potassium ions, sodium ions and chloride ions in the potassium fluoride aqueous solution are respectively 0.11 g/L-10 g/L.
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