CN115353491B - Preparation method and application of dehydroabietyl bis-benzimidazole salicylaldehyde three-ion functional fluorescent probe - Google Patents
Preparation method and application of dehydroabietyl bis-benzimidazole salicylaldehyde three-ion functional fluorescent probe Download PDFInfo
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- CN115353491B CN115353491B CN202210901189.6A CN202210901189A CN115353491B CN 115353491 B CN115353491 B CN 115353491B CN 202210901189 A CN202210901189 A CN 202210901189A CN 115353491 B CN115353491 B CN 115353491B
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- methyl ester
- reaction
- dehydroabietic acid
- bromo
- acid methyl
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- 239000007850 fluorescent dye Substances 0.000 title claims abstract description 43
- 238000002360 preparation method Methods 0.000 title claims abstract description 25
- -1 bis-benzimidazole salicylaldehyde Chemical compound 0.000 title claims description 31
- PGZCJOPTDHWYES-UHFFFAOYSA-N methyl 1,4a-dimethyl-7-propan-2-yl-2,3,4,9,10,10a-hexahydrophenanthrene-1-carboxylate Chemical compound CC(C)C1=CC=C2C3(C)CCCC(C(=O)OC)(C)C3CCC2=C1 PGZCJOPTDHWYES-UHFFFAOYSA-N 0.000 claims abstract description 85
- 238000006243 chemical reaction Methods 0.000 claims abstract description 50
- SMQUZDBALVYZAC-UHFFFAOYSA-N salicylaldehyde Chemical compound OC1=CC=CC=C1C=O SMQUZDBALVYZAC-UHFFFAOYSA-N 0.000 claims abstract description 24
- NFWKVWVWBFBAOV-MISYRCLQSA-N dehydroabietic acid Chemical compound OC(=O)[C@]1(C)CCC[C@]2(C)C3=CC=C(C(C)C)C=C3CC[C@H]21 NFWKVWVWBFBAOV-MISYRCLQSA-N 0.000 claims abstract description 23
- DTQVDTLACAAQTR-UHFFFAOYSA-N Trifluoroacetic acid Chemical compound OC(=O)C(F)(F)F DTQVDTLACAAQTR-UHFFFAOYSA-N 0.000 claims abstract description 20
- 125000003037 imidazol-2-yl group Chemical group [H]N1C([*])=NC([H])=C1[H] 0.000 claims abstract description 19
- QUUCYKKMFLJLFS-UHFFFAOYSA-N Dehydroabietan Natural products CC1(C)CCCC2(C)C3=CC=C(C(C)C)C=C3CCC21 QUUCYKKMFLJLFS-UHFFFAOYSA-N 0.000 claims abstract description 17
- NFWKVWVWBFBAOV-UHFFFAOYSA-N Dehydroabietic acid Natural products OC(=O)C1(C)CCCC2(C)C3=CC=C(C(C)C)C=C3CCC21 NFWKVWVWBFBAOV-UHFFFAOYSA-N 0.000 claims abstract description 17
- 229940118781 dehydroabietic acid Drugs 0.000 claims abstract description 17
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims abstract description 16
- 239000002253 acid Substances 0.000 claims abstract description 14
- 150000004702 methyl esters Chemical class 0.000 claims abstract description 13
- GEYOCULIXLDCMW-UHFFFAOYSA-N 1,2-phenylenediamine Chemical compound NC1=CC=CC=C1N GEYOCULIXLDCMW-UHFFFAOYSA-N 0.000 claims abstract description 12
- INAAIJLSXJJHOZ-UHFFFAOYSA-N pibenzimol Chemical compound C1CN(C)CCN1C1=CC=C(N=C(N2)C=3C=C4NC(=NC4=CC=3)C=3C=CC(O)=CC=3)C2=C1 INAAIJLSXJJHOZ-UHFFFAOYSA-N 0.000 claims abstract description 12
- 238000000034 method Methods 0.000 claims abstract description 11
- 238000005886 esterification reaction Methods 0.000 claims abstract description 8
- 230000031709 bromination Effects 0.000 claims abstract description 4
- 238000005893 bromination reaction Methods 0.000 claims abstract description 4
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- 125000002252 acyl group Chemical group 0.000 claims abstract description 3
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- 239000000523 sample Substances 0.000 claims description 27
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- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 24
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- 230000035484 reaction time Effects 0.000 claims description 14
- FYSNRJHAOHDILO-UHFFFAOYSA-N thionyl chloride Chemical compound ClS(Cl)=O FYSNRJHAOHDILO-UHFFFAOYSA-N 0.000 claims description 14
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 12
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- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical compound [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 claims description 8
- ILEIUTCVWLYZOM-UHFFFAOYSA-N 2-hydroxy-5-methylbenzaldehyde Chemical compound CC1=CC=C(O)C(C=O)=C1 ILEIUTCVWLYZOM-UHFFFAOYSA-N 0.000 claims description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 6
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- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 5
- 229910001431 copper ion Inorganic materials 0.000 claims description 5
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 5
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- MICMHFIQSAMEJG-UHFFFAOYSA-N 1-bromopyrrolidine-2,5-dione Chemical compound BrN1C(=O)CCC1=O.BrN1C(=O)CCC1=O MICMHFIQSAMEJG-UHFFFAOYSA-N 0.000 claims description 2
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- UIIMBOGNXHQVGW-DEQYMQKBSA-M Sodium bicarbonate-14C Chemical class [Na+].O[14C]([O-])=O UIIMBOGNXHQVGW-DEQYMQKBSA-M 0.000 claims description 2
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- PGZCJOPTDHWYES-HMXCVIKNSA-N methyl (1r,4as,10ar)-1,4a-dimethyl-7-propan-2-yl-2,3,4,9,10,10a-hexahydrophenanthrene-1-carboxylate Chemical compound CC(C)C1=CC=C2[C@@]3(C)CCC[C@](C(=O)OC)(C)[C@@H]3CCC2=C1 PGZCJOPTDHWYES-HMXCVIKNSA-N 0.000 claims description 2
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Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D235/00—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, condensed with other rings
- C07D235/02—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, condensed with other rings condensed with carbocyclic rings or ring systems
- C07D235/04—Benzimidazoles; Hydrogenated benzimidazoles
- C07D235/18—Benzimidazoles; Hydrogenated benzimidazoles with aryl radicals directly attached in position 2
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K49/00—Preparations for testing in vivo
- A61K49/001—Preparation for luminescence or biological staining
- A61K49/0013—Luminescence
- A61K49/0017—Fluorescence in vivo
- A61K49/0019—Fluorescence in vivo characterised by the fluorescent group, e.g. oligomeric, polymeric or dendritic molecules
- A61K49/0021—Fluorescence in vivo characterised by the fluorescent group, e.g. oligomeric, polymeric or dendritic molecules the fluorescent group being a small organic molecule
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
- C09K11/06—Luminescent, e.g. electroluminescent, chemiluminescent materials containing organic luminescent materials
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
- G01N21/62—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light
- G01N21/63—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light optically excited
- G01N21/64—Fluorescence; Phosphorescence
- G01N21/6428—Measuring fluorescence of fluorescent products of reactions or of fluorochrome labelled reactive substances, e.g. measuring quenching effects, using measuring "optrodes"
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
- C09K2211/10—Non-macromolecular compounds
- C09K2211/1003—Carbocyclic compounds
- C09K2211/1007—Non-condensed systems
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
- C09K2211/10—Non-macromolecular compounds
- C09K2211/1018—Heterocyclic compounds
- C09K2211/1025—Heterocyclic compounds characterised by ligands
- C09K2211/1044—Heterocyclic compounds characterised by ligands containing two nitrogen atoms as heteroatoms
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
- G01N21/62—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light
- G01N21/63—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light optically excited
- G01N21/64—Fluorescence; Phosphorescence
- G01N21/6428—Measuring fluorescence of fluorescent products of reactions or of fluorochrome labelled reactive substances, e.g. measuring quenching effects, using measuring "optrodes"
- G01N2021/6432—Quenching
Abstract
The invention discloses a preparation method and application of a dehydroabietyl bisbenzimidazole salicylaldehyde three-ion functional fluorescent probe, wherein the dehydroabietic acid is subjected to acyl chlorination, methyl esterification, bromination and dinitration reaction to prepare 12-bromo-13, 14-dinitrodehydroabietic acid methyl ester; reducing the 12-bromo-13, 14-dinitrodehydroabietic acid methyl ester by Fe/HCl to obtain 12-bromo-13, 14-diamino deisopropyl dehydroabietic acid methyl ester; o-phenylenediamine and 5-bromosalicylaldehyde undergo a cyclization reaction and then react with trifluoroacetic acid to prepare 3- (1H-benzo [ d ]]Imidazol-2-yl) -2-hydroxy-5-methylbenzaldehyde; 12-bromo-13, 14-diamino deisopropyl dehydroabietyl acid methyl ester and 3- (1H-benzo [ d ]]Imidazole-2-yl) -2-hydroxy-5-methylbenzaldehyde reacts to prepare a fluorescent probe which can be used as the fluorescent probe to detect Zn 2+ 、Cu 2+ 、ClO － The method comprises the steps of carrying out a first treatment on the surface of the And effectively identify Zn in biological imaging 2+ 、Cu 2+ 、ClO － 。
Description
Technical Field
The invention belongs to the field of organic synthesis, and particularly relates to a preparation method and application of a dehydroabietyl bis-benzimidazole salicylaldehyde three-ion functional fluorescent probe.
Background
Zinc ions are the second most abundant transition metal ion in the human body and are present in proteins, so that the homeostasis of zinc ions is maintained by many proteins, which once destroyed can lead to the onset of a range of diseases, such as: parkinson's disease, alzheimer's disease, amyotrophic lateral sclerosis, cerebral ischemia (ischemic stroke), epilepsy, prostate cancer, diabetes, immune dysfunction and infantile diarrhea.
Copper ions are the third most abundant transition metal ions involved in various physiological processes such as enzyme function, blood formation, transcription of respiratory and biological processes, neurotransmitter synthesis and metabolism, and antioxidant defenses. However, once the homeostasis is lost, various diseases such as coronary heart disease, liver disease, anemia, etc. are caused. Hypochlorous acid (HClO) is an important component of Reactive Oxygen Species (ROS), and is widely used in home bleaching, drinking water disinfection, etc., and is a natural protective barrier against invasion and inflammation of microorganisms, and a large amount of HClO is a great hazard to the health of organisms, resulting in tissue necrosis and diseases such as cardiovascular diseases, neuronal cytopathy, liver, lung injury, cancer, etc.
The fluorescent probe method has the advantages of high detection speed, wide detection environment, high sensitivity, strong specificity and the like. Thus overcoming the shortcomings of traditional ion detection such as atomic absorption, spectrophotometry, cyclic voltammetry and the like.
In recent years, many fluorescent probes have been studied for metal detection technologies, such as coumarin fluorescent probes for mercury ion detection and rhodamine fluorescent probes for ferric ion detection, but all the existing studies are single-channel detection probes.
Disclosure of Invention
This section is intended to outline some aspects of embodiments of the invention and to briefly introduce some preferred embodiments. Some simplifications or omissions may be made in this section as well as in the description summary and in the title of the application, to avoid obscuring the purpose of this section, the description summary and the title of the invention, which should not be used to limit the scope of the invention.
The present invention has been made in view of the above and/or problems occurring in the prior art.
Therefore, the invention aims to overcome the defects in the prior art and provide the dehydroabietyl bisbenzimidazole salicylaldehyde three-ion functional fluorescent probe.
In order to solve the technical problems, the invention provides the following technical scheme: the dehydroabietyl bis-benzimidazole salicylaldehyde three-ion functional fluorescent probe is named as methyl-2- (3- (1H-benzo [ d ] imidazol-2-yl) -2-hydroxy-5-methylphenyl) -11-bromo-6, 9 a-dimethyl-4, 5a,6,7,8,9 a-octahydro-3H-phenanthroline [1,2-d ] imidazole-6-methyl ester, and has the structural formula:
the invention further aims to overcome the defects in the prior art and provide a preparation method of the dehydroabietyl bisbenzimidazole salicylaldehyde three-ion functional fluorescent probe.
In order to solve the technical problems, the invention provides the following technical scheme: a preparation method of dehydroabietyl bis-benzimidazole salicylaldehyde three-ion functional fluorescent probe comprises,
the dehydroabietic acid is subjected to acyl chlorination, methyl esterification, bromination and dinitration reaction to prepare 12-bromo-13, 14-dinitrodehydroabietic acid methyl ester;
reducing the 12-bromo-13, 14-dinitrodehydroabietic acid methyl ester by Fe/HCl to obtain 12-bromo-13, 14-diamino deisopropyl dehydroabietic acid methyl ester;
o-phenylenediamine and 5-bromosalicylaldehyde undergo a cyclization reaction and then react with trifluoroacetic acid to prepare 3- (1H-benzo [ d ] imidazole-2-yl) -2-hydroxy-5-methylbenzaldehyde;
the fluorescent probe is prepared by reacting methyl 12-bromo-13, 14-diamino deisopropyl dehydroabietate with 3- (1H-benzo [ d ] imidazol-2-yl) -2-hydroxy-5-methylbenzaldehyde.
As a preferable scheme of the preparation method of the dehydroabietyl bisbenzimidazole salicylaldehyde three-ion functional fluorescent probe, the preparation method comprises the following steps: the preparation method of the 12-bromo-13, 14-nitro dehydroabietic acid methyl ester comprises the following steps of,
adding thionyl chloride into the dehydroabietic acid toluene solution for reaction, performing vacuum spin-drying after the reaction is finished, adding methanol for methyl esterification reaction, performing spin-drying after the reaction is finished, and adding ethanol for dissolution and crystallization to obtain dehydroabietic acid methyl ester; wherein the concentration of the dehydroabietic acid toluene solution is 0.4-0.6 g/mL, the dosage ratio of dehydroabietic acid to thionyl chloride is 1 g:0.2-0.3 mL, and the dosage ratio of dehydroabietic acid to methanol is 1 g:1-3 mL; the reaction temperature of dehydroabietic acid and thionyl chloride is 75-80 ℃ and the reaction time is 2-4 h; the methyl esterification reaction temperature is 75-80 ℃ and the reaction time is 2-4 h;
adding N-bromosuccinimide NBS into an acetonitrile solution of methyl dehydroabietate, carrying out a light-shielding normal-temperature reaction, carrying out rotary evaporation after the reaction is finished, washing with dichloromethane twice, and dissolving and crystallizing with methanol to obtain 12-bromodehydroabietate; wherein the concentration of the dehydroabietic acid methyl ester acetonitrile solution is 0.15-0.20 g/mL, the dosage ratio of the dehydroabietic acid methyl ester to NBS is 1:1.2-1:1.5, and the reaction time is 20-24 h;
under the ice bath condition, adding the 12-bromine dehydroabietic acid methyl ester into mixed acid which is formed by fully mixing fuming nitric acid and concentrated sulfuric acid, stirring, directly pouring the mixed acid into ice water after the reaction is finished, standing, carrying out reduced pressure suction filtration, washing for multiple times, and purifying by using petroleum ether and ethyl acetate in a volume ratio of 500:1-200:1 through a column to obtain pure 12-bromine-13, 14-dinitrodehydroabietic acid methyl ester; wherein the dosage ratio of the 12-bromine dehydroabietic acid methyl ester to fuming nitric acid is 1 g:6-7 ml, the dosage ratio of the 12-bromine dehydroabietic acid methyl ester to concentrated sulfuric acid is 1-3 g:1ml, and the digestion reaction is carried out for 0.5-1.5 h under the ice bath condition.
As a preferable scheme of the preparation method of the dehydroabietyl bisbenzimidazole salicylaldehyde three-ion functional fluorescent probe, the preparation method comprises the following steps: the preparation method of the 12-bromo-13, 14-diamino deisopropyl dehydroabietic acid methyl ester comprises the following steps of,
dissolving 12-bromo-13, 14-dinitrodeisopropyl dehydroabietic acid methyl ester in HFIP and distilled water, reacting with iron powder and concentrated hydrochloric acid, stirring and refluxing, filtering the iron powder after the reaction is finished, neutralizing to be neutral by using saturated sodium bicarbonate, purifying by using petroleum ether and ethyl acetate in a volume ratio of 28:1, and obtaining pure 12-bromo-13, 14-diamino deisopropyl dehydroabietic acid methyl ester;
wherein the dosage ratio of the 12-bromo-13, 14-dinitrate dehydroabietic acid methyl ester to distilled water is 0.22g to 1ml, the dosage ratio of the 12-bromo-13, 14-dinitrate dehydroabietic acid methyl ester to iron powder is 0.22g to 0.5g, the dosage ratio of the 12-bromo-13, 14-dinitrate dehydroabietic acid methyl ester to concentrated hydrochloric acid is 0.22g to 800 mul, and the dosage ratio of the 12-bromo-13, 14-dinitrate dehydroabietic acid methyl ester to HFIP is 1g to 4-5 ml, and the reaction time is 4.5h.
As a preferable scheme of the preparation method of the dehydroabietyl bisbenzimidazole salicylaldehyde three-ion functional fluorescent probe, the preparation method comprises the following steps: the preparation method of the 3- (1H-benzo [ d ] imidazole-2-yl) -2-hydroxy-5-methylbenzaldehyde comprises the following steps of,
under the protection of nitrogen, absolute ethyl alcohol is used as an organic solvent, o-phenylenediamine and 5-methyl salicylaldehyde react, sodium sulfite is used as a catalyst, absolute ethyl alcohol is used for recrystallization after stirring reflux reaction is finished, and pure benzimidazole 2- (1H-benzo [ d ] imidazole-2-yl) -4-cresol is prepared; wherein the dosage ratio of the o-phenylenediamine to the 5-methyl salicylaldehyde is 1.22g to 1.56g, the dosage ratio of the o-phenylenediamine to the anhydrous sodium sulfate is 1.22g to 1.59g, the reaction temperature is 78 ℃, and the reaction time is 12 hours;
reacting trifluoroacetic acid with benzimidazole 2- (1H-benzo [ d ] imidazole-2-yl) -4-cresol, taking hexamethylenetetramine as a catalyst, and purifying by using petroleum ether and ethyl acetate in a volume ratio of 100-20:1 to prepare pure 3- (1H-benzo [ d ] imidazole-2-yl) -2-hydroxy-5-methylbenzaldehyde; wherein the dosage ratio of trifluoroacetic acid to benzimidazole 2- (1H-benzo [ d ] imidazol-2-yl) -4-cresol is 0.3g to 5ml, the dosage ratio of hexamethylenetetramine to benzimidazole 2- (1H-benzo [ d ] imidazol-2-yl) -4-cresol is 0.3g to 0.9g, the reaction temperature is 110 ℃, and the reaction time is 12H.
As a preferable scheme of the preparation method of the dehydroabietyl bisbenzimidazole salicylaldehyde three-ion functional fluorescent probe, the preparation method comprises the following steps: the reaction of the 12-bromo-13, 14-diamino deisopropyl dehydroabietic acid methyl ester and 3- (1H-benzo [ d ] imidazol-2-yl) -2-hydroxy-5-methylbenzaldehyde takes DMA as an organic solvent, sodium bisulfite as a catalyst, and the reaction dosage mole ratio of the 3- (1H-benzo [ d ] imidazol-2-yl) -2-hydroxy-5-methylbenzaldehyde to the pure 12-bromo-13, 14-diamino deisopropyl dehydroabietic acid methyl ester is 1:1, the reaction temperature is 110 ℃, and the reaction time is 10-12H; after the reaction, the solid was precipitated by standing at room temperature to prepare a pure probe.
The invention further aims to overcome the defects in the prior art and provide an application of the dehydroabietyl bisbenzimidazole salicylaldehyde three-ion functional fluorescent probe in detecting copper ions, hypochlorite ions and zinc ions, wherein: under the action of copper ions, the fluorescence intensity of the fluorescent probe is reduced to be quenched, and the lowest detection limit of copper is reduced to 3.8nM level; under the action of hypochlorite ions, the fluorescence changes from yellow green to cyan, and the minimum detection limit is 0.5 mu M; under the action of zinc ions, the fluorescence is changed from yellow green to blue-violet, and the minimum detection limit is 0.3 mu M; fluorescent probe pair Cu 2+ 、ClO - 、Zn 2+ The detection of ions is not interfered by other coexisting ions.
The invention further aims to overcome the defects in the prior art and provide an application of the dehydroabietyl bisbenzimidazole salicylaldehyde three-ion functional fluorescent probe in cell imaging and zebra fish imaging.
The invention has the beneficial effects that:
the invention uses dehydroabietic acid extracted from natural renewable resources disproportionated rosin as raw material to prepare methyl-2- (3- (1H-benzo [ d ])]Imidazol-2-yl) -2-hydroxy-5-methylphenyl) -11-bromo-6, 9 a-dimethyl-4, 5a,6,7,8,9 a-octahydro-3H-phenanthroline [1,2-d]Imidazole-6-methyl ester (CPS), capable of selectively reacting with Cu 2+ Complexing, fluorescence quenching, and ClO － The reaction is that the fluorescence is changed from yellow green to cyan, and the fluorescence is changed from Zn 2+ Complexing, changing fluorescence from yellow-green to blue-violet, the compound can be used as fluorescent probe to detect Zn 2+ 、Cu 2+ 、ClO － The method comprises the steps of carrying out a first treatment on the surface of the And effectively identify Zn in biological imaging 2+ 、Cu 2+ 、ClO － 。
Drawings
In order to more clearly illustrate the technical solutions of the embodiments of the present invention, the drawings that are needed in the description of the embodiments will be briefly described below, it being obvious that the drawings in the following description are only some embodiments of the present invention, and that other drawings may be obtained according to these drawings without inventive effort for a person skilled in the art. Wherein:
FIG. 1 is a schematic diagram of a process for synthesizing methyl-2- (3- (1H-benzo [ d ] imidazol-2-yl) -2-hydroxy-5-methylphenyl) -11-bromo-6, 9 a-dimethyl-4, 5a,6,7,8,9 a-octahydro-3H-phenanthroline [1,2-d ] imidazol-6-methyl ester according to an embodiment of the present invention.
FIG. 2 shows the addition of Zn to CPS solutions of fluorescent probes in accordance with an embodiment of the present invention 2+ Is a fluorescent absorption spectrum of (2).
FIG. 3 shows Cu addition to CPS solution of fluorescent probe in the embodiment of the present invention 2+ Is a fluorescent absorption spectrum of (2).
FIG. 4 shows the addition of ClO to CPS solution of fluorescent probe according to an embodiment of the present invention － Is a fluorescent absorption spectrum of (2).
FIG. 5 shows the CPS and Zn of the fluorescent probe under 365nm ultraviolet light in an embodiment of the present invention 2+ 、Cu 2+ 、ClO － Contrast photographs of other ions.
FIG. 6 is a graph showing fluorescence absorption spectra of CPS of fluorescent probe and different ions according to the present invention.
FIG. 7 is a fluorescence imaging of probes and the addition of different detection ions in onion epidermal cells according to an embodiment of the present invention.
FIG. 8 is a fluorescence imaging of zebra fish with the addition of different detection ions in an embodiment of the present invention.
Detailed Description
In order that the above-recited objects, features and advantages of the present invention will become more apparent, a more particular description of the invention will be rendered by reference to specific embodiments thereof which are illustrated in the appended drawings.
In the following description, numerous specific details are set forth in order to provide a thorough understanding of the present invention, but the present invention may be practiced in other ways other than those described herein, and persons skilled in the art will readily appreciate that the present invention is not limited to the specific embodiments disclosed below.
Further, reference herein to "one embodiment" or "an embodiment" means that a particular feature, structure, or characteristic can be included in at least one implementation of the invention. The appearances of the phrase "in one embodiment" in various places in the specification are not necessarily all referring to the same embodiment, nor are separate or alternative embodiments mutually exclusive of other embodiments.
Disproportionated rosin of the present invention was purchased from Guangdong Walin Co., ltd (dehydroabietic acid content 59.93%); chromatographic silica gel (300-400 meshes) purchased from Qingdao ocean chemical plant and chemically pure; ethanolamine, purchased from Anhui Zengsheng technologies Co., ltd., analytically pure; iron powder, available from Tianjin Fengsha chemical reagent technology Co., ltd., analytically pure; o-phenylenediamine is purchased from Chengdu Kelong chemical reagent factories and is analytically pure; 5-methyl salicylaldehyde, available from saen chemical technologies, inc; trifluoroacetic acid, purchased from Anhui Zengsheng technologies, inc., analytically pure.
Example 1
The embodiment provides a preparation method of a dehydroabietyl bis-benzimidazole salicylaldehyde three-ion functional fluorescent probe, which comprises the following specific steps:
(1) The preparation of the 12-bromo-13, 14-dinitrodehydroabietic acid methyl ester comprises the steps of methyl esterification, bromination and nitration of dehydroabietic acid, and the specific process is as follows:
weighing 30g dehydroabietic acid, dissolving in 60mL of toluene, adding 11mL of thionyl chloride, reacting for 3h at 78-80 ℃, spin-drying in vacuum, adding 60mL of methanol, reacting for 3h at 78-80 ℃, spin-drying, adding 30mL of ethanol, dissolving and crystallizing to obtain dehydroabietic acid methyl ester;
accurately weighing 5g of dehydroabietic acid methyl ester, dissolving in 30mL of acetonitrile, adding 4g of N-bromosuccinimide, reacting for 24 hours at normal temperature in a dark place, performing rotary evaporation, washing twice with dichloromethane, and dissolving and crystallizing with 100mL of methanol to obtain 12-bromodehydroabietic acid methyl ester;
12-bromo-13, 14-dinitrodehydroabietic acid methyl ester:
3g of methyl 12-bromodehydroabietate is accurately weighed and dissolved in 19mL of fuming nitric acid and 1.5mL of concentrated sulfuric acid, the mixture is reacted for 1h under ice bath condition, after the reaction is finished, the mixture is poured into ice water, the mixture is extracted three times by methylene dichloride, washed three times by water, washed once by saturated sodium bicarbonate water solution, washed once by saturated salt, dried by anhydrous sodium sulfate for water removal, and recrystallized by 20mL of ethanol to obtain light yellow methyl 12-bromo-13, 14-dinitrodehydroabietate.
12-bromo-13, 14-diamino deisopropyl dehydroabietyl methyl ester:
0.44g of 12-bromo-13, 14-dinitrodehydroabietic acid methyl ester is accurately weighed and dissolved in 10mL of ethanol, 0.56g of iron powder and 20mL of hydrochloric acid solution (2 mol/L) are added, stirring reaction is carried out for 1h at 45 ℃, ethyl acetate is used for extraction three times after the reaction is finished, water washing is carried out three times, saturated sodium bicarbonate water solution is used for washing once, saturated salt water is used for washing once, anhydrous sodium sulfate is used for drying and dewatering, and crude oily 12-bromo-13, 14-diamino dehydroabietic acid methyl ester is obtained after spin drying.
(2) The preparation of 3- (1H-benzo [ d ] imidazole-2-yl) -2-hydroxy-5-methylbenzaldehyde comprises the steps of reacting o-phenylenediamine with 5-bromosalicylaldehyde and then reacting with trifluoroacetic acid, wherein the specific process is as follows:
1.22g of o-phenylenediamine, 1.56g of 5-methyl salicylaldehyde and 1.59g of sodium sulfite are accurately weighed and mixed in 22ml of absolute ethyl alcohol, the temperature is 78 ℃, the mixture is stirred and refluxed for 17 hours under the protection of nitrogen, and after the reaction is finished, the mixture is stood still at room temperature for recrystallization, thus obtaining pure benzimidazole 2- (1H-benzo [ d ] imidazole-2-yl) -4-cresol.
Accurately weighing 0.3g of hexamethylenetetramine, carrying out ultrasonic treatment on the hexamethylenetetramine and 0.9g of benzimidazole 2- (1H-benzo [ d ] imidazol-2-yl) -4-cresol in 5ml of trifluoroacetic acid at the temperature of 110 ℃, refluxing and stirring overnight, extracting with ethyl acetate three times after the reaction is finished, washing with water three times, washing with saturated sodium bicarbonate aqueous solution once, washing with saturated salt once, drying with anhydrous sodium sulfate to remove water, carrying out spin-drying to obtain yellow oily matter, and purifying by a silica gel column and obtaining pure 3- (1H-benzo [ d ] imidazol-2-yl) -2-hydroxy-5-methylbenzaldehyde.
(3) The preparation of the probe CPS, the reaction of the methyl 12-bromo-13, 14-diamino deisopropyl dehydroabietate and 3- (1H-benzo [ d ] imidazole-2-yl) -2-hydroxy-5-methylbenzaldehyde comprises the following specific steps:
accurately weighing 0.44g of 12-bromo-13, 14-diamino deisopropyl dehydroabietic acid methyl ester and 0.16g of 3- (1H-benzo [ d ] imidazol-2-yl) -2-hydroxy-5-methylbenzaldehyde, ultrasonically adding 120mg of sodium bisulphite into 10ml of DMA, refluxing and stirring overnight at 110 ℃, and standing at room temperature for recrystallization after the reaction is finished to obtain the pure probe CPS.
The characterization data of the product are M.p.160.2-161.3 ℃; 1 H NMR(600MHz,DMSO-d 6 ) 1 H NMR(600MHz,DMSO-d 6 )δ1.25(d,J＝8.9Hz,6H),1.41(dt,J＝14.1,7.1Hz,1H),1.49(dd,J＝13.0,7.8Hz,1H),1.60–1.65(m,1H),1.70(qd,J＝10.2,7.7,3.5Hz,2H),1.74–1.82(m,1H),1.86–1.98(m,1H),2.18(dd,J＝12.6,2.1Hz,1H),2.46(s,4H),2.79(s,0H),2.90–3.00(m,1H),3.19(dd,J＝17.3,6.7Hz,1H),3.66(s,3H),7.24(dq,J＝6.5,3.3Hz,2H),7.43(s,1H),7.65–7.72(m,2H),8.22–8.27(m,2H),12.98(s,3H).ESI-MS:m/z calcd for C 33 H 33 BrN 4 O 3 [M+H] + 612.1736,found 613.1822。
example 2
Optimization of the preparation method of dehydroabietyl Schiff base derivatives:
test 1: accurately weighing 0.44g of 12-bromo-13, 14-diamino deisopropyl dehydroabietic acid methyl ester and 0.16g of 3- (1H-benzo [ d ] imidazol-2-yl) -2-hydroxy-5-methylbenzaldehyde, ultrasonically adding 120mg of sodium bisulphite into 10ml of DMA, refluxing and stirring for 12 hours at the temperature of 110 ℃, standing at room temperature after the reaction is finished, and recrystallizing to obtain pure probe CPS with the yield of 90 percent
Test 2: 0.44g of methyl 12-bromo-13, 14-diaminodeisopropyl dehydroabietate and 0.16g of 3- (1H-benzo [ d ] imidazol-2-yl) -2-hydroxy-5-methylbenzaldehyde are accurately weighed, and added with 120mg of p-toluenesulfonic acid in 10ml of DMA by ultrasound, at 110 ℃, stirred under reflux for 12H, and recrystallized at room temperature after the reaction is finished to obtain pure probe CPS with a yield of 61%.
Test 3: 0.44g of methyl 12-bromo-13, 14-diaminodeisopropyl dehydroabietate and 0.16g of 3- (1H-benzo [ d ] imidazol-2-yl) -2-hydroxy-5-methylbenzaldehyde are accurately weighed, the mixture is ultrasonically stirred in 10ml of DMA at 78 ℃ under reflux for 12 hours, and after the reaction is finished, the mixture is placed at room temperature for recrystallization to obtain pure probe CPS, and the yield is 30%.
Test 4: 0.44g of methyl 12-bromo-13, 14-diaminodeisopropyl dehydroabietate and 0.16g of 3- (1H-benzo [ d ] imidazol-2-yl) -2-hydroxy-5-methylbenzaldehyde are accurately weighed, the mixture is ultrasonically stirred in 10ml of DMA at 110 ℃ under reflux for 5 hours, and after the reaction is finished, the mixture is placed at room temperature for recrystallization to obtain pure probe CPS, and the yield is 45%.
Test 5: 0.44g of methyl 12-bromo-13, 14-diaminodeisopropyl dehydroabietate and 0.16g of 3- (1H-benzo [ d ] imidazol-2-yl) -2-hydroxy-5-methylbenzaldehyde are accurately weighed, the mixture is ultrasonically treated in 10ml of ethanol at 110 ℃, reflux and stirring are carried out for 12 hours, and after the reaction is finished, the mixture is placed at room temperature for recrystallization to obtain pure probe CPS, and the yield is 60%.
TABLE 1 yields of probe CPS under different conditions
Note that: and/indicates no catalyst.
As can be seen from Table 1, the conditions of run 1 gave higher reaction yields relative to the other reaction conditions, and thus the reaction was conducted using this preferred condition.
Example 3
Dissolving CPS probe in absolute ethanol to obtain 1×10 solution -3 M solution, 100. Mu.L stock solution is added into 10ml ethanol water solution (ethanol: water 2:8) to prepare 10×10 -6 M solution, 5. Mu.L of Zn was added each time 2+ (1×10 -2 M),10μL ClO - (1×10 -2 M),5μL Cu 2+ (1×10 -2 M), measuring the absorption spectrum of the ion pair probe CPS with different concentrations.
As shown in FIG. 2, zn is added 2+ After that, along with Zn 2+ The concentration increases, green fluorescence at 515nm gradually decreases and quenches gradually, and fluorescence at 440nm gradually increases, and it can be seen that Zn at 0 to 50. Mu.M 2+ In the concentration range, the fluorescence intensity of the compound CPS has good linear correlation with the concentration of ions, and a linear regression equation y=0.01029x+0.75383, R 2 = 0.99404, calculate Zn 2+ The detection limit of (2) was 0.3. Mu.M.
As shown in FIG. 3, cu was added at different concentrations 2+ After that, with Cu 2+ As can be seen from the increase in concentration, the green fluorescence at 515nm gradually decreased straightTo quench at 0 to 85 mu M of Cu 2+ In the concentration range, the image shows that the fluorescence intensity of the compound CPS has good linear correlation with the concentration of ions, and the linear regression equation y= -8.60459x+770.57489, R 2 = 0.99401, calculated Cu 2+ The limit of detection of (2) is 3.8nM.
As shown in fig. 4, with ClO － The green fluorescence at 515nm gradually decreased while the blue fluorescence at 467nm gradually increased with increasing concentration. In a linear relationship in the concentration range of 0-100 mu M. The linear equation is y= -0.02825x-0.04261, r2= 0.99575. ClO-minimum limit of detection was 0.5. Mu.M.
The above results demonstrate that CPS can be combined with Zn 2+ And Cu 2+ Complexing with ClO － The reaction takes place.
Example 4
Dissolving CPS probe in absolute ethanol to obtain 1×10 solution -3 M solution, 100. Mu.L stock solution is added into 10ml ethanol water solution (ethanol: water 2:8) to prepare 1X 10 -5 M solution, 100. Mu.L (1X 10) -3 M)Cu 2+ ,ClO － ，Zn 2+ And equimolar amounts of other ions, e.g. Hg 2+ ,Al 3+ ,Cr 3+ ,Cd 2+ ，Mg 2+ ,Mn 2+ ,La 3+ ,Fe 2+ ，ONOO - ,PO 4 3- ,HPO 4 2- ，SO 4 2- ,CO 3 2- ,NO 4- ，BuOO,H 2 O 2 ,SO 4 2- ，BuOOH,HSO 3 - ，H 2 PO 4 - ,NO 2 - ,SO 3 - As shown in FIG. 5, cu was added when observed under a 365nm ultraviolet lamp 2+ After that, the green fluorescence is gradually weakened until quenching, clO is added － The green fluorescence gradually weakens, the cyan fluorescence gradually appears and gradually increases, and Zn is added 2+ The green fluorescence gradually becomes smaller and quenched, the blue-violet fluorescence gradually becomes stronger, and the fluorescence is not changed obviously when other ions are added, as shown in figure 6, the fluorescence intensity is not changed obviously when other ions are added, which indicates that the compound and Cu are 2+ 、Hg 2+ Complexing withClO － React with other ions, but not with other ions. The compound can be used for effectively recognizing Cu 2+ 、ClO － 、Zn 2+ Fluorescent probes for ions.
Example 5
Application of biological imaging of probes:
to explore CPY versus cell Cu 2+ 、ClO － 、Zn 2+ Sensing applicability, taking white part of inner core of fresh onion from vegetable market, tearing off epidermis, placing epidermis into six-hole plate containing water, adding probe (10 μm) into six-hole plate, soaking for half an hour, adding Cu of 0 μm, 15 μm, 30 μm 2+ 、ClO － 、Zn 2+ Then soaked overnight. The next day, the excess ions were removed by washing 3 times with clean water. And then imaged under a confocal laser microscope. As shown in fig. 7, CPS entry into cells showed yellow-green fluorescence, indicating that the probe could penetrate the cell membrane and effectively perform cell imaging.
As shown in FIG. 7 (a), zn is added 2+ Then quenching the yellow-green fluorescence, gradually generating blue-violet fluorescence and gradually enhancing the blue-violet fluorescence; as shown in FIG. 7 (b), clO is added － Changing from yellow green to cyan; as shown in FIG. 7 (c), cu is added 2+ The yellowish green color gradually disappears. Indicating that ions can diffuse into cells and act on the probe, indicating that the probe is successfully used for cell imaging and has the function of detecting Zn in cells 2+ 、ClO － 、Cu 2+ Is effective in (1). It can be seen that CPS shows yellowish green fluorescence into cells, indicating that the probe can penetrate cell membranes and effectively perform cell imaging; as shown in FIG. 7 (a), with Zn 2+ The concentration increased, the yellow-green fluorescence gradually disappeared, and the blue-violet fluorescence gradually increased, as shown in FIG. 7 (b), with ClO － With increasing concentration, the yellow-green fluorescence gradually disappeared, and the cyan fluorescence gradually appeared and increased, as shown in FIG. 7 (c), with Cu 2+ The increasing concentration of (2) gradually reduces fluorescence until it disappears, indicating that ions can diffuse into the cell and act on the probe, indicating that the probe was successfully used for cell imaging.
Example 6
Pouring zebra fish eggs into a beaker, adding nutrient solution, placing the beaker into a constant-temperature water bath kettle filled with water, adjusting the temperature to 26 ℃, standing for 1-3 days for hatching, placing young fish in six pore plates for hatching zebra fish, respectively adding probes (10 mu M), wherein one pore is not added with ions for comparison, and respectively adding Cu of 0 mu M, 15 mu M and 30 mu M into the other three pores 2+ 、ClO － 、Zn 2+ Culturing at constant temperature for 3h.
Subsequent imaging under a confocal laser microscope, CPS showed yellowish green fluorescence in the fish body as shown in FIG. 8, indicating that the probe could enter the fish body and effectively image as shown in FIG. 8 (a), with Zn 2+ The concentration increased, the yellow-green fluorescence gradually disappeared, and the blue-violet fluorescence gradually increased, as shown in FIG. 8 (b), with ClO － With increasing concentration, the yellow-green fluorescence gradually disappeared, and the cyan fluorescence gradually appeared and increased, as shown in FIG. 8 (c), with Cu 2+ The concentration of (2) increases and the fluorescence gradually decreases until it disappears, indicating that ions can diffuse into the fish body and act on the probe, indicating that the probe was successfully used for biological imaging, with Cu detection 2+ 、ClO - 、Zn 2+ Is effective in (1).
It should be noted that the above embodiments are only for illustrating the technical solution of the present invention and not for limiting the same, and although the present invention has been described in detail with reference to the preferred embodiments, it should be understood by those skilled in the art that the technical solution of the present invention may be modified or substituted without departing from the spirit and scope of the technical solution of the present invention, which is intended to be covered in the scope of the claims of the present invention.
Claims (10)
1. A dehydroabietyl bis-benzimidazole salicylaldehyde three-ion functional fluorescent probe is characterized in that: the structural formula of the compound of the fluorescent probe is as follows:
。
2. the method for preparing the dehydroabietyl bisbenzimidazole salicylaldehyde three-ion functional fluorescent probe according to claim 1, which is characterized in that: comprising the steps of (a) a step of,
the dehydroabietic acid is subjected to acyl chlorination, methyl esterification, bromination and dinitration reaction to prepare 12-bromo-13, 14-dinitro deisopropyl dehydroabietic acid methyl ester;
reducing the 12-bromo-13, 14-dinitro deisopropyl dehydroabietic acid methyl ester by Fe/HCl to obtain 12-bromo-13, 14-diamino deisopropyl dehydroabietic acid methyl ester;
o-phenylenediamine and 5-methyl salicylaldehyde undergo a cyclization reaction and then react with trifluoroacetic acid to prepare 3- (1H-benzo [ d ] imidazole-2-yl) -2-hydroxy-5-methylbenzaldehyde;
12-bromo-13, 14-diamino deisopropyl dehydroabietic acid methyl ester and 3- (1)HBenzo [ d ]]The imidazole-2-yl) -2-hydroxy-5-methylbenzaldehyde reacts to prepare the fluorescent probe.
3. The method for preparing the dehydroabietyl bis-benzimidazole salicylaldehyde three-ion functional fluorescent probe according to claim 2, which is characterized in that: the preparation method of the 12-bromo-13, 14-dinitro deisopropyl dehydroabietic acid methyl ester comprises the steps of adding thionyl chloride into dehydroabietic acid toluene solution for reaction, performing vacuum spin-drying after the reaction is finished, adding methanol for methyl esterification reaction, performing spin-drying after the reaction is finished, adding ethanol for dissolution and crystallization, and obtaining dehydroabietic acid methyl ester; the concentration of the dehydroabietic acid toluene solution is 0.4-0.6 g/mL, the dosage ratio of dehydroabietic acid to thionyl chloride is 1 g:0.2-0.3 mL, and the dosage ratio of dehydroabietic acid to methanol is 1 g:1-3 mL; the reaction temperature of dehydroabietic acid and thionyl chloride is 75-80 ℃, and the reaction time is 2-4 hours; the methyl esterification reaction temperature is 75-80 ℃ and the reaction time is 2-4 hours;
adding N-bromosuccinimide NBS into an acetonitrile solution of methyl dehydroabietate, carrying out a light-shielding normal-temperature reaction, carrying out rotary evaporation after the reaction is finished, washing with dichloromethane twice, and dissolving and crystallizing with methanol to obtain 12-bromodehydroabietate; wherein the concentration of the dehydroabietyl methyl ester acetonitrile solution is 0.15-0.20 g/mL, the dosage ratio of dehydroabietyl methyl ester to NBS is 1:1.2-1:1.5, and the reaction time is 20-24 h;
under the ice bath condition, adding the 12-bromine dehydroabietic acid methyl ester into mixed acid which is formed by fully mixing fuming nitric acid and concentrated sulfuric acid, stirring, directly pouring the mixed acid into ice water after the reaction is finished, standing, carrying out reduced pressure suction filtration, washing for multiple times, purifying by using petroleum ether and ethyl acetate in a volume ratio of 500:1-200:1 through a column, and obtaining the 12-bromine-13, 14-dinitrodeisopropyl dehydroabietic acid methyl ester; the ratio of the dosage of the 12-bromine dehydroabietic acid methyl ester to the fuming nitric acid is 1g to 6-7 ml, the ratio of the dosage of the 12-bromine dehydroabietic acid methyl ester to the dosage of the concentrated sulfuric acid is 1-3 g to 1ml, and the nitration reaction is carried out for 0.5-1.5 h under the ice bath condition.
4. The method for preparing the dehydroabietyl bis-benzimidazole salicylaldehyde three-ion functional fluorescent probe according to claim 2, which is characterized in that: the preparation method of the 12-bromo-13, 14-diamino deisopropyl dehydroabietic acid methyl ester comprises the steps of dissolving the 12-bromo-13, 14-dinitro deisopropyl dehydroabietic acid methyl ester in HFIP and distilled water, reacting with iron powder and concentrated hydrochloric acid, stirring and refluxing, filtering the iron powder after the reaction is finished, neutralizing to be neutral by using saturated sodium bicarbonate, purifying by using petroleum ether with the volume ratio of ethyl acetate of 28:1, and obtaining the 12-bromo-13, 14-diamino deisopropyl dehydroabietic acid methyl ester;
the reaction time is 4.5h, wherein the dosage ratio of the 12-bromo-13, 14-dinitrodeisopropyl dehydroabietic acid methyl ester to distilled water is 0.22g to 1ml, the dosage ratio of the 12-bromo-13, 14-dinitrodeisopropyl dehydroabietic acid methyl ester to iron powder is 0.22g to 0.5g, the dosage ratio of the 12-bromo-13, 14-dinitrodeisopropyl dehydroabietic acid methyl ester to concentrated hydrochloric acid is 0.22g to 800 μl, and the dosage ratio of the 12-bromo-13, 14-dinitrodeisopropyl dehydroabietic acid methyl ester to HFIP is 1g to 4-5 ml.
5. The method for preparing the dehydroabietyl bis-benzimidazole salicylaldehyde three-ion functional fluorescent probe according to claim 2, which is characterized in that: the preparation method of the 3- (1H-benzo [ d ] imidazole-2-yl) -2-hydroxy-5-methylbenzaldehyde comprises the steps of reacting o-phenylenediamine with 5-methyl salicylaldehyde as a catalyst and sodium sulfite as a catalyst under the protection of nitrogen and using absolute ethyl alcohol to recrystallize after stirring reflux reaction to obtain benzimidazole 2- (1H-benzo [ d ] imidazole-2-yl) -4-cresol; wherein the dosage ratio of the o-phenylenediamine to the 5-methyl salicylaldehyde is 1.22g to 1.56g, the dosage ratio of the o-phenylenediamine to the sodium sulfite is 1.22g to 1.59g, the reaction temperature is 78 ℃, and the reaction time is 12 hours;
reacting trifluoroacetic acid with benzimidazole 2- (1H-benzo [ d ] imidazole-2-yl) -4-cresol, taking hexamethylenetetramine as a catalyst, and purifying by using petroleum ether and ethyl acetate in a volume ratio of 100-20:1 to prepare 3- (1H-benzo [ d ] imidazole-2-yl) -2-hydroxy-5-methylbenzaldehyde; wherein the dosage ratio of trifluoroacetic acid to benzimidazole 2- (1H-benzo [ d ] imidazol-2-yl) -4-cresol is 0.3g to 5ml, the dosage ratio of hexamethylenetetramine to benzimidazole 2- (1H-benzo [ d ] imidazol-2-yl) -4-cresol is 0.3g to 0.9g, the reaction temperature is 110 ℃, and the reaction time is 12H.
6. The method for preparing the dehydroabietyl bis-benzimidazole salicylaldehyde three-ion functional fluorescent probe according to claim 2, which is characterized in that: the 12-bromo-13, 14-diamino deisopropyl dehydroabietic acid methyl ester and 3- (1)HBenzo [ d ]]Imidazole-2-yl) -2-hydroxy-5-methylbenzaldehyde reaction, wherein DMA is used as an organic solvent, sodium bisulphite is used as a catalyst, and 3- (1H-benzo [ d)]The molar ratio of the imidazole-2-yl) -2-hydroxy-5-methylbenzaldehyde to the 12-bromo-13, 14-diamino deisopropyl dehydroabietic acid methyl ester is 1:1, the reaction temperature is 110 ℃, and the reaction time is 10-12 h; after the reaction, the solid was precipitated by standing at room temperature to prepare a probe.
7. The use of the dehydroabietyl bisbenzimidazole salicylaldehyde three-ion functional fluorescent probe according to claim 1 for detecting copper ions, hypochlorite ions and zinc ions.
8. The use according to claim 7, wherein: under the action of copper ions, the fluorescence intensity of the fluorescent probe is reduced to be quenched, and the lowest detection limit of copper is reduced to 3.8nM level;
under the action of hypochlorite ions, the fluorescence changes from yellow green to cyan, and the minimum detection limit is 0.5 mu M;
under the action of zinc ions, the fluorescence changes from yellow-green to blue-violet, and the minimum detection limit is 0.3 mu M.
9. The use according to claim 7, wherein: fluorescent probe pair Cu 2+ 、ClO - 、Zn 2+ The detection of ions is not interfered by other coexisting ions.
10. The use according to claim 7, wherein: the dehydroabietyl bisbenzimidazole salicylaldehyde three-ion functional fluorescent probe is applied to cell imaging and zebra fish imaging.
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| CN111675657A (en) * | 2020-07-20 | 2020-09-18 | 南京林业大学 | Dehydroabietic acid based 2, 4-diaryl benzimidazole ferric ion and mercury ion fluorescent probe and preparation method and application thereof |
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