CN115340507B - Dual-functional fluorescent probe for identifying aluminum ions and gallium ions, and preparation method and application thereof - Google Patents

Dual-functional fluorescent probe for identifying aluminum ions and gallium ions, and preparation method and application thereof Download PDF

Info

Publication number
CN115340507B
CN115340507B CN202210992696.5A CN202210992696A CN115340507B CN 115340507 B CN115340507 B CN 115340507B CN 202210992696 A CN202210992696 A CN 202210992696A CN 115340507 B CN115340507 B CN 115340507B
Authority
CN
China
Prior art keywords
compound
ions
fluorescent probe
gallium
reacting
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Active
Application number
CN202210992696.5A
Other languages
Chinese (zh)
Other versions
CN115340507A (en
Inventor
邢志勇
王俊利
黄云彤
陈祥凤
赵艳
范传滨
董明右
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Youjiang Medical University for Nationalities
Original Assignee
Youjiang Medical University for Nationalities
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Youjiang Medical University for Nationalities filed Critical Youjiang Medical University for Nationalities
Priority to CN202210992696.5A priority Critical patent/CN115340507B/en
Publication of CN115340507A publication Critical patent/CN115340507A/en
Application granted granted Critical
Publication of CN115340507B publication Critical patent/CN115340507B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D277/00—Heterocyclic compounds containing 1,3-thiazole or hydrogenated 1,3-thiazole rings
    • C07D277/60—Heterocyclic compounds containing 1,3-thiazole or hydrogenated 1,3-thiazole rings condensed with carbocyclic rings or ring systems
    • C07D277/62—Benzothiazoles
    • C07D277/64—Benzothiazoles with only hydrocarbon or substituted hydrocarbon radicals attached in position 2
    • C07D277/66—Benzothiazoles with only hydrocarbon or substituted hydrocarbon radicals attached in position 2 with aromatic rings or ring systems directly attached in position 2
    • 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"
    • 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
    • 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
    • G01N21/6447—Fluorescence; Phosphorescence by visual observation
    • 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
    • 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
    • C09K2211/1029—Heterocyclic compounds characterised by ligands containing one nitrogen atom as the heteroatom
    • C09K2211/1037—Heterocyclic compounds characterised by ligands containing one nitrogen atom as the heteroatom with sulfur
    • 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
    • G01N2021/6417—Spectrofluorimetric devices
    • 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

Landscapes

  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Physics & Mathematics (AREA)
  • Immunology (AREA)
  • Organic Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Analytical Chemistry (AREA)
  • Nuclear Medicine, Radiotherapy & Molecular Imaging (AREA)
  • Biochemistry (AREA)
  • General Health & Medical Sciences (AREA)
  • General Physics & Mathematics (AREA)
  • Pathology (AREA)
  • Molecular Biology (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Materials Engineering (AREA)
  • Optics & Photonics (AREA)
  • Engineering & Computer Science (AREA)
  • Investigating Or Analysing Materials By The Use Of Chemical Reactions (AREA)
  • Investigating Or Analyzing Non-Biological Materials By The Use Of Chemical Means (AREA)

Abstract

Aluminum identificationA difunctional fluorescent probe of ions and gallium ions and a preparation method and application thereof relate to a difunctional fluorescent probe and a preparation method and application thereof. Aims to solve the problems of the prior art that Al is identified simultaneously 3+ And Ga 3+ The sensitivity of the multifunctional probe is low. The preparation method of the fluorescent probe with the double-function recognition of aluminum ions and gallium ions comprises the following steps: 1. 3-methoxy salicylaldehyde reacts with 2-amino thiophenol to obtain a compound 1; 2. reacting the compound 1 obtained in the step one with ethyl bromoacetate to obtain a compound 2; 3. reacting the compound 2 obtained in the second step with hydrazine hydrate to obtain a compound 3; 4. and (3) reacting the compound 3 obtained in the step (III) with 5-methyl salicylaldehyde to obtain a target compound BMP. The invention realizes that the probe can identify both aluminum ions and gallium ions, and has good selectivity, strong capability of resisting interference of other metal ions and low detection limit. The dual-function fluorescent probe is used for detecting heavy metal ions.

Description

Dual-functional fluorescent probe for identifying aluminum ions and gallium ions, and preparation method and application thereof
Technical Field
The invention relates to a difunctional fluorescent probe and a preparation method and application thereof.
Background
Aluminum is known to be the third most abundant metal element on earth, and its compounds are widely used in various fields such as clinical medicines, packaging materials, food additives, water treatment, etc. As a non-essential element of the human body, the widespread use of aluminum has led to the ingestion of excessive amounts of aluminum. According to the recommended national health organization, the intake of aluminum ions in humans should be limited to 7mg/kg. High levels of aluminum ions accumulated in the human body can pose significant health hazards including alzheimer's disease, osteomalacia, and induction of various cancers. Also, gallium ions are closely related to human life. For example, gallium nitrate is often used as an anticancer drug; gallium arsenide is commonly used in industrial integrated circuits. Whether it is used in industry or medical treatment, gallium ions are most likely to accumulate in human body through food chains, and toxic and side effects such as dizziness and hypodynamia can be caused. In view of the wide existence of aluminum ions and gallium ions in our life and the harm to human health, the method has important significance for measuring the content of the aluminum ions and the gallium ions in an environment system and a life system.
Although various methods have been used to detect metal ions, such as atomic absorption spectrometry, atomic fluorescence spectrometry, electrochemical analysis, inductively coupled plasma mass spectrometry, etc., the method based on fluorescent molecular sensor detection is an excellent method compared to these methods, and has advantages of high selectivity, rapid analysis, high sensitivity, etc. More importantly, the method is convenient and quick in the process of detecting the metal ions, is nondestructive to the sample, and can be used for convenient visual qualitative identification.
2- (2-Hydroxyphenyl) Benzothiazole (HBT) fluorescent dyes are often used as fluorescent precursors for fluorescent probe molecules because of their stable optical properties, large Stokes shift, etc. So far, many methods have been developed to detect Al separately 3+ And Ga 3+ Is provided. However, development of Al at the same time 3+ And Ga 3+ Multifunctional probes with high sensitivity remain a challenge. Based on this, a novel dual function assay Al was developed 3+ And Ga 3+ The fluorescent probe of (2) gives a detection curve to judge the level of aluminum ions and gallium ions, and has important research value for performing fluorescent imaging diagnosis and analysis on two metal ions in a life system.
Disclosure of Invention
The invention aims to solve the problems of complicated synthesis steps, low selectivity and low sensitivity of the existing probe for separately identifying aluminum ions or gallium ions, and provides a difunctional fluorescent probe for identifying aluminum ions and gallium ions, and a preparation method and application thereof.
The structural formula of the difunctional fluorescent probe for identifying aluminum ions and gallium ions is as follows:
the invention relates to a preparation method of a difunctional fluorescent probe for identifying aluminum ions and gallium ions, which comprises the following steps:
1. 3-methoxy salicylaldehyde reacts with 2-amino thiophenol to obtain a compound 1:
dissolving 3-methoxy salicylaldehyde in N, N-dimethylformamide, sequentially adding sodium metabisulfite and 2-amino thiophenol, stirring in an oil bath, reacting for 3-4 hours at the temperature of 110-120 ℃, detecting the reaction by using a TCL plate, cooling to room temperature after the reaction is completed, adding deionized water into the solution to precipitate, filtering the precipitate, washing and drying to obtain a compound 1;
wherein the molar ratio of the 3-methoxy salicylaldehyde to the 2-amino thiophenol is 1:1; the molar ratio of the 3-methoxy salicylaldehyde to the sodium metabisulfite is (0.6-1.2): 1;
2. reacting the compound 1 obtained in the step one with ethyl bromoacetate to obtain a compound 2:
addition of Compound 1, ethyl bromoacetate and K to acetonitrile 2 CO 3 Heating to 85-90 ℃, reacting for 2-3 hours, cooling to room temperature after stopping the reaction, filtering the precipitate, washing with deionized water, purifying by a silica gel column, and drying to obtain a compound 2;
wherein compound 1, ethyl bromoacetate and K 2 CO 3 The mol ratio of (1) to (1.05): (1.5-2);
3. reacting the compound 2 obtained in the step two with hydrazine hydrate to obtain a compound 3:
adding the compound 2 and hydrazine hydrate into ethanol, heating and refluxing, reacting for 6-7 hours at the temperature of 80-85 ℃, detecting the reaction by using a TCL plate, cooling to room temperature after the reaction is completed, filtering the precipitate, washing with ethanol, and drying to obtain a compound 3; wherein the molar ratio of the compound 2 to the hydrazine hydrate is 1:1, a step of;
4. reacting the compound 3 obtained in the step three with 5-methyl salicylaldehyde to obtain a target compound BMP:
adding the compound 3 and 5-methyl salicylaldehyde into ethanol, heating and refluxing, reacting for 2-3 hours at the temperature of 80-85 ℃, detecting the reaction by using a TCL plate, cooling to room temperature after the reaction is completed, filtering the precipitate, washing with ethanol, and drying to obtain a target compound BMP; wherein the molar ratio of the compound 3 to the 5-methyl salicylaldehyde is 1:1.
in the fourth step, after the compound 3 and 5-methyl salicylaldehyde are added into ethanol, glacial acetic acid is also added until the pH value of the reaction system is 5-6. Glacial acetic acid acts as a catalyst to accelerate the reaction rate.
The invention relates to an application of a bifunctional fluorescent probe for aluminum ions and gallium ions in heavy metal ion detection. The method is used for sensing and detecting the content of aluminum ions and gallium ions in a water environment system, wherein the sensing and detecting comprises fluorescence detection, ultraviolet ratio detection, visual qualitative detection, gallium ion reversible detection and test paper detection; the fluorescent imaging detection method is used for carrying out fluorescent imaging detection on aluminum ions and gallium ions in cells.
Can also be prepared by adding Na 2 EDTA achieves repeated detection of gallium ions.
The preparation reaction formula of the difunctional fluorescent probe of aluminum ions and gallium ions is as follows:
in the reaction formula, 1 is a compound 1,2 is a compound 2,3 is a compound 3, and BMP is a bifunctional fluorescent probe of aluminum ions and gallium ions. The invention has the beneficial effects that:
1) The synthesis of the probe can be completed in four steps, the raw materials are economical, and the post-treatment process is relatively simple;
2) The invention realizes the sensing detection of the probe which can recognize aluminum ions and gallium ions, and has good selectivity, strong capability of resisting the interference of other metal ions and low detection limit. Aluminum ions: the fluorescence detection limit is 1.5162 multiplied by 10 -6 M, ultraviolet detection limit is 9.4011 ×10 -8 M. Gallium ions: the fluorescence detection limit is 4.2816 multiplied by 10 -6 M, ultraviolet detection limit is 3.2019 ×10 -8 M。
In addition, in the case of the optical fiber,the fluorescent probe has obvious fluorescent color change observed under ultraviolet lamp, and can distinguish the identification of aluminum ions and gallium ions through different fluorescent colors, and is provided with a chromogenic sensing function. Compared with other fluorescent probes for quantitatively detecting metal ions by only fluorescence spectrum, the probe can also quantitatively detect ultraviolet ratio by ultraviolet spectrum. Based on the specific and obvious color change, the reagent can be used as a specific indicator for displaying the existence of aluminum ions or gallium ions in the aqueous solution, and can be used for real-time qualitative and quantitative visual colorimetric detection. And more importantly, the sensing detection of gallium ions can be achieved by using Na 2 EDTA achieves rapid reversible repeat detection. In addition, the invention can also be applied to the fluorescent imaging identification of aluminum ions or gallium ions in cells. Therefore, the invention is a simple, quick and sensitive aluminum ion and gallium ion dual-function detection reagent, and has wide application prospect in the water sample environment and the life system field.
Drawings
FIG. 1 shows the probe BMP (concentration 1X 10) -5 mol/L) in DMF/H 2 Selectivity to different metal ions under O;
FIG. 2 is a graph showing the effect of coexisting ions on aluminum ion measurement;
FIG. 3 is an illustration of the effect of coexisting ions on gallium ion measurement;
FIG. 4 shows the probe BMP (concentration 1X 10) -5 mol/L) in DMF/H 2 For Al with different concentrations under O 3+ Is a fluorescence spectrum response diagram of (1);
FIG. 5 shows the probe BMP (concentration 1X 10) -5 mol/L) in DMF/H 2 For Al with different concentrations under O 3+ Is a UV spectrum response diagram of (1);
FIG. 6 shows the probe BMP (concentration 1X 10) -5 mol/L) in DMF/H 2 For Ga at different concentrations under O 3+ Is a fluorescence spectrum response diagram of (1);
FIG. 7 shows the probe BMP (concentration 1X 10) -5 mol/L) in DMF/H 2 For Ga at different concentrations under O 3+ Is a UV spectrum response diagram of (1);
FIG. 8 is a graph showing fluorescence emission at 365nm of an ultraviolet lamp after adding aluminum ions and gallium ions to the probe BMP, respectively;
FIG. 9 is a graph showing the reversible changes in the recognition of gallium ions by the probe BMP;
FIG. 10 is a diagram of an open-hole visual detection of aluminum ions and gallium ions by dip-dyeing with a test paper;
FIG. 11 is a graph showing the fluorescence recognition of aluminum ions and gallium ions by the application of the probe BMP to cells.
Detailed Description
The technical scheme of the invention is not limited to the specific embodiments listed below, and also includes any combination of the specific embodiments.
The first embodiment is as follows: the structural formula of the bifunctional fluorescent probe for recognizing aluminum ions and gallium ions in the embodiment is as follows:
the dual-function fluorescent probe for detecting aluminum ions and gallium ions is recorded as a probe BMP, the probe does not have fluorescence due to isomerization of a PET mechanism and C=N, and after the fluorescent probe BMP acts on the aluminum ions and the gallium ions, isomerization of the PET mechanism and the C=N is inhibited, so that fluorescence of a detection system is enhanced and fluorescence color is changed.
The second embodiment is as follows: the preparation method of the difunctional fluorescent probe for identifying aluminum ions and gallium ions comprises the following steps:
1. 3-methoxy salicylaldehyde reacts with 2-amino thiophenol to obtain a compound 1:
dissolving 3-methoxy salicylaldehyde in N, N-dimethylformamide, sequentially adding sodium metabisulfite and 2-amino thiophenol, stirring in an oil bath, reacting for 3-4 hours at the temperature of 110-120 ℃, detecting the reaction by using a TCL plate, cooling to room temperature after the reaction is completed, adding deionized water into the solution to precipitate, filtering the precipitate, washing and drying to obtain a compound 1;
wherein the molar ratio of the 3-methoxy salicylaldehyde to the 2-amino thiophenol is 1:1; the molar ratio of the 3-methoxy salicylaldehyde to the sodium metabisulfite is (0.6-1.2): 1;
2. reacting the compound 1 obtained in the step one with ethyl bromoacetate to obtain a compound 2:
addition of Compound 1, ethyl bromoacetate and K to acetonitrile 2 CO 3 Heating to 85-90 ℃, reacting for 2-3 hours, cooling to room temperature after stopping the reaction, filtering the precipitate, washing with deionized water, purifying by a silica gel column, and drying to obtain a compound 2;
wherein compound 1, ethyl bromoacetate and K 2 CO 3 The mol ratio of (1) to (1.05): (1.5-2);
3. reacting the compound 2 obtained in the step two with hydrazine hydrate to obtain a compound 3:
adding the compound 2 and hydrazine hydrate into ethanol, heating and refluxing, reacting for 6-7 hours at the temperature of 80-85 ℃, detecting the reaction by using a TCL plate, cooling to room temperature after the reaction is completed, filtering the precipitate, washing with ethanol, and drying to obtain a compound 3; wherein the molar ratio of the compound 2 to the hydrazine hydrate is 1:1, a step of;
4. reacting the compound 3 obtained in the step three with 5-methyl salicylaldehyde to obtain a target compound BMP:
adding the compound 3 and 5-methyl salicylaldehyde into ethanol, heating and refluxing, reacting for 2-3 hours at the temperature of 80-85 ℃, detecting the reaction by using a TCL plate, cooling to room temperature after the reaction is completed, filtering the precipitate, washing with ethanol, and drying to obtain a target compound BMP; wherein the molar ratio of the compound 3 to the 5-methyl salicylaldehyde is 1:1.
and a third specific embodiment: the second difference between this embodiment and the second embodiment is that: and step two, washing with deionized water for 5 times. The other is the same as in the second embodiment.
The specific embodiment IV is as follows: this embodiment differs from the second or third embodiment in that: in the second step, ethyl acetate/petroleum ether is used as an eluent to be separated and purified by a silica gel column chromatography. The other is the same as the second or third embodiment.
Fifth embodiment: the present embodiment differs from the second to fourth embodiments in that: and in the third step and the fourth step, ethanol is used for washing 3-5 times. The others are the same as in the second to fourth embodiments.
Specific embodiment six: the application of the dual-function fluorescent probe in heavy metal ion detection is provided.
Seventh embodiment: the sixth embodiment differs from the first embodiment in that: the dual-function fluorescent probe is particularly used for sensing and detecting the content of aluminum ions and gallium ions in a water environment system. The other is the same as in the fourth embodiment.
Eighth embodiment: this embodiment differs from the sixth or seventh embodiment in that: the sensing detection comprises fluorescence detection, ultraviolet ratio detection, visual qualitative detection, gallium ion reversible detection or test paper detection. The others are the same as in the sixth or seventh embodiment.
According to the embodiment, naked eye visual detection of aluminum ions and gallium ions can be realized in a dip-dyeing mode by using test paper.
Detailed description nine: this embodiment differs from one of the sixth to eighth embodiments in that: na is also added 2 EDTA achieves repeated detection of gallium ions. The others are the same as in one of the sixth to eighth embodiments.
Detailed description ten: this embodiment differs from one of the sixth to ninth embodiments in that: the dual-function fluorescent probe is used for carrying out fluorescent imaging detection on aluminum ions and gallium ions in cells. The others are the same as in one of the sixth to ninth embodiments.
The following examples of the present invention are described in detail, and are provided by taking the technical scheme of the present invention as a premise, and the detailed embodiments and specific operation procedures are given, but the scope of the present invention is not limited to the following examples.
Example 1:
the preparation method of the bifunctional fluorescent probe for identifying aluminum ions and gallium ions in the embodiment comprises the following steps:
(1) Synthesis of Compound 1:
3-Methoxysalicylaldehyde (0.85 g,5.60 mmol) was dissolved in 15mL of LDMF, followed by sodium metabisulfite (1.28 g,6.72 mmol) and 2-aminophenylthiophenol (0.60 mL,5.60 mmol) added in sequence and stirred in an oil bath at 110deg.C. TLC monitors the progress of the reaction, after the reaction was completed, the mixture was cooled to room temperature, 20mL of deionized water at 0℃was poured into the mixture, a large amount of yellow solid was precipitated, the precipitate was filtered, the obtained cake was washed 5 times with absolute ethanol, and compound 1 was obtained after drying as a pale yellow solid in 80.5% yield.
(2) Synthesis of Compound 2:
to a round bottom flask containing 25mL of acetonitrile was added compound 1 (0.46 g,1.80 mmol), followed by potassium carbonate (1.28 g,3.60 mmol) and ethyl bromoacetate (0.20 mL,1.83 mmol), and heated to reflux to the end of the reaction (TLC monitoring), heating temperature was 90 ℃. After the reaction solution is cooled, filtering, washing with deionized water to obtain a crude product, separating and purifying by a silica gel column chromatography with ethyl acetate/petroleum ether as an eluent, and drying to obtain the compound 2, a white solid, with the yield of 76.0%.
(3) Synthesis of Compound 3:
compound 2 (0.41 g,1.20 mmol) was dissolved in 20mL absolute ethanol, 1.20mmol of hydrazine hydrate was added at room temperature, and heated to reflux until the starting material disappeared (TLC followed by reaction) at 80 ℃. Stopping the reaction, standing for 30min, precipitating a large amount of precipitate, filtering, washing the precipitate with absolute ethyl alcohol for three times, and drying to obtain the compound 3, which is a white solid with the yield of 91.1%.
(4) Synthesis of the target compound:
compound 3 (164 mg,0.50 mmol) and 5-methylsalicylaldehyde (68 mg,0.50 mmol) were added to 15mL of absolute ethanol, two drops of glacial acetic acid were added dropwise thereto, the mixture was refluxed under heating at 80℃for 2.5 hours, the reaction was detected with a TCL plate, after the reaction was completed, the mixture was cooled to room temperature, the precipitate was filtered, and was washed with absolute ethanol for 5 times, and the product was dried to give the objective compound BMP in a yield of 81.3%.
Example 2:
the application of a bifunctional fluorescent probe BMP for recognizing aluminum ions and gallium ions.
The fluorescence probe BMP with dual recognition of aluminum ion and gallium ion synthesized in example 1 was dissolved in DMF to prepare a concentration of 1X 10 -5 DMF/H of mol/L 2 O (2/3, v/v), detecting fluorescence selectivity of the probe to different metal ions by using a spectrophotometer, wherein FIG. 1 is a fluorescence selectivity spectrogram, and as can be seen in FIG. 1, the probe has almost no fluorescence emission under excitation of 370nm wavelength; after different metal ions are added, the fluorescence intensity change is detected by a fluorescence spectrophotometer, and the result is shown in figure 1, after aluminum ions are added, the maximum emission wavelength of fluorescence is observed at 472nm, and the fluorescence intensity is obviously enhanced; the maximum emission wavelength of fluorescence after gallium ions are added is 482nm, the fluorescence intensity is obviously enhanced, and the addition of other metal ions has almost no change.
To further confirm that the selectivity to aluminum ions and gallium ions was not affected in the presence of other metal ions, competitive fluorescence experiments were performed, and as shown in fig. 2 and 3, fluorescence spectroscopic analysis showed that the recognition of aluminum ions and gallium ions by the probe was not affected in the presence of other metal ions.
FIG. 2 is a graph showing the effect of coexisting ions on the measurement of aluminum ions, labeled "Al" in FIG. 2 3+ "1.0X10 -5 The fluorescence intensity of the system when the mol/L aluminum ions exist alone, and the balance is the fluorescence intensity of the system when the aluminum ions with the same concentration and various metal ions with the same concentration multiple coexist. The black bars represent fluorescence intensity of the probe and the probe when various metal ions are added separately, and the gray diagonal bars represent coexistence of aluminum ions with the same concentration and various metal ions with the same concentration multipleFluorescence intensity of the time system. As can be seen, al is added 3+ The fluorescence of the rear probe is enhanced, and the existence of the coexisting ions does not significantly change the detection result of the probe molecule on aluminum ions.
FIG. 3 is an effect of coexisting ions on gallium ion measurement, labeled "Ga" in FIG. 3 3+ "1.0X10 -5 The fluorescence intensity of the system when the gallium ions exist alone in mol/L, and the balance is the fluorescence intensity of the system when the gallium ions with the same concentration and various metal ions with the same concentration multiple coexist. The black bars represent fluorescence intensity when the probe and the probe are added with various metal ions alone, and the gray diagonal bars represent fluorescence intensity of the system when aluminum ions with the same concentration coexist with various metal ions with the same concentration multiple. As can be seen, ga is added 3+ The fluorescence of the rear probe is enhanced, and the existence of the coexisting ions does not significantly change the detection result of the probe molecule on gallium ions.
The aluminum ions with different concentrations are added into the solution, and the change of the fluorescence intensity and the ultraviolet absorption intensity is detected, as shown in the fluorescence spectrum analysis of fig. 4 and 5, the concentration of the added aluminum ions is 0 to 5 multiplied by 10 -5 In the mol/L range, the change of fluorescence intensity and ultraviolet absorption intensity has good linear relation curve with the added concentration respectively, thus realizing the quantitative detection of aluminum ions.
FIG. 4 shows the probe BMP (concentration 1X 10) -5 mol/L) in DMF/H 2 For Al with different concentrations under O (2/3, v/v) 3+ Is a fluorescence spectrum response diagram of (2). In FIG. 4, the abscissa is wavelength (nm), the ordinate is fluorescence intensity, and the excitation wavelength is 370nm. The concentration of aluminum ions is from 0 to 5X 10 -5 mol/L, detection limit is 1.5162 ×10 -6 M。
FIG. 5 shows the probe BMP (concentration 1X 10) -5 mol/L) in DMF/H 2 For Al with different concentrations under O (2/3, v/v) 3+ Is a graph of ultraviolet spectral response of (c). In fig. 5, the abscissa indicates wavelength (nm) and the ordinate indicates ultraviolet absorption intensity. The concentration of aluminum ions is from 0 to 5X 10 -5 mol/L, detection limit is 9.4011 ×10 -8 M。
Gallium ions with different concentrations are added into the solution, and the fluorescence intensity and the ultraviolet absorption intensity of the solution are detectedThe change in the degree, as shown in the fluorescence spectrum analysis of FIG. 6 and FIG. 7, showed that the concentration of gallium ions was 0 to 1.5X10 when added -4 In the mol/L range, the change of fluorescence intensity and ultraviolet absorption intensity has good linear relation curve with the added concentration respectively, thus realizing the quantitative detection of gallium ions.
FIG. 6 shows the probe BMP (concentration 1X 10) -5 mol/L) in DMF/H 2 Ga at different concentrations under O (2/3, v/v) 3+ Is a fluorescence spectrum response diagram of (2). In FIG. 6, the abscissa is wavelength (nm), the ordinate is fluorescence intensity, and the excitation wavelength is 370nm. Gallium ion concentration is from 0 to 1.5X10 -4 mol/L, detection limit is 4.2816 ×10 -6 M。
FIG. 7 shows the probe BMP (concentration 1X 10) -5 mol/L) in DMF/H 2 Ga at different concentrations under O (2/3, v/v) 3+ Is a graph of ultraviolet spectral response of (c). In fig. 7, the abscissa indicates wavelength (nm) and the ordinate indicates ultraviolet absorption intensity. Gallium ion concentration is from 0 to 1.5X10 -4 mol/L, detection limit is 3.2019 ×10 -8 M。
FIG. 8 is a graph showing fluorescence emission at 365nm of an ultraviolet lamp after adding aluminum ion and gallium ion to the probe BMP, respectively. To 1X 10 -5 5X 10 mol/L Probe solution was added -5 mol/L aluminum ion and 5×10 -5 After the mol/L gallium ions are placed under an ultraviolet lamp, the fluorescence color changes (from non-fluorescence to blue and blue-green fluorescence respectively) under 365nm irradiation, so that the visual qualitative detection of aluminum ions and gallium ions is realized. As can be seen, after adding aluminum ions, the solution can emit blue fluorescence; after gallium ions are added, the solution can emit blue-green fluorescence.
FIG. 9 is a view of a direction of 1X 10 -5 5X 10 mol/L Probe solution was added -5 After mol/L gallium ion, adding 5X 10 -5 mol/L Na 2 Reversible change after EDTA can realize more than 3 times of cyclic detection on gallium ions. Reversible change of probe BMP on gallium ion recognition, after gallium ion is added into BMP solution, fluorescence is obviously increased, and then equivalent Na is added 2 The fluorescence resumes the quenched state after EDTA and reversible recognition of gallium ions by the probe BMP can be repeated at least 3 times.
FIG. 10 is a schematic representation of dip-dyeing with test paperNaked eye visual detection of aluminum ions and gallium ions is realized in a mode, and the upper row is respectively BMP and 5 mu MAl from left to right 3+ 、10μMAl 3+ 、15μMAl 3+ 、20μMAl 3+ The method comprises the steps of carrying out a first treatment on the surface of the The lower row is respectively 10 mu MGa from left to right 3+ 、20μMGa 3 + 、40μMGa 3+ 、80μMGa 3+ . Test paper is put into a test paper containing probe BMP (10 mu M) and Al with different concentrations 3+ (0-20. Mu.M) or Ga 3+ (0-80 mu M) in the solution, soaking for two hours, taking out, and drying in air. The dry test paper is put under 365nm irradiation of an ultraviolet lamp and is along with Al 3+ Or Ga 3+ The test paper showed a visible color change from colorless to bright blue or colorless to bluish green with increasing concentration. This phenomenon indicates that the probe BMP can be loaded on the test paper for Al 3+ Or Ga 3+ And (5) performing fluorescence colorimetric detection.
FIG. 11 shows fluorescence recognition of aluminum and gallium ions by using a probe BMP in cells, wherein the fluorescence emission in cells can be observed by confocal laser fluorescence microscopy after the BMP (100. Mu.M) and aluminum or gallium ions are incubated with A549 cells, respectively. A549 cells were selected as subjects. Using Al for cells 3+ Or Ga 3+ After 2h of (50. Mu.M) incubation, the cells were fixed by adding 4% paraformaldehyde after 3 washes in serum-free medium. After 1h, paraformaldehyde was washed off with PBS and further incubated with probe BMP (10 μm) for 2h, rinsed three times with PBS and finally imaged under laser confocal. The fluorescence imaging result shows that only when probes BMP and Al are used 3+ Or Ga 3+ Fluorescence signal was observed in the co-incubated experimental group, indicating that the probe BMP could be used for intracellular Al 3+ Or Ga 3+ And performing fluorescence imaging identification.

Claims (8)

1. A bifunctional fluorescent probe for identifying aluminum ions and gallium ions, characterized in that the bifunctional fluorescent probe has the following structural formula:
2. the method for preparing a bifunctional fluorescent probe recognizing aluminum ions and gallium ions as recited in claim 1, wherein the method for preparing the bifunctional fluorescent probe comprises the steps of:
1. 3-methoxy salicylaldehyde reacts with 2-amino thiophenol to obtain a compound 1:
dissolving 3-methoxy salicylaldehyde in N, N-dimethylformamide, sequentially adding sodium metabisulfite and 2-amino thiophenol, stirring in an oil bath, reacting for 3-4 hours at the temperature of 110-120 ℃, detecting the reaction by using a TCL plate, cooling to room temperature after the reaction is completed, adding deionized water into the solution to precipitate, filtering the precipitate, washing and drying to obtain a compound 1; the structural formula of the compound 1 is as follows:
wherein the molar ratio of the 3-methoxy salicylaldehyde to the 2-amino thiophenol is 1:1; the molar ratio of the 3-methoxy salicylaldehyde to the sodium metabisulfite is (0.6-1.2): 1;
2. reacting the compound 1 obtained in the step one with ethyl bromoacetate to obtain a compound 2:
addition of Compound 1, ethyl bromoacetate and K to acetonitrile 2 CO 3 Heating to 85-90 ℃, reacting for 2-3 hours, cooling to room temperature after stopping the reaction, filtering the precipitate, washing with deionized water, purifying by a silica gel column, and drying to obtain a compound 2; the structural formula of the compound 2 is as follows:
wherein compound 1, ethyl bromoacetate and K 2 CO 3 The mol ratio of (1) to (1.05): (1.5-2);
3. reacting the compound 2 obtained in the step two with hydrazine hydrate to obtain a compound 3:
adding the compound 2 and hydrazine hydrate into ethanol, heating and refluxing, reacting for 6-7 hours at the temperature of 80-85 ℃, detecting the reaction by using a TCL plate, cooling to room temperature after the reaction is completed, filtering the precipitate, washing with ethanol, and drying to obtain a compound 3; the structural formula of the compound 3 is as follows:
wherein the molar ratio of the compound 2 to the hydrazine hydrate is 1:1, a step of;
4. reacting the compound 3 obtained in the step three with 5-methyl salicylaldehyde to obtain a target compound BMP:
adding the compound 3 and 5-methyl salicylaldehyde into ethanol, heating and refluxing, reacting for 2-3 hours at the temperature of 80-85 ℃, detecting the reaction by using a TCL plate, cooling to room temperature after the reaction is completed, filtering the precipitate, washing with ethanol, and drying to obtain a target compound BMP; wherein the molar ratio of the compound 3 to the 5-methyl salicylaldehyde is 1:1.
3. the method for preparing a bifunctional fluorescent probe recognizing aluminum ions and gallium ions as recited in claim 2, wherein the second step is washing with deionized water 5 times.
4. The method for preparing a bifunctional fluorescent probe recognizing aluminum ions and gallium ions as recited in claim 2, wherein in the second step, ethyl acetate/petroleum ether is used as an eluent for separation and purification by silica gel column chromatography.
5. The method for preparing a bifunctional fluorescent probe recognizing aluminum ions and gallium ions as recited in claim 2, wherein the steps three and four are each washed 3 to 5 times with ethanol.
6. The use of the bifunctional fluorescent probe of claim 1 in sensing and detecting the content of aluminum ions and gallium ions in an aqueous environment system.
7. The use of claim 6, wherein the sensing comprises fluorescence detection, ultraviolet ratio detection, visual qualitative detection, reversible detection of gallium ions, or dipstick detection.
8. The method of claim 6, further comprising adding Na 2 EDTA achieves repeated detection of gallium ions.
CN202210992696.5A 2022-08-18 2022-08-18 Dual-functional fluorescent probe for identifying aluminum ions and gallium ions, and preparation method and application thereof Active CN115340507B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN202210992696.5A CN115340507B (en) 2022-08-18 2022-08-18 Dual-functional fluorescent probe for identifying aluminum ions and gallium ions, and preparation method and application thereof

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN202210992696.5A CN115340507B (en) 2022-08-18 2022-08-18 Dual-functional fluorescent probe for identifying aluminum ions and gallium ions, and preparation method and application thereof

Publications (2)

Publication Number Publication Date
CN115340507A CN115340507A (en) 2022-11-15
CN115340507B true CN115340507B (en) 2023-07-25

Family

ID=83952623

Family Applications (1)

Application Number Title Priority Date Filing Date
CN202210992696.5A Active CN115340507B (en) 2022-08-18 2022-08-18 Dual-functional fluorescent probe for identifying aluminum ions and gallium ions, and preparation method and application thereof

Country Status (1)

Country Link
CN (1) CN115340507B (en)

Family Cites Families (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR101539821B1 (en) * 2012-05-08 2015-07-28 서울과학기술대학교 산학협력단 Agent For Selecting Aluminium Ion Comprising ο-phenolsalicylimine And Its Derivative, Detecting Method Using The Same And Detecting Device Thereof
CN109438386B (en) * 2018-11-02 2021-05-07 东北农业大学 Difunctional fluorescent probe for identifying aluminum ions and zinc ions as well as preparation method and application thereof
CN109722241B (en) * 2019-01-08 2021-07-27 东北农业大学 Bifunctional fluorescent probe for identifying copper ions and mercury ions and preparation method and application thereof
CN109942509B (en) * 2019-05-08 2023-01-13 东北农业大学 Fluorescent probe for identifying copper ions under alkaline condition and preparation method and application thereof

Also Published As

Publication number Publication date
CN115340507A (en) 2022-11-15

Similar Documents

Publication Publication Date Title
Liu et al. A fluorescent probe for hydrazine based on a newly developed 1-indanone-fused coumarin scaffold
CN108752331A (en) Synthesis and application a kind of while that distinguish detection Cys, Hcy and GSH Multifunction fluorescent molecular probe
Tian et al. A novel turn-on Schiff-base fluorescent sensor for aluminum (III) ions in living cells
CN109942509B (en) Fluorescent probe for identifying copper ions under alkaline condition and preparation method and application thereof
CN101735277A (en) Fluorescent probe compounds, preparation method and use thereof
CN110483461B (en) Nitrite ion detection fluorescent probe and preparation method and use method thereof
Han et al. Colorimetric hydrazine detection and fluorescent hydrogen peroxide imaging by using a multifunctional chemical probe
CN108752377B (en) Fluorescent probe for detecting peroxynitrite anion, synthetic method and application
CN111073636B (en) Fluorescent probe for formaldehyde detection and preparation method and application thereof
CN113121520B (en) Fluorescent dye and fluorescent probe with AIE + ESIPT + ICT mechanism, and preparation method and application thereof
CN109867611A (en) A kind of for red wine and in vivo water-soluble two-photon hydrogen sulfide fluorescence probe and its preparation method and application of sulfurated hydrogen detection
CN110028471A (en) A kind of Coumarins schiff bases Cu2+Fluorescence probe and the preparation method and application thereof
WO2023093399A1 (en) Benzothiazole-parent-based fluorescent probe for detection of palladium ions, and preparation method therefor and use thereof
CN113264954A (en) Fluorescent probe molecule for detecting hydrogen peroxide and preparation method thereof
Jiang et al. New NIR spectroscopic probe with a large Stokes shift for Hg2+ and Ag+ detection and living cells imaging
CN113004256B (en) Ratio type probe for detecting mercury ions and preparation method and application thereof
CN109320537A (en) A kind of soluble two-photon fluorescence probe and its preparation method and application of for flour and in vivo benzoyl peroxide detection
CN115340507B (en) Dual-functional fluorescent probe for identifying aluminum ions and gallium ions, and preparation method and application thereof
CN110483513B (en) Fluorescent molecule, preparation method and application thereof, and fluorescence detection reagent
CN115651006B (en) Hydrogen peroxide ratio type near infrared fluorescent probe with large Stokes displacement and preparation method and application thereof
CN108641714B (en) Hg based on rhodamine derivatives2+Fluorescent probe and preparation method and application thereof
Mei et al. A novel fluorescence probe for the selective detection of cysteine in aqueous solutions and imaging in living cells and mice
CN108444962B (en) Perylene-based formaldehyde colorimetric probe and formaldehyde fluorescent test paper, and preparation method and use method thereof
CN114380792B (en) Off-on type ion detection fluorescent probe, ion detection kit, preparation method and application
CN108949159B (en) Fluorescent probe for detecting palladium ions and synthetic method and application thereof

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
GR01 Patent grant
GR01 Patent grant