CN114958346B - Fluorescent viscosity probe with aggregation-induced emission and preparation method and application thereof - Google Patents
Fluorescent viscosity probe with aggregation-induced emission and preparation method and application thereof Download PDFInfo
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- 239000000523 sample Substances 0.000 title claims abstract description 53
- 230000002776 aggregation Effects 0.000 title claims abstract description 28
- 238000004220 aggregation Methods 0.000 title claims abstract description 28
- 238000002360 preparation method Methods 0.000 title abstract description 9
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims abstract description 18
- XCGLXUJEPIVZJM-UHFFFAOYSA-N 4-(4-methyl-n-(4-methylphenyl)anilino)benzaldehyde Chemical compound C1=CC(C)=CC=C1N(C=1C=CC(C=O)=CC=1)C1=CC=C(C)C=C1 XCGLXUJEPIVZJM-UHFFFAOYSA-N 0.000 claims abstract description 17
- 239000002904 solvent Substances 0.000 claims abstract description 16
- 239000011259 mixed solution Substances 0.000 claims abstract description 14
- NFPYJDZQOKCYIE-UHFFFAOYSA-N 4-amino-3-hydroxybenzoic acid Chemical compound NC1=CC=C(C(O)=O)C=C1O NFPYJDZQOKCYIE-UHFFFAOYSA-N 0.000 claims abstract description 13
- 238000000034 method Methods 0.000 claims abstract description 12
- 239000000203 mixture Substances 0.000 claims abstract description 12
- 229960000583 acetic acid Drugs 0.000 claims abstract description 9
- 239000012362 glacial acetic acid Substances 0.000 claims abstract description 9
- USFZMSVCRYTOJT-UHFFFAOYSA-N Ammonium acetate Chemical compound N.CC(O)=O USFZMSVCRYTOJT-UHFFFAOYSA-N 0.000 claims abstract description 8
- 239000005695 Ammonium acetate Substances 0.000 claims abstract description 8
- 229940043376 ammonium acetate Drugs 0.000 claims abstract description 8
- 235000019257 ammonium acetate Nutrition 0.000 claims abstract description 8
- 239000012065 filter cake Substances 0.000 claims abstract description 7
- 238000005406 washing Methods 0.000 claims abstract description 5
- 238000003756 stirring Methods 0.000 claims abstract description 4
- 238000001914 filtration Methods 0.000 claims abstract description 3
- 239000012467 final product Substances 0.000 claims abstract description 3
- 238000002156 mixing Methods 0.000 claims abstract description 3
- 239000000243 solution Substances 0.000 claims description 42
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical group CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 28
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 27
- 229910052782 aluminium Inorganic materials 0.000 claims description 18
- -1 aluminium ions Chemical class 0.000 claims description 18
- 238000001514 detection method Methods 0.000 claims description 11
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 4
- 239000002798 polar solvent Substances 0.000 claims description 4
- 125000003172 aldehyde group Chemical group 0.000 claims description 3
- 239000000376 reactant Substances 0.000 claims description 3
- 238000001953 recrystallisation Methods 0.000 claims description 2
- 239000004411 aluminium Substances 0.000 claims 1
- 230000008859 change Effects 0.000 abstract description 14
- 229910001385 heavy metal Inorganic materials 0.000 abstract description 7
- 230000004044 response Effects 0.000 abstract description 7
- 239000007788 liquid Substances 0.000 abstract description 4
- 238000004090 dissolution Methods 0.000 abstract description 2
- 150000002500 ions Chemical class 0.000 description 21
- 239000000047 product Substances 0.000 description 16
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 10
- 229910021645 metal ion Inorganic materials 0.000 description 9
- 239000007850 fluorescent dye Substances 0.000 description 8
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 7
- 238000006243 chemical reaction Methods 0.000 description 7
- RVPVRDXYQKGNMQ-UHFFFAOYSA-N lead(2+) Chemical compound [Pb+2] RVPVRDXYQKGNMQ-UHFFFAOYSA-N 0.000 description 7
- 150000001450 anions Chemical class 0.000 description 6
- 150000001768 cations Chemical class 0.000 description 6
- 239000000126 substance Substances 0.000 description 5
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 5
- 239000002262 Schiff base Substances 0.000 description 4
- 150000004753 Schiff bases Chemical class 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 238000000691 measurement method Methods 0.000 description 4
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 description 3
- JLVVSXFLKOJNIY-UHFFFAOYSA-N Magnesium ion Chemical compound [Mg+2] JLVVSXFLKOJNIY-UHFFFAOYSA-N 0.000 description 3
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 description 3
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 3
- 239000012490 blank solution Substances 0.000 description 3
- 229910001431 copper ion Inorganic materials 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 229910001425 magnesium ion Inorganic materials 0.000 description 3
- 230000003287 optical effect Effects 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
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- 229910001415 sodium ion Inorganic materials 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- HSJKGGMUJITCBW-UHFFFAOYSA-N 3-hydroxybutanal Chemical compound CC(O)CC=O HSJKGGMUJITCBW-UHFFFAOYSA-N 0.000 description 2
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-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
- 235000013361 beverage Nutrition 0.000 description 2
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 2
- 238000012512 characterization method Methods 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 208000012839 conversion disease Diseases 0.000 description 2
- JTRONPPAUSSTQI-UHFFFAOYSA-N ethane-1,2-diol;ethanol Chemical compound CCO.OCCO JTRONPPAUSSTQI-UHFFFAOYSA-N 0.000 description 2
- 239000012530 fluid Substances 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 2
- 238000011065 in-situ storage Methods 0.000 description 2
- 239000003446 ligand Substances 0.000 description 2
- 229910017604 nitric acid Inorganic materials 0.000 description 2
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- QAKMXYFDVPDIPT-UHFFFAOYSA-N 1,1,2,3,4,5-hexakis-phenylsilole Chemical compound C1=CC=CC=C1C(C(=C([Si]1(C=2C=CC=CC=2)C=2C=CC=CC=2)C=2C=CC=CC=2)C=2C=CC=CC=2)=C1C1=CC=CC=C1 QAKMXYFDVPDIPT-UHFFFAOYSA-N 0.000 description 1
- UJPKMTDFFUTLGM-UHFFFAOYSA-N 1-aminoethanol Chemical compound CC(N)O UJPKMTDFFUTLGM-UHFFFAOYSA-N 0.000 description 1
- 238000005160 1H NMR spectroscopy Methods 0.000 description 1
- 229920000858 Cyclodextrin Polymers 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 238000005481 NMR spectroscopy Methods 0.000 description 1
- 150000001299 aldehydes Chemical class 0.000 description 1
- 230000004075 alteration Effects 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- IZJSTXINDUKPRP-UHFFFAOYSA-N aluminum lead Chemical compound [Al].[Pb] IZJSTXINDUKPRP-UHFFFAOYSA-N 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000008280 blood Substances 0.000 description 1
- 210000004369 blood Anatomy 0.000 description 1
- VTJUKNSKBAOEHE-UHFFFAOYSA-N calixarene Chemical class COC(=O)COC1=C(CC=2C(=C(CC=3C(=C(C4)C=C(C=3)C(C)(C)C)OCC(=O)OC)C=C(C=2)C(C)(C)C)OCC(=O)OC)C=C(C(C)(C)C)C=C1CC1=C(OCC(=O)OC)C4=CC(C(C)(C)C)=C1 VTJUKNSKBAOEHE-UHFFFAOYSA-N 0.000 description 1
- 239000012295 chemical reaction liquid Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 150000003983 crown ethers Chemical class 0.000 description 1
- 229940097362 cyclodextrins Drugs 0.000 description 1
- 239000000412 dendrimer Substances 0.000 description 1
- 229920000736 dendritic polymer Polymers 0.000 description 1
- 230000001419 dependent effect Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000004896 high resolution mass spectrometry Methods 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 238000003384 imaging method Methods 0.000 description 1
- 150000002466 imines Chemical group 0.000 description 1
- 238000004020 luminiscence type Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000003068 molecular probe Substances 0.000 description 1
- VOFUROIFQGPCGE-UHFFFAOYSA-N nile red Chemical compound C1=CC=C2C3=NC4=CC=C(N(CC)CC)C=C4OC3=CC(=O)C2=C1 VOFUROIFQGPCGE-UHFFFAOYSA-N 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 238000010791 quenching Methods 0.000 description 1
- 230000000171 quenching effect Effects 0.000 description 1
- 238000007348 radical reaction Methods 0.000 description 1
- 238000011897 real-time detection Methods 0.000 description 1
- 230000027756 respiratory electron transport chain Effects 0.000 description 1
- 238000002390 rotary evaporation Methods 0.000 description 1
- 230000000087 stabilizing effect Effects 0.000 description 1
- PJANXHGTPQOBST-UHFFFAOYSA-N stilbene Chemical class C=1C=CC=CC=1C=CC1=CC=CC=C1 PJANXHGTPQOBST-UHFFFAOYSA-N 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- JLZUZNKTTIRERF-UHFFFAOYSA-N tetraphenylethylene Chemical group C1=CC=CC=C1C(C=1C=CC=CC=1)=C(C=1C=CC=CC=1)C1=CC=CC=C1 JLZUZNKTTIRERF-UHFFFAOYSA-N 0.000 description 1
- 125000005259 triarylamine group Chemical group 0.000 description 1
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- C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
- C09K11/06—Luminescent, e.g. electroluminescent, chemiluminescent materials containing organic luminescent materials
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C249/00—Preparation of compounds containing nitrogen atoms doubly-bound to a carbon skeleton
- C07C249/02—Preparation of compounds containing nitrogen atoms doubly-bound to a carbon skeleton of compounds containing imino groups
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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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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
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- 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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- Y02P20/00—Technologies relating to chemical industry
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Abstract
Fluorescent viscosity probes with aggregation-induced emission are disclosed. The probe has higher fluorescence signal response to liquid viscosity change and heavy metals. The invention also provides a preparation method of the fluorescent viscosity probe with aggregation-induced emission, which comprises the steps of mixing 4- (di-p-toluylamino) benzaldehyde and 4-amino-3-hydroxybenzoic acid to obtain a mixture, adding a solvent into the mixture for dissolution, then adding glacial acetic acid or ammonium acetate to form a mixed solution, stirring the mixed solution at 20-80 ℃ for 6-12h, filtering, washing a filter cake, and recrystallizing to obtain a final product. The method for preparing the probe is simple, efficient and high in yield.
Description
Technical Field
The invention belongs to the technical field of fluorescent probes, and particularly relates to a fluorescent viscosity probe with aggregation-induced emission property.
Background
Currently common viscosity measurement methods include capillary, ball drop, spin, and vibration methods. These measurement methods are dependent on the specific equipment, typically done in a laboratory, and require a certain amount of time and cost. The viscosity measurement method described above is generally not capable of detecting the viscosity of a fluid in a microenvironment such as a cell, due to limitations such as the size and volume of the apparatus. Therefore, the viscosity measurement method based on the fluorescent probe is receiving attention gradually due to the characteristics of high sensitivity, quick response, convenient operation, capability of performing in-situ detection in a small-volume sample, and the like.
Fluorescent probes generally have two properties: the first is optically active and the other is chemically active. Optical activity refers to the change in optical properties (e.g., intensity, wavelength, etc.) of a probe after it interacts with a substance to be measured. The chemical activity refers to the reaction (such as coordination, inclusion, bond breaking, radical reaction, etc.) that can occur between the active group of the probe and the substance to be detected.
The fluorescent molecular probe is established on the basis of the organic combination of a fluorescent group and a recognition group of the probe, the recognition of molecules is realized by obtaining information through the change of specific optical activity and chemical activity, and the molecular combination information is converted into a fluorescent signal which is easy to detect through a corresponding conducted fluorescent signal, so that the in-situ and real-time detection on the single molecule level is realized. Currently, more common recognition groups are cyclodextrins, crown ethers, calixarenes, dendrimers, schiff bases, and the like.
Fluorescent probes for viscosity detection typically feature molecular rotors, including nile red, boron-dipyrromethene (BODIPY) derivatives, stilbene derivatives, triarylamine series compounds, and the like.
Compared to these probe molecules, probe molecules having aggregation-induced emission (AIE) properties have a higher sensitivity. The AIE probe molecules have a very weak fluorescence intensity in solution, whereas the fluorescence intensity is significantly enhanced when the aggregates are formed or in a rigid environment. Studies have shown that the luminescent properties of AIE molecules are derived from an intramolecular restricted motion (RIM) mechanism. To date, AIE fluorescent probes have been used for viscosity detection, for example, document analysis, 2020,145,844-850 discloses the detection of viscosity of liquid beverages to determine whether they are spoiled; document chem. Res. Chinese Universities, DOI:2022,38,500-504 discloses visualizing viscosity and molecular weight changes during the imaging polymer preparation using AIE fluorescent probes;
although AIE probes have advantages in viscosity detection sensitivity, the existing main AIE molecular structures (hexaphenyl silole, tetraphenyl ethylene, etc.) have higher requirements on synthetic processes and correspondingly higher preparation costs.
Therefore, it is needed to design a convenient and low-cost process method for preparing an AIE probe, and the prepared AIE probe has high fluorescence signal response to viscosity change and heavy metals, and can realize independent or collaborative detection of multiple parameters.
Disclosure of Invention
The invention provides a fluorescent viscosity probe with aggregation-induced emission, which has higher fluorescent signal response to liquid viscosity change and heavy metals, and the method for preparing the probe is simple, efficient and high in yield.
A fluorescent viscosity probe with aggregation-induced emission, having the structural formula:
the invention also provides a preparation method of the fluorescent viscosity probe with aggregation-induced emission, which comprises the following steps:
mixing 4- (di-p-toluylamino) benzaldehyde and 4-amino-3-hydroxybenzoic acid to obtain a mixture, adding a solvent into the mixture for dissolution, then adding glacial acetic acid or ammonium acetate to form a mixed solution, stirring the mixed solution at 20-80 ℃ for 6-12h, filtering, washing a filter cake, and recrystallizing to obtain a final product.
The specific reaction route is as follows:
the fluorescent viscosity probe with Schiff base ligand is formed by condensing 4-amino-3-hydroxybenzoic acid and 4- (di-p-toluylamino) benzaldehyde through aldehyde ammonia, wherein hydroxyl and carboxyl provided by the 4-amino-3-hydroxybenzoic acid can react with aluminum metal and lead to form coordination, so that aggregation is formed between molecules of the probe, the intramolecular movement is limited (wherein when the probe is coordinated with aluminum ions, electron transfer of the probe to the metal ions can be induced to quench fluorescence due to the fact that the aluminum ions have an unfilled 3d shell, and the aggregation-induced luminescence effect and fluorescence quenching effect are combined to ensure that the fluorescence enhancement degree of the probe to the aluminum ions is smaller than the fluorescence enhancement degree of the probe to the lead ions, so that the concentration of the metal can be detected.
If the temperature is lower than 20 ℃, the reaction conversion rate is seriously affected no matter how long the stirring time is, and the obtained reaction liquid is a mixture of raw materials of 4- (di-p-toluylamino) benzaldehyde, 4-amino-3-hydroxybenzoic acid and a target product SP-1, and is difficult to separate and purify. And due to the interference of fluorescence of the raw material 4- (di-p-toluylamino) benzaldehyde, the obtained product cannot be used for accurately detecting the change of the viscosity of a system and the existence of metal ions.
The molar ratio of the 4- (di-p-toluylamino) benzaldehyde to the 4-amino-3-hydroxybenzoic acid is 1:1-1.5:1.
if the molar ratio of 4- (di-p-toluylamino) benzaldehyde is less than 1 equivalent, it is difficult to separate the complete 4-amino-3-hydroxybenzoic acid from the product. The component can complex metal ions, so that the fluorescent probe SP-1 cannot be combined with the metal ions to be detected, and the detection of the metal ions cannot be realized. If the molar ratio of 4- (di-p-toluylamino) benzaldehyde is too high, the residue thereof in the product may cause fluorescence interference; if the concentration is too high, the fluorescence emission peak of the SP-1 may be partially covered up, so that the SP-1 cannot accurately reflect the changes of the viscosity and the concentration of the metal ions.
The solvent is ethanol or acetonitrile.
The molar ratio of the solvent to the mixture was 50:1-200:1.
the molar equivalent of the aldehyde group reactant in the glacial acetic acid or ammonium acetate is 2-5%. Glacial acetic acid or ammonium acetate is 2% -5% of the molar equivalent of the aldehyde group reactant. If the molar ratio of glacial acetic acid or ammonium acetate is less than 2%, the reaction conversion rate is too low to obtain a high-purity product; if the molar ratio is too high, the pH value of the reaction system is too low, and the obtained Schiff base product is easy to decompose.
The solvent for washing the filter cake is ethanol or acetonitrile at 0-10 ℃. Low temperature solvents can reduce product losses.
The solvent for recrystallization is a polar solvent, and the polar solvent is ethanol, acetonitrile or acetone.
The invention also provides application of the fluorescent viscosity probe with aggregation-induced emission in detection of heavy metal ions and solution concentration.
Compared with the prior art, the invention has the beneficial effects that:
(1) The fluorescent viscosity probe provided by the application can have stronger fluorescent signal response to liquid viscosity change and heavy metal ions, and can be used for stabilizing and visually detecting the viscosity of beverages and blood systems and the heavy metal ions by utilizing the direct bonding effect of hydroxyl and carboxyl and heavy metal ions.
(2) The preparation method for the fluorescent viscosity probe with the Schiff base ligand by condensing 4-amino-3-hydroxybenzoic acid and 4- (di-p-toluylamino) benzaldehyde through aldol in one step is simple and efficient, short in period and high in yield, and the yield is 90-95%.
(3) The fluorescent viscosity probe with aggregation-induced emission property provided by the invention has stronger fluorescence emission intensity in an aggregation state, is easy to endow the fluorescent viscosity probe with more abundant functions by simply modifying substituents, and can adapt to the needs of various purposes.
Drawings
FIG. 1 is a graph showing the relationship between the water volume ratio and the fluorescence emission intensity and the wavelength of a mixed solution of pure tetrahydrofuran solution and water, wherein FIG. 1 (a) is a graph showing the relationship between the water volume ratio and the wavelength and the fluorescence intensity, and FIG. 1 (b) is a graph showing the relationship between the water volume ratio and the fluorescence emission intensity, wherein the graph is provided in application example 1;
FIG. 2 is a graph showing the relationship between the ethanol content and the fluorescence emission intensity and the wavelength of the fluorescent viscosity probe with aggregation-induced emission property in an ethanol-ethylene glycol system solution, wherein FIG. 2 (a) is a graph showing the relationship between the viscosity change and the fluorescence intensity, and FIG. 2 (b) is a graph showing the relationship between the viscosity logarithmic value and the fluorescence intensity;
FIG. 3 is a graph showing the relationship between the wavelength and fluorescence intensity of the fluorescent viscosity probe with aggregation-induced emission property provided in application example 3 and different ionic solutions;
FIG. 4 is a graph showing the relationship between fluorescence intensity of a fluorescent viscosity probe with aggregation-induced emission properties and various ionic solutions provided in application example 3;
FIG. 5 is a graph showing the fluorescence response intensity histogram of a fluorescence viscosity probe having aggregation-induced emission properties in the presence of other anions and cations for lead ions provided in application example 4;
FIG. 6 is a graph showing fluorescence response intensity of fluorescence viscosity probe having aggregation-induced emission properties in the presence of other anions and cations provided in application example 5 to aluminum ions;
FIG. 7 is a graph showing the relationship between the fluorescence intensity of the fluorescent viscosity probe having aggregation-induced emission property and the concentration of aluminum ions provided in application example 6;
FIG. 8 is a graph showing the relationship between the fluorescence intensity of the fluorescent viscosity probe having aggregation-induced emission property and the concentration of lead ions provided in application example 6.
Detailed Description
The following detailed description of the present invention is provided in connection with the accompanying examples, and it should be noted that the detailed description is merely illustrative of the invention and should not be taken as limiting the invention. The present invention is capable of numerous modifications, substitutions and alterations herein, all of which are within the scope of the present invention. The experimental methods in the following examples, without specific description, are all conventional methods; the adopted materials are purchased by the manufacturers of conventional biochemical reagents without special description.
Example 1
4- (Di-p-toluylamino) benzaldehyde (6.02 g,20 mmol) and 4- (di-p-toluylamino) benzaldehyde and 4-amino-3-hydroxybenzoic acid (3.06 g,20 mmol) were dissolved in 100mL of acetonitrile, and 2 drops of glacial acetic acid were added dropwise. After the completion of the charging, the reaction mixture was stirred at room temperature for 12 hours. After stopping heating, the reaction solution was filtered under reduced pressure, and the cake was washed with acetonitrile at 0 ℃. The filter cake was collected and recrystallized from acetonitrile. The recrystallized product was filtered, the resulting solid was collected and dried in vacuo to give 8.26g of product SP-1 in 93% yield.
Structural characterization data for compound SP-1 are as follows: 1H NMR (500 MHz, CDCl3, delta): 12.48 (s, 1H), 10.06 (s, 1H), 8.28 (s, 1H), 7.71-7.67 (M, 3H), 7.21 (d, J=7.0 Hz, 2H), 7.15 (d, J=7.0 Hz, 4H), 7.09 (d, J=7.0 Hz, 4H), 7.01 (d, J=7.0 Hz, 2H), 2.36 (s, 6H) HRMS (ESI) M/z: [ M] + calcd for C28H24N2O3,436.1787；found,436.1791。
Example 2
4- (Di-p-toluylamino) benzaldehyde (4.53 g,15 mmol) and 4- (di-p-toluylamino) benzaldehyde and 4-amino-3-hydroxybenzoic acid (1.53 g,10 mmol) were dissolved in 100mL of ethanol and 0.1g of ammonium acetate was added. After the completion of the charging, the reaction mixture was stirred at 80℃for 6 hours. After stopping heating, the reaction solution was filtered under reduced pressure, and the cake was washed with ethanol at 5 ℃. The filter cake was collected and recrystallized from ethanol. The recrystallized product was filtered, the resulting solid was collected and dried in vacuo to give 3.92g of product SP-1 in 90% yield. The characterization result of the obtained product is the same as that of the product obtained by the method 1.
Comparative example 1
4- (Di-p-toluylamino) benzaldehyde (3.01 g,10 mmol) and 4- (di-p-toluylamino) benzaldehyde and 4-amino-3-hydroxybenzoic acid (3.06 g,20 mmol) were dissolved in 100mL of ethanol and 0.5g of glacial acetic acid was added. After the completion of the charging, the reaction mixture was stirred at 0℃for 24 hours. After the heating was stopped, the reaction solution was subjected to rotary evaporation, and the obtained solid was collected, and weighed 5.52g in total. High resolution mass spectrometry, peaks of m=153, 301 and 436 are present in the product at the same time. The nuclear magnetic resonance hydrogen spectrum has a signal peak with chemical shift of 9.89 (free aldehyde matrix), 5.27 (free amino proton) and weak signal at 8.28 (imine proton signal), which indicates that the product is a mixture of two reaction raw materials and a small amount of product. The maximum emission peak of the spectrum of the mixture is 490nm, and the emission peak does not change in intensity with the addition of aluminum ions and lead ions.
Compound performance test:
application example 1
Preparing mixed solutions with the water volume ratio of 0%,20%,40%,60% and 100% respectively, and adding the SP-1 prepared in the example 1 into the mixed solutions respectively, wherein the fluorescence emission intensity of the SP-1 is gradually reduced in the mixed solutions with the water volume ratio of less than 90% and the pure tetrahydrofuran solution as shown in (a) and (b) in fig. 1; when the water volume ratio f w Above 90%, the fluorescence emission intensity of SP-1 increases significantly due to the formation of aggregates.
Application example 2
Adding glycol into ethanol, and preparing ethanol content fractionThe SP-1 prepared in example 1 was added to the ethanol-ethylene glycol system solutions of 100%, 90%, 80%, 70%, 60%, 50%, 40%, 30%, 20%, 10% and 5%, respectively, and as shown in FIGS. 2 (a) and (b), the fluorescence intensity of the SP-1 was significantly increased when the ethylene glycol content was increased and the system viscosity was increased. Wherein, the fluorescence intensity logarithmic value and the viscosity logarithmic value at 535nm show a better linear relation LgI =0.56 Lgeta+1.02 (R 2 =0.992). This indicates that SP-1 can be used for quantitative determination of fluid viscosity and has higher reliability.
Application example 3
Preparing blank solutions without any metal ions (the solvent ratio is water: tetrahydrofuran=1:1, the solvents of the rest solutions are all the same ratio), lead ion solution, aluminum ion solution, magnesium ion solution, copper ion solution, sodium ion solution, aluminum ion solution, sulfate ion solution, nitric acid and ion solution, and the ion solution concentration is 1×10 -5 M, SP-1 prepared in example 1 was added to the above ion solutions, respectively, as shown in FIG. 3, the fluorescence emission intensity of SP-1 was significantly enhanced when lead ions were present, and the fluorescence intensity was also enhanced but smaller in magnitude than when lead ions were present. The presence of other common cations and anions does not change the fluorescence intensity of the probe molecule in detail, as shown in fig. 4, the fluorescence intensity of the molecule is enhanced by 13 times compared with that of the blank solution when lead ions exist, and the fluorescence intensity is enhanced by 9 times when aluminum ions exist. In the solution in which other anions and cations exist, the fluorescence intensity is equivalent to that of the blank solution, and no obvious change is shown. The result shows that the fluorescent probe has certain selectivity for detecting lead ions and aluminum ions.
Application example 4
The concentration of the preparation is 1 multiplied by 10 -5 M lead ion solutions each having a concentration of 1X 10 -5 M magnesium ion solution, copper ion solution, sodium ion solution, aluminum ion solution, sulfate ion solution, nitric acid and ion solution are added into lead ion solution (the solvent ratio of the above solutions is water: tetrahydrofuran=1:1), and then SP-1 is added into the above mixture respectivelyIn the solution, as shown in FIG. 5, the probe molecules still can show strong fluorescence intensity in the presence of lead ions in the presence of other ions. This indicates that SP-1 detection of lead ions is not interfered by common anions and cations.
Application example 5
The concentration of the preparation is 1 multiplied by 10 -5 M, respectively adding a magnesium ion solution, a copper ion solution, a sodium ion solution, an aluminum ion solution, a sulfate ion solution and an ion solution into a lead ion solution (the solvent ratio of the solutions is water: tetrahydrofuran=1:1), then respectively adding SP-1 into the mixed solution, wherein the fluorescence intensity is shown in figure 6, and the probe molecules still can show strong fluorescence intensity in the presence of aluminum ions under the condition that other ions exist. This indicates that the detection of the SP-1 on aluminum ions is not interfered by common anions and cations.
Application example 6
At 25 ℃. Preparing ethanol/glycol mixed solutions with viscosity of 60cP and 350cP, and adding aluminum ion and lead ion into each mixed solution to make their concentrations be 1×10 respectively -7 M、1×10 -6 M、1×10 -5 M、1×10 -4 M and 1X 10 -3 M. SP-1 was then added to the above mixed solution, respectively, and the fluorescence intensities were as shown in FIG. 7 (aluminum ion) and FIG. 8 (lead ion). The basic fluorescence intensity of the probe molecules is different under different viscosities; on this basis, the probe molecules can respond to the change of the metal ion concentration by increasing the fluorescence intensity. Wherein, the linear relation exists between the fluorescence intensity of the probe at 60cP and 350cP and the change of the aluminum ion concentration, which are respectively I=192LgM+1534 (R 2 =0.996) and i=161lgm+1668 (R 2 =0.996); there is also a good linear relationship between the fluorescence intensity of the probe at 60cP and 350cP and the change in lead ion concentration, i=411volgm+3121 (R 2 =0.996) and i=362lgm+3140 (R 2 =0.996) demonstrates that it still has the ability to detect metal ions and their concentrations in environments of different viscosities.
Claims (7)
1. A fluorescent viscosity probe with aggregation-induced emission, characterized by the following structural formula:
。
2. a method of preparing a fluorescent viscosity probe with aggregation-induced emission according to claim 1, comprising:
mixing 4- (di-p-toluylamino) benzaldehyde and 4-amino-3-hydroxybenzoic acid to obtain a mixture, adding a solvent into the mixture, then adding glacial acetic acid or ammonium acetate to form a mixed solution, stirring the mixed solution at 20-80 ℃ for 6-12h, filtering, washing a filter cake, and recrystallizing to obtain a final product;
the molar ratio of the 4- (di-p-toluylamino) benzaldehyde to the 4-amino-3-hydroxybenzoic acid is 1:1-1.5:1, a step of;
the molar equivalent of the aldehyde group reactant in the glacial acetic acid or ammonium acetate is 2-5%.
3. The method for preparing a fluorescent viscosity probe with aggregation-induced emission according to claim 2, wherein the solvent is ethanol or acetonitrile.
4. The method of preparing a fluorescent viscosity probe with aggregation-induced emission according to claim 2, wherein the molar ratio of the solvent to the mixture is 50:1-200:1.
5. the method for preparing a fluorescent viscosity probe with aggregation-induced emission according to claim 2, wherein the solvent for washing the filter cake is ethanol or acetonitrile at 0-10 ℃.
6. The method for preparing a fluorescent viscosity probe with aggregation-induced emission according to claim 2, wherein the solvent for recrystallization is a polar solvent, and the polar solvent is ethanol, acetonitrile or acetone.
7. Use of a fluorescent viscosity probe with aggregation-induced emission according to claim 1 for the detection of lead and aluminium ions and solution viscosity.
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| CN110157413A (en) * | 2019-05-31 | 2019-08-23 | 浙江师范大学 | A kind of Selective recognition lead ion and aluminum ions aggregation-induced emission molecular probe and its preparation method and application |
| CN112552208A (en) * | 2021-01-25 | 2021-03-26 | 井冈山大学 | Fluorescent molecule for eye drop quality detection and preparation and application thereof |
| CN113896677A (en) * | 2021-08-23 | 2022-01-07 | 浙江科技学院 | Reversible force photochromic material with aggregation-induced emission property and preparation method thereof |
| CN113913182A (en) * | 2021-08-27 | 2022-01-11 | 华南理工大学 | Fluorescent probe for cosmetic deterioration viscosity detection and preparation method and application thereof |
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| CN110157413A (en) * | 2019-05-31 | 2019-08-23 | 浙江师范大学 | A kind of Selective recognition lead ion and aluminum ions aggregation-induced emission molecular probe and its preparation method and application |
| CN112552208A (en) * | 2021-01-25 | 2021-03-26 | 井冈山大学 | Fluorescent molecule for eye drop quality detection and preparation and application thereof |
| CN113896677A (en) * | 2021-08-23 | 2022-01-07 | 浙江科技学院 | Reversible force photochromic material with aggregation-induced emission property and preparation method thereof |
| CN113913182A (en) * | 2021-08-27 | 2022-01-11 | 华南理工大学 | Fluorescent probe for cosmetic deterioration viscosity detection and preparation method and application thereof |
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