CN117447465B - On-off-on fluorescent probe, reagent, chemical sensor, preparation method and application - Google Patents
On-off-on fluorescent probe, reagent, chemical sensor, preparation method and application Download PDFInfo
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- 239000007850 fluorescent dye Substances 0.000 title claims abstract description 110
- 239000003153 chemical reaction reagent Substances 0.000 title claims abstract description 12
- 238000002360 preparation method Methods 0.000 title claims abstract description 11
- 239000000126 substance Substances 0.000 title abstract description 16
- 238000001514 detection method Methods 0.000 claims abstract description 36
- 150000002500 ions Chemical class 0.000 claims abstract description 34
- 239000000575 pesticide Substances 0.000 claims abstract description 27
- 239000005562 Glyphosate Substances 0.000 claims abstract description 24
- XDDAORKBJWWYJS-UHFFFAOYSA-N glyphosate Chemical compound OC(=O)CNCP(O)(O)=O XDDAORKBJWWYJS-UHFFFAOYSA-N 0.000 claims abstract description 24
- 229940097068 glyphosate Drugs 0.000 claims abstract description 24
- 239000002351 wastewater Substances 0.000 claims abstract description 6
- 239000010865 sewage Substances 0.000 claims abstract description 5
- 238000000034 method Methods 0.000 claims description 18
- 239000002904 solvent Substances 0.000 claims description 8
- 238000006243 chemical reaction Methods 0.000 claims description 7
- 238000010992 reflux Methods 0.000 claims description 4
- 201000010099 disease Diseases 0.000 claims 1
- 208000037265 diseases, disorders, signs and symptoms Diseases 0.000 claims 1
- 229910021645 metal ion Inorganic materials 0.000 abstract description 19
- 239000010949 copper Substances 0.000 description 56
- 239000000523 sample Substances 0.000 description 41
- 239000000243 solution Substances 0.000 description 40
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- 238000002189 fluorescence spectrum Methods 0.000 description 15
- 239000012086 standard solution Substances 0.000 description 15
- 238000004448 titration Methods 0.000 description 14
- IOJUPLGTWVMSFF-UHFFFAOYSA-N benzothiazole Chemical group C1=CC=C2SC=NC2=C1 IOJUPLGTWVMSFF-UHFFFAOYSA-N 0.000 description 13
- 150000001875 compounds Chemical class 0.000 description 12
- 229910052802 copper Inorganic materials 0.000 description 12
- JKMHFZQWWAIEOD-UHFFFAOYSA-N 2-[4-(2-hydroxyethyl)piperazin-1-yl]ethanesulfonic acid Chemical compound OCC[NH+]1CCN(CCS([O-])(=O)=O)CC1 JKMHFZQWWAIEOD-UHFFFAOYSA-N 0.000 description 11
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- 210000004027 cell Anatomy 0.000 description 6
- VKYKSIONXSXAKP-UHFFFAOYSA-N hexamethylenetetramine Chemical compound C1N(C2)CN3CN1CN2C3 VKYKSIONXSXAKP-UHFFFAOYSA-N 0.000 description 6
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- 239000012491 analyte Substances 0.000 description 5
- XJHABGPPCLHLLV-UHFFFAOYSA-N benzo[de]isoquinoline-1,3-dione Chemical compound C1=CC(C(=O)NC2=O)=C3C2=CC=CC3=C1 XJHABGPPCLHLLV-UHFFFAOYSA-N 0.000 description 5
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- 230000008859 change Effects 0.000 description 4
- MVVGSPCXHRFDDR-UHFFFAOYSA-N 2-(1,3-benzothiazol-2-yl)phenol Chemical compound OC1=CC=CC=C1C1=NC2=CC=CC=C2S1 MVVGSPCXHRFDDR-UHFFFAOYSA-N 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
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- 239000004480 active ingredient Substances 0.000 description 3
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- 238000010586 diagram Methods 0.000 description 3
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- 235000010299 hexamethylene tetramine Nutrition 0.000 description 3
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- 238000002211 ultraviolet spectrum Methods 0.000 description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- 238000005481 NMR spectroscopy Methods 0.000 description 2
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- IAJOBQBIJHVGMQ-UHFFFAOYSA-N 2-amino-4-[hydroxy(methyl)phosphoryl]butanoic acid Chemical compound CP(O)(=O)CCC(N)C(O)=O IAJOBQBIJHVGMQ-UHFFFAOYSA-N 0.000 description 1
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 description 1
- 239000005959 Fosthiazate Substances 0.000 description 1
- 239000005561 Glufosinate Substances 0.000 description 1
- 108010043121 Green Fluorescent Proteins Proteins 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 239000005578 Mesotrione Substances 0.000 description 1
- 239000005590 Oxyfluorfen Substances 0.000 description 1
- OQMBBFQZGJFLBU-UHFFFAOYSA-N Oxyfluorfen Chemical compound C1=C([N+]([O-])=O)C(OCC)=CC(OC=2C(=CC(=CC=2)C(F)(F)F)Cl)=C1 OQMBBFQZGJFLBU-UHFFFAOYSA-N 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
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- 229910045601 alloy Inorganic materials 0.000 description 1
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- 238000010668 complexation reaction Methods 0.000 description 1
- 229910001431 copper ion Inorganic materials 0.000 description 1
- 239000012043 crude product Substances 0.000 description 1
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- 238000002474 experimental method Methods 0.000 description 1
- 238000012921 fluorescence analysis Methods 0.000 description 1
- DUFVKSUJRWYZQP-UHFFFAOYSA-N fosthiazate Chemical compound CCC(C)SP(=O)(OCC)N1CCSC1=O DUFVKSUJRWYZQP-UHFFFAOYSA-N 0.000 description 1
- 210000004024 hepatic stellate cell Anatomy 0.000 description 1
- 125000005842 heteroatom Chemical group 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 150000002475 indoles Chemical class 0.000 description 1
- 238000002329 infrared spectrum Methods 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- KPUREKXXPHOJQT-UHFFFAOYSA-N mesotrione Chemical compound [O-][N+](=O)C1=CC(S(=O)(=O)C)=CC=C1C(=O)C1C(=O)CCCC1=O KPUREKXXPHOJQT-UHFFFAOYSA-N 0.000 description 1
- 229960001952 metrifonate Drugs 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000003068 molecular probe Substances 0.000 description 1
- 239000000447 pesticide residue Substances 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
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- 230000001376 precipitating effect Effects 0.000 description 1
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- 239000000047 product Substances 0.000 description 1
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 1
- 238000010791 quenching Methods 0.000 description 1
- 230000000171 quenching effect Effects 0.000 description 1
- 230000035945 sensitivity Effects 0.000 description 1
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- 125000001424 substituent group Chemical group 0.000 description 1
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- 239000000725 suspension Substances 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- NFACJZMKEDPNKN-UHFFFAOYSA-N trichlorfon Chemical compound COP(=O)(OC)C(O)C(Cl)(Cl)Cl NFACJZMKEDPNKN-UHFFFAOYSA-N 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
- C07D417/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for by group C07D415/00
- C07D417/02—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for by group C07D415/00 containing two hetero rings
- C07D417/12—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for by group C07D415/00 containing two hetero rings linked by a chain containing hetero atoms as chain links
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- C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
- C09K11/02—Use of particular materials as binders, particle coatings or suspension media therefor
- C09K11/025—Use of particular materials as binders, particle coatings or suspension media therefor non-luminescent particle coatings or suspension media
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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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- 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"
- G01N21/643—Measuring fluorescence of fluorescent products of reactions or of fluorochrome labelled reactive substances, e.g. measuring quenching effects, using measuring "optrodes" non-biological material
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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
- G01N21/645—Specially adapted constructive features of fluorimeters
- G01N21/6456—Spatial resolved fluorescence measurements; Imaging
- G01N21/6458—Fluorescence microscopy
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- C09K2211/1037—Heterocyclic compounds characterised by ligands containing one nitrogen atom as the heteroatom with sulfur
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- 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 application relates to the technical field of fluorescent probes, in particular to an on-off-on fluorescent probe, a reagent, a chemical sensor, a preparation method and application. The embodiment discloses the "on-off-on" type fluorescent probe as shown in the formula (I) and a reagent containing the "on-off-on" type fluorescent probe. The embodiment also discloses a chemical sensor which comprises a surface and the on-off-on fluorescent probe covalently bonded on the surface, and is used for detecting metal ions or pesticides in sewage or wastewater. The fluorescent probe can specifically identify that ions are Fe 3+ 、Cu 2+ And CN ‑ The complex [ I+Cu ] formed 2+ ]And [ I+Fe 3+ ]Glyphosate can be further detected, and the identification detection limits are respectively 0.22 mu M and 0.21 mu M, which are obviously lower than the similar fluorescent probes in the prior art.
Description
Technical Field
The application relates to the technical field of fluorescent probes, in particular to an on-off-on fluorescent probe, a reagent, a chemical sensor, a preparation method and application.
Background
The fluorescent probe is a fluorescence analysis means for quantitatively detecting the target analyte by utilizing the change of the self-fluorescence spectrum property caused by the specific physical or chemical reaction between the probe and the target analyte and with the assistance of a fluorescence spectrophotometer.
By "on-off-on" type fluorescent probe, it is meant that the fluorescent probe itself can generate fluorescence, and upon recognition or interaction with the analyte, fluorescence quenching occurs, and the analyte and fluorescent probe typically form a complex by complexation; when another analyte interacts with the complex, the complex breaks bonds to recover to the original fluorescent probe according to the coordination competition principle, and the fluorescence opening phenomenon occurs.
Disclosure of Invention
The synthesis process of the benzothiazole structure is mature and simple, generally has longer fluorescence emission wavelength and quantum yield, and the heteroatom of the structural unit can be used as a coordination point to participate in chelation of metal ions, so that the benzothiazole structure has good application prospect in the field of metal cation fluorescence imaging. The inventor of the present application developed a novel "on-off-on" type fluorescent probe based on benzothiazole. The on-off-on fluorescent probe not only can effectively detect metal cations, but also can detect pesticide residues (glyphosate) in wastewater. Therefore, the embodiment of the application at least discloses the following technical scheme:
in a first aspect, the embodiments disclose an "on-off-on" fluorescent probe of formula I
In a second aspect, the embodiments disclose a reagent comprising the "on-off-on" type fluorescent probe of the first aspect and a solvent for dissolving the "on-off-on" type fluorescent probe.
In a third aspect, embodiments disclose a chemical sensor for ion detection, the chemical sensor comprising a surface and an "on-off-on" fluorescent probe covalently attached to the surface.
In a fourth aspect, embodiments disclose a chemical sensor for the detection of pesticides in sewage or wastewater, the chemical sensor comprising a surface and the "on-off-on" fluorescent probe of the first aspect covalently attached to the surface.
In a fifth aspect, an embodiment discloses a method for preparing the "on-off-on" type fluorescent probe according to the first aspect, which comprises the step of carrying out reflux reaction on 3- (benzothiazole) -4-hydroxybenzaldehyde and N-N-butyl-4-hydrazino-1, 8-naphthalimide for 7-9 hours at 70-90 ℃ to obtain the "on-off-on" type ion and pesticide detection fluorescent probe.
In a sixth aspect, embodiments disclose the use of the "on-off-on" fluorescent probe of the first aspect or the reagent of the second aspect for ion detection and/or pesticide detection in sewage or wastewater.
Drawings
FIG. 1 shows the fluorescence spectra (a) of the fluorescent probe of formula I in different solvents and the fluorescence response (b) in different DMSO to water ratio solutions, as provided in the examples.
Fig. 2 (a) and (b) are graphs showing the effect of different metal ions on the ultraviolet and fluorescence spectra of the fluorescent probe of formula I.
FIG. 3 (a) and (b) are graphs showing the effect of different anions on the ultraviolet and fluorescence spectra of the fluorescent probe of formula I.
In FIG. 4, (a), (b) and (c) are the fluorescent probes of formula I in the presence of Fe respectively 3+ 、Cu 2+ And CN - Fluorescence intensity at ion vs.
In FIG. 5, (a), (b) and (c) are the fluorescent probes of formula I in the presence of Fe respectively 3+ 、Cu 2+ And CN - Fluorescence intensity at different pH when ions are changed.
In FIG. 6, (a) and (b) are added with Fe in different volumes 3+ Titration spectrum contrast and fluorescence of fluorescent probe shown in the following formula IFluorescence intensity of the probe and different Fe 3+ Concentration linear relationship graph. In the figure, (a), 0-7 equivalents are as follows in the arrow direction: 0. 0.5, 1, 1.5, 2, 2.5, 3, 3.5, 4, 4.5, 5, 5.5, 6, 6.5 and 7 equivalents.
In FIG. 7, (a) and (b) are sequentially added Cu in different volumes 2+ Titration spectrum contrast diagram of fluorescent probe shown in the following formula I and fluorescence intensity of fluorescent probe and different Cu 2+ Concentration linear relationship graph. In the figure, (a), 0-6 equivalents are as follows in the arrow direction: 0. 0.5, 1, 2, 2.5, 3, 3.5, 4, 4.5, 5, 5.5 and 6 equivalents.
In FIG. 8, (a) and (b) are added with different volumes CN in turn - Titration spectrum contrast diagram of fluorescent probe shown in the following formula I and fluorescence intensity of fluorescent probe and different CN - Concentration linear relationship graph. In the figure, (a), 0-3 equivalents are as follows in the arrow direction: 0. 0.5, 0.7, 0.9, 1.1, 1.3, 1.5, 1.7, 1.9, 2.1, 2.3, 2.5, 2.7 and 3.0 equivalents.
In FIG. 9, (a), (b) and (c) are the fluorescent probes represented by formula I and Cu, respectively 2+ 、Fe 3+ 、CN - Job graph of (a).
Fig. 10 is a fluorescence imaging diagram of the fluorescent probe shown in formula I.
In FIG. 11, (a) and (b) are the fluorescent probes of formula I and Cu, respectively, after adding the pesticide 2+ 、Fe 3+ Fluorescence spectrum change of the solution after formation of the complex.
In FIG. 12, (a) and (b) are shown in the sequence of formula I, the fluorescent probe and Cu 2+ 、Fe 3+ Comparison of fluorescence intensity in the presence of glyphosate after formation of the complex.
In FIG. 13, (a), (b), (c) and (d) are the fluorescent probe and Cu of formula I after adding different volumes of glyphosate 2+ A titration spectrum comparison graph after forming a complex and a graph of linear relation between the titration spectrum comparison graph and different glyphosate concentrations; fluorescent probe shown in formula I and Fe after adding different volumes of glyphosate 3+ Titration spectra after complex formation and a plot of the linear relationship with different glyphosate concentrations.
Detailed Description
In order to make the objects, technical solutions and advantages of the present application more apparent, the present application will be further described in detail with reference to examples. It should be understood that the specific embodiments described herein are for purposes of illustration only and are not intended to limit the present application. Reagents not specifically and individually described in this application are all conventional reagents and are commercially available; methods which are not specifically described in detail are all routine experimental methods and are known from the prior art.
As a classical fluorescent dye molecule, the benzothiazole fluorophore has the advantages of strong photostability, high quantum yield, strong coordination capacity, easy structure modification and the like. Benzothiazole derivatives are therefore a very potential class of fluorescent molecular probes. The naphthalimide fluorescent probe is based on a larger electron-withdrawing and electron-donating conjugated system in the naphthalimide structure, is easy to be subjected to light irradiation to generate transition, so that strong fluorescence can be generated, and the naphthalimide fluorescent probe has been widely applied to the field of fluorescent probes. The N-,3-, 4-position of naphthalimide is introduced with substituent groups to design and synthesize naphthalimide derivatives, so that a novel fluorescent probe is constructed, metal ions and pesticides in actual samples can be detected, and the method has important significance for industrial and agricultural and environmental protection.
The fluorescent probe shown in the formula I disclosed in the embodiment of the application is an on-off-on type ion and pesticide detection fluorescent probe, and can specifically identify the ion as Fe 3+ 、Cu 2+ And CN - The detection limits of the identification are respectively 0.22 mu M, 0.15 mu M and 0.061 mu M; the complex [ I+Cu ] formed 2+ ]And [ I+Fe 3+ ]Glyphosate can be further detected, and the identification detection limits are respectively 0.22 mu M and 0.21 mu M, which are obviously lower than the similar fluorescent probes in the prior art. In addition, the detection method adopted by the application is simple and easy to operate, and has potential application value in the aspects of monitoring anions, cations, pesticides and the like in polluted water.
To this end, the examples also disclose a reagent comprising the "on-off-on" type fluorescent probe of formula (I) and a solvent for dissolving the "on-off-on" type fluorescent probe. In some embodiments, the solvent is selected from at least one of methanol, ethanol, propanol, acetonitrile, acetone, ethyl acetate, ethylene glycol, dimethyl sulfoxide, and water.
Due to the fluorescent nature of the "on-off-on" type fluorescent probe of formula (I), embodiments also disclose a chemical sensor for ion detection that includes a surface and the "on-off-on" type fluorescent probe of formula (I) covalently attached to the surface. For example, the "on-off-on" type fluorescent probe of formula (I) is covalently bound to the surface of a carbon nanotube, thereby producing a chemical sensor for metal ion detection. In some embodiments, the ion is selected from Fe 3+ 、Cu 2+ And CN - 。
Due to the fluorescent nature of the "on-off-on" type fluorescent probe of formula (I), embodiments also disclose a chemical sensor for the detection of pesticides in sewage or wastewater, the chemical sensor comprising a surface and the "on-off-on" type fluorescent probe of formula (I) covalently attached to the surface. For example, the "on-off-on" type fluorescent probe of formula (I) is covalently bound to the surface of a carbon nanotube, thereby producing a chemical sensor for pesticide detection. In some embodiments, the ion is selected from Fe 3+ 、Cu 2+ And CN - . In some embodiments, the pesticide is selected from the group consisting of glyphosate,
In some embodiments, the step of covalently binding the "on-off-on" fluorescent probe of formula (I) to the surface of the carbon nanotube can be performed by the method disclosed in "indole derivative modified carbon nanotube copper ion fluorescent sensor, guangzhou chemical, volume 47, stage 1, 2019, month 1".
Some embodiments also disclose a preparation method of the on-off-on type fluorescent probe shown in the formula (I), which comprises the step of carrying out reflux reaction on 3- (benzothiazole) -4-hydroxybenzaldehyde and N-N-butyl-4-hydrazino-1, 8-naphthalimide for 7-9 h at 70-90 ℃ to obtain the on-off-on type ion and pesticide detection fluorescent probe.
In some examples of the preparation method, the reaction molar ratio of the 3- (benzothiazole) -4-hydroxybenzaldehyde to the N-N-butyl-4-hydrazino-1, 8-naphthalimide is (1 to 3): 1.
In some examples of the preparation method, the preparation method of the 3- (benzothiazole) -4-hydroxybenzaldehyde comprises the step of stirring and refluxing 2- (2-hydroxyphenyl) -benzothiazole and hexamethylenetetramine at 70-90 ℃ for 24-30 hours.
In some embodiments of the preparation process, the molar ratio of 2- (2-hydroxyphenyl) -benzothiazole to hexamethylenetetramine is 1 (1.5-3.5).
An example of a method for preparing an "on-off-on" type fluorescent probe of formula (I) includes the steps of:
(1) Synthesis of 3- (benzothiazole) -4-hydroxybenzaldehyde
0.02mol of 2- (2-hydroxyphenyl) -benzothiazole and 0.06mol of hexamethylenetetramine were dissolved in 80mL of TFA. The contents were refluxed at 80℃for 24h. The solution was cooled to room temperature and then neutralized with 1M HCl. The precipitate was filtered and then washed 3 times with distilled water. The residue was dried and purified, followed by column chromatography on silica gel (CH 2 Cl 2 MeOH,100:l, V/V) to give the compound 3- (benzothiazole) -4-hydroxybenzaldehyde in 52.6% yield;
(2) Synthesis of 2- (benzothiazole) phenol-4- (N-butyl) hydrazino-1, 8-naphthalimide
0.012mol of the compound 3- (benzothiazole) -4-hydroxybenzaldehyde obtained in step (1) was dissolved in 50mL of ethanol solution, N-N-butyl-4-hydrazino-1, 8-naphthalimide (0.01 mol) was added, and the reaction was stirred at room temperature of 78℃for 8 hours. Standing after the reaction is finished, precipitating solid, carrying out suction filtration, washing for three times, and drying to obtain a crude product. Purifying by ethyl acetate/petroleum ether silica gel column chromatography to obtain 2- (benzothiazole) phenol-4- (N-butyl) hydrazino-1, 8-naphthalimide (namely a compound shown in a formula (I)) with a yield of 63.6% and a melting point of 249.3-250.1 ℃.
The infrared spectrum peak data of the compound shown in the formula (I) are as follows:
3184(N-H),2924,2853(C-H),1697,1662(C＝O)。
the nuclear magnetic resonance hydrogen spectrum data of the compound shown in the formula (I) are as follows:
12.82(s,1H),11.56(s,1H),8.88–8.73(m,2H),8.48–8.41(m,1H),8.38–8.32(m,1H),8.17(t,J＝8.5Hz,1H),8.12–8.00(m,2H),7.95(d,J＝7.5Hz,1H),7.75(d,J＝7.7Hz,1H),7.65–7.53(m,2H),7.48(d,J＝15.1,7.4Hz,1H),7.21–7.10(m,1H),4.05–3.98(m,2H),1.43–1.28(m,2H),1.18(t,J＝7.1Hz,2H),0.99–0.86(m,3H)。
the nuclear magnetic resonance carbon spectrum data of the compound shown in the formula (I) are as follows:
167.68,164.15,163.47,155.79,151.72,146.69,141.32,141.20,133.69,131.14,130.14,128.69,127.65,127.34,127.00,126.25,125.38,125.19,123.10,122.58,120.66,119.45,118.56,118.38,107.49,107.42,41.06,40.85,40.64,40.43,40.22,40.02,39.81,30.35,20.24,14.01,13.97。
from the above, it is understood that the objective compound prepared in this example is 2- (benzothiazole) phenol-4- (N-butyl) hydrazino-1, 8-naphthalimide.
Performance testing of compounds of formula (I):
1. selectivity test for different solvents
The method comprises the following steps: respectively DMF, DMSO, CH 3 OH、CH 3 CH 2 OH or CH 3 Preparation of HEPES buffer containing CN and different proportions of the compound represented by formula (I) at a concentration of 1X 10 -5 And taking mol/L as probe liquid, and respectively performing fluorescence spectrum test to determine the optimal solvent of the probe.
As a result, as shown in fig. 1, it was determined that the mixing at ph=7, DMSO to HEPES volume ratio of 3:7 was easily the optimal solvent.
2. Selective testing of different metal ions
The method comprises the following steps: respectively preparing 50mL standard solutions of different metal ions by using ultrapure water, wherein each standard solution contains K + 、Na + 、Mg 2+ 、Al 3 + 、Ba 2+ 、Cu 2+ 、Zn 2+ 、Ni 2+ 、Sn 2+ 、Fe 3+ 、Ca 2+ 、Hg 2+ 、Pb 2+ 、Mn 2+ 、Co 2+ 、Cr 3+ The concentration of (2) is 10 -2 mol/L is used as metal ion liquid. The concentration of fluorescent probe containing the probe represented by formula I was 1X 10 in DMSO: HEPES (3:7, V/V, pH=7) solution -5 The mol/L is the probe liquid. Preparing a plurality of 10mL samples to be detected from the probe liquid and the metal ion liquid containing different metal ions according to the volume ratio of 1:5, and dividingUltraviolet spectrum and fluorescence spectrum tests are respectively carried out, so that the target object which can be identified by the probe can be determined.
As a result, as shown in FIG. 2, only Fe was added 3+ The maximum absorption peak of the ultraviolet visible spectrum of the solution generates obvious blue shift when the ion is carried out, and the absorption value is reduced. In the fluorescence spectrum of the compound shown in the formula I, cu is added 2+ /Fe 3+ The fluorescence of the system is obviously quenched when two ions are added, and the addition of other metal ions has no obvious influence on the fluorescence intensity. This demonstrates that the compound of formula I is specific to Cu 2+ /Fe 3+ Is a response to the test signal.
3. Selective testing of anions
The method comprises the following steps: 50mL of the solution containing 10% of the active ingredient was prepared with ultrapure water -2 Standard solution of different anions in mol/L, wherein the anions are Ac - 、I - 、HSO 4 - 、ClO - 、NO 2- 、F - 、Cl - 、SCN - 、HPO 4 - 、CN - 、Br - The method comprises the steps of carrying out a first treatment on the surface of the The concentration of fluorescent probe containing the probe represented by formula I was 1X 10 in DMSO: HEPES (3:7, V/V, pH=7) solution －5 The mol/L is the probe liquid. Preparing the probe liquid and standard liquid containing different anions into a plurality of 10mL samples to be tested according to the volume ratio of 1:5, and respectively carrying out ultraviolet spectrum and fluorescence spectrum tests to determine the target object identifiable by the probe.
As shown in FIG. 3, when different anions are added into the solution, the ultraviolet visible spectrum of the system has no obvious change; while observing the fluorescence spectrum, only CN is added - When ions are generated, the fluorescence intensity of the system is obviously reduced. This demonstrates that the compound of formula I is useful for CN - Is a response to the test signal.
4. Detection of anti-negative ion interference
The method comprises the following steps: 50mL of the solution containing 10% of the active ingredient was prepared with ultrapure water -2 Standard solution of different ions in mol/L, wherein the metal ion is K + 、Na + 、Mg 2+ 、Al 3+ 、Ba 2+ 、Cu 2+ 、Zn 2+ 、Ni 2+ 、Sn 2+ 、Fe 3+ 、Ca 2+ 、Hg 2+ 、Pb 2+ 、Mn 2+ 、Co 2+ 、Cr 3+ The anion is Ac - 、I - 、HSO4 - 、ClO - 、NO 2- 、F - 、Cl - 、SCN - 、HPO 4 - 、CN - 、Br - . The concentration of fluorescent probe containing the probe represented by formula I was 1X 10 in DMSO: HEPES (3:7, V/V, pH=7) solution －5 The mol/L is the probe liquid. Preparing a plurality of identical samples to be tested from the probe liquid and standard liquid containing different ions according to the volume ratio of 1:5, and then respectively adding 10-containing substances with identical volumes -2 Fe of mol/L 3+ 、Cu 2+ 、CN - As interfering ions, detecting the Fe respectively identified by the fluorescent probes shown in the formula I in the presence of different ions 3+ 、Cu 2+ 、CN - Is used for the anti-interference capability of the battery.
As a result, as shown in FIG. 4, when other ions are present, the fluorescence intensity is still significantly reduced by adding the detection ion. The above results indicate that the presence of other interfering ions does not affect the Fe in the fluorescent probe of formula I 3+ 、Cu 2+ And CN - And (3) specific detection of ions.
5. PH detection
The method comprises the following steps: respectively preparing 50mL standard solutions of different ions by using ultrapure water, wherein Cu is contained in each standard solution 2+ 、Fe 3+ And CN - The concentration of (2) is 10 -2 mol/L; the concentration of fluorescent probe containing the probe represented by formula I was 1X 10 in DMSO: HEPES (3:7, V/V, pH=7) solution -5 The mol/L is the probe liquid. And preparing a plurality of 10mL samples to be tested by the probe liquid and different metal ion standard liquids according to the volume ratio of 1:5, and then testing fluorescence spectrum by using HCl and NaOH to adjust a system without pH.
As shown in FIG. 5, the fluorescence intensity is significantly different in the pH range of 4 to 8, and the fluorescent probe of formula I can specifically detect Cu 2+ 、Fe 3+ And CN - 。
6. The fluorescent probe shown in formula I is specific to metal ion Fe 3+ 、Cu 2+ 、CN - Titration detection of (c):
the method comprises the following steps: 50mL of the solution containing 10% of the active ingredient was prepared with ultrapure water -2 Fe of mol/L 3+ 、Cu 2+ 、CN - A titration solution; the concentration of fluorescent probe containing the probe represented by formula I was 1X 10 in DMSO: HEPES (3:7, V/V, pH=7) solution －5 The mol/L is the probe liquid. Different volumes of Fe3+ (0-7 equivalent) and Cu 2+ (0-6 equivalent) CN - Adding (0-3 equivalent) ion standard solution into the probe solution to prepare to-be-detected solutions with different concentration ratios; fluorescence spectrum test is carried out on the solution to determine the concentration of Fe in different probe pairs 3+ 、Cu 2+ 、CN - Is a function of the identification ability of the device.
As a result, as shown in FIG. 6, when Fe is contained 3+ The volume ratio of titration solution to probe solution was increased from 0 to 7 equivalents, the fluorescence of the solution was gradually quenched, and reached the highest at 7 equivalents. Fluorescence intensity and Fe 3+ There is a good linear relationship between the concentrations (R 2 =0.99). Through calculation, the detection limit is as low as 0.22 mu M, thereby realizing the Fe-based alloy 3+ Is a quantitative detection of (a).
As a result, as shown in FIG. 7, when Cu is contained 2+ The volume ratio of titration solution to probe solution was increased from 0 to 6 equivalents, the fluorescence of the solution was gradually quenched, and reached maximum at 6 equivalents. Fluorescence intensity and Cu 2+ There is a good linear relationship between the concentrations (R 2 =0.98). Through calculation, the detection limit is as low as 0.15 mu M, thereby realizing Cu 2+ Is a quantitative detection of (a).
The results are shown in FIG. 8 when CN is contained - The volume ratio of titration solution to probe solution was increased from 0 to 3 equivalents, the fluorescence of the solution was gradually quenched, and reached maximum at 3 equivalents. Fluorescence intensity and CN - There is a good linear relationship between the concentrations (R 2 =0.98). Through calculation, the detection limit is as low as 0.061 mu M, and the CN is realized - Is a quantitative detection of (a).
7. Fluorescent probe and ionic Cu shown in formula I 2+ 、Fe 3+ 、CN - Complex ratio test of (2)
The method comprises the following steps: respectively preparing 50mL of the mixture with the concentration of 10 -2 Cu in mol/L 2+ 、Fe 3+ 、CN - Is a titration solution of (2); the concentration of fluorescent probe containing the probe represented by formula I was 1X 10 in DMSO: HEPES (3:7, V/V, pH=7) solution －5 The mol/L is the probe liquid. Probe liquid and Cu respectively 2+ 、Fe 3+ 、CN - Preparing solutions with different proportions respectively according to the volume ratio of 0.1 to 0.9 of the titration solution; subjecting the above solution to fluorescence spectrum test to determine the probe pair Cu 2+ 、Fe 3+ 、CN - Coordination ratio of (3).
As shown in FIG. 9, cu is added 2+ And Fe (Fe) 3+ The maximum emission intensity was measured to be 0.5 mole fraction, indicating that the fluorescent probe of formula I was compared to Cu 2+ And Fe (Fe) 3+ Forming a complex in a stoichiometric ratio of 1:1; when adding CN - At the point of intersection at molar ratio=0.6, indicating that the fluorescent probe represented by probe formula I was hybridized with CN - The coordination ratio is about 1:2.
8. Fluorescent probes of formula I for imaging test in cells
Adding fluorescent probe shown in formula I into 106cells/mL human hepatic stellate cell (HSC, product number: CP-H046, prinocetary) suspension to make the concentration of fluorescent probe 10 μm, incubating at 37deg.C for 30min, and adding Fe into the system 3+ 、Cu 2+ 、CN - The added ion concentrations were 20. Mu.M, and the cells were again incubated for 30min and then observed with a laser confocal microscope to give a picture.
FIG. 10 shows HSC cells without added ions and fluorescent probes of formula I, fluorescence of the non-ionic cells can be observed. The fluorescence in the cells was quenched significantly by addition of 10. Mu.M of the different ions, respectively. The above results show that the fluorescent probe shown in the probe formula I can be used for living cell imaging and can detect whether Fe exists in cells 3+ 、Cu 2+ And CN - 。
9. Fluorescent probe and Cu shown in formula I 2+ 、Fe 3+ And testing the detection capability of the formed complex on different pesticides:
the method comprises the following steps: respectively preparing 50mL standard solutions of different metal ions by using ultrapure water, wherein Cu is contained in each standard solution 2+ 、Fe 3+ The concentration of (2) is 10 -2 mol/L; the concentration of fluorescent probe containing the probe represented by formula I was 1X 10 in DMSO: HEPES (3:7, V/V, pH=7) solution -5 The mol/L is the probe liquid. Preparing a plurality of 10mL samples to be tested from the probe liquid and different metal ion standard liquids according to the volume ratio of 1:5, and respectively adding the fluorescent probe shown in the formula I and Cu 2+ 、Fe 3+ Different pesticides are added into the formed complex system as samples, and fluorescence spectra are tested, wherein the pesticides are respectively selected from glyphosate, glufosinate, trichlorfon, fosthiazate, aluminum triethyl phosphate, mesotrione and oxyfluorfen.
As shown in FIG. 11, only the fluorescent probe represented by formula I and Cu 2+ 、Fe 3+ The formed complex system can cause obvious fluorescence enhancement when glyphosate is added, the color change is shown as an inserting chart, and the fluorescent probe shown as a formula I and Cu of the rest pesticides under the same condition 2+ 、Fe 3+ The effect in the complex system formed is negligible. As can be seen in the inset, the fluorescent probe of formula I and Cu were clearly observed only when glyphosate was added 2+ 、Fe 3+ The complex system formed is strong green fluorescent. The result shows that the fluorescent probe shown in the formula I and Cu 2+ 、Fe 3+ The formed complex system can be used for specifically recognizing glyphosate in various pesticides.
10. Pesticide pair formula I fluorescent probe and Cu 2+ 、Fe 3+ Interference test of the detection ability of the formed complexes:
the method comprises the following steps: respectively preparing 50mL standard solutions of different metal ions by using ultrapure water, wherein Cu is contained in each standard solution 2+ 、Fe 3+ The concentration of (2) is 10 -2 mol/L; the concentration of fluorescent probe containing the probe represented by formula I was 1X 10 in DMSO: HEPES (3:7, V/V, pH=7) solution －5 The mol/L is the probe liquid. Preparing a plurality of 10mL samples to be tested from the probe liquid and different metal ion standard liquids according to the volume ratio of 1:5, and respectively adding the fluorescent probe shown in the formula I and Cu 2+ 、Fe 3+ Adding 5 equivalents of different pesticides into the formed complex systemAs a sample, simultaneously adding the glyphosate solution with the same volume as an intervention pesticide, and detecting the fluorescent probe and Cu shown in the formula I in the presence of different pesticides 2+ 、Fe 3+ The complex system formed recognizes the anti-interference capability of glyphosate.
As shown in FIG. 12, the fluorescent probe of formula I and Cu 2+ 、Fe 3+ The formed complex system has higher sensitivity to glyphosate, and does not influence the fluorescent probe shown in the formula I and Cu when other pesticides exist 2+ 、Fe 3+ And (3) identifying the glyphosate by the formed complex system.
11. Pesticide pair formula I fluorescent probe and Cu 2+ 、Fe 3+ Titration detection of glyphosate by the formed complex
The method comprises the following steps: respectively preparing 50mL standard solutions of different metal ions by using ultrapure water, wherein Cu is contained in each standard solution 2+ 、Fe 3+ The concentration of (2) is 10 -2 mol/L; the concentration of fluorescent probe containing the probe represented by formula I was 1X 10 in DMSO: HEPES (3:7, V/V, pH=7) solution －5 The mol/L is the probe liquid. The probe solution is respectively mixed with Cu 2+ 、Fe 3+ Preparing a plurality of samples to be tested of 10mL from the ion standard solution according to the volume ratio of 1:5, and respectively adding the fluorescent probe shown in the formula I and Cu 2+ 、Fe 3+ Adding glyphosate standard solutions with different volumes into the formed complex system to prepare to-be-detected solutions with different concentration ratios; performing fluorescence spectrum test on the solution to determine the fluorescent probe shown in the formula I and Cu 2+ 、Fe 3+ The recognition capability of the formed complex system to glyphosate with different concentrations.
As shown in FIG. 13, when the concentration of glyphosate reached 50. Mu.M, the fluorescent probe of formula I was shown to be compatible with Cu 2+ The fluorescence intensity of the formed complex system reaches the highest; fluorescent probe shown in formula I and Fe 3+ The fluorescence intensity of the formed complex system reaches a plateau when the concentration of the glyphosate reaches 60 mu M. And fluorescent probe and Cu shown in formula I 2+ 、Fe 3+ The fluorescence intensity of the formed complex system gradually increases, and the detection limits are 0.22 mu M and 0.21 mu M respectively.
In summary, the fluorescent probe shown in the formula I disclosed in the embodiment is an "on-off-on" type ion and pesticide detection fluorescent probe, and can specifically identify Fe 3+ 、Cu 2+ And CN - The detection limits are respectively 0.22 mu M, 0.15 mu M and 0.061 mu M; fluorescent probe and Cu shown in formula I 2+ The complex formed by Fe < 3+ > can further detect glyphosate, and the detection limits are respectively 0.22 mu M and 0.21 mu M, which are obviously lower than the similar fluorescent probes in the prior art. In addition, the detection method adopted by the application is simple and easy to operate, and has potential application value in the aspects of monitoring ions, pesticides and the like in polluted water.
The foregoing is merely a preferred embodiment of the present application, but the scope of the present application is not limited thereto, and any changes or substitutions easily contemplated by those skilled in the art within the technical scope of the present application should be covered by the scope of the present application.
Claims (5)
1. An on-off-on fluorescent probe shown in formula I
(I)。
2. A reagent comprising the "on-off-on" type fluorescent probe of claim 1 and a solvent that dissolves the "on-off-on" type fluorescent probe.
3. A method for preparing an "on-off-on" type fluorescent probe according to claim 1, comprising the step of carrying out reflux reaction on 3- (benzothiazole) -4-hydroxybenzaldehyde and N-N-butyl-4-hydrazino-1, 8-naphthalimide at 70-90 ℃ for 7-9 hours to obtain the "on-off-on" type fluorescent probe.
4. The preparation method according to claim 3, wherein the molar ratio of the 3- (benzothiazole) -4-hydroxybenzaldehyde to the N-N-butyl-4-hydrazino-1, 8-naphthalimide is (1-3): 1.
5. Use of an "on-off-on" fluorescent probe according to claim 1 or a reagent according to claim 2 for the detection of ions selected from the group consisting of Fe and/or for the detection of pesticides in sewage or wastewater 3+ 、Cu 2+ And CN - The ion detection is not used for treating and diagnosing diseases, and the pesticide is glyphosate.
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