CN115340507A - Difunctional fluorescent probe for identifying aluminum ions and gallium ions and preparation method and application thereof - Google Patents
Difunctional fluorescent probe for identifying aluminum ions and gallium ions and preparation method and application thereof Download PDFInfo
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Abstract
A difunctional fluorescent probe for identifying aluminum 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 of simultaneously identifying Al 3+ And Ga 3+ The multifunctional probe of (2) has low sensitivity. The preparation method of the fluorescent probe for bifunctional recognition of aluminum ions and gallium ions comprises the following steps: 1. reacting 3-methoxy salicylaldehyde with 2-aminothiophenol 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 step two with hydrazine hydrate to obtain a compound 3; 4. and (4) reacting the compound 3 obtained in the step three with 5-methyl salicylaldehyde to obtain a target compound BMP. The invention realizes that the probe can identify the aluminum ions and the gallium ions, andgood selectivity, strong anti-interference ability of other metal ions and low detection limit. The bifunctional fluorescent probe is used for detecting heavy metal ions.
Description
Technical Field
The invention relates to a bifunctional fluorescent probe and a preparation method and application thereof.
Background
As is well known, aluminum is 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 and water treatment. The widespread use of aluminum, a non-essential element for the human body, has caused people to ingest too much aluminum. According to the recommendation of the world health organization of the United nations, the intake of aluminum ions in the human body is limited to 7mg/kg. High levels of aluminum ions accumulated in the human body pose significant health risks, including alzheimer's disease, osteomalacia, and the induction of various cancers. Also, gallium ions are closely related to human life. For example, gallium nitrate is often used as an anti-cancer drug; gallium arsenide is commonly used in industrial integrated circuits. In both industrial and medical applications, gallium ions are most likely to accumulate in the human body through the food chain, causing toxic and side effects such as dizziness, fatigue and the like. In view of the wide existence of aluminum ions and gallium ions in our lives and the harm to human health, the method has important significance for measuring the contents of the aluminum ions and the gallium ions in an environmental 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 detection by a fluorescent molecular sensor is an excellent method, having advantages of high selectivity, rapid analysis, high sensitivity, etc., as compared to these methods. More importantly, the method is convenient and fast in the process of detecting the metal ions, can not damage the sample and can also carry out convenient visual qualitative identification.
2- (2-Hydroxyphenyl) Benzothiazole (HBT) fluorescent dye has optical propertyCan be stable, has large Stokes shift and the like, and is often used as a fluorescent parent of a fluorescent probe molecule. So far, many reagents capable of separately detecting Al have been developed 3+ And Ga 3+ The fluorescent probe of (1). However, development was simultaneously conducted on Al 3+ And Ga 3+ Multifunctional probes with high sensitivity are still challenging. Based on the above, a novel bifunctional detection Al is developed 3+ And Ga 3+ The fluorescent probe gives a detection curve to judge the level of aluminum ions and gallium ions, and has important research value in the fluorescent imaging diagnosis and analysis of two metal ions in a life system.
Disclosure of Invention
The invention aims to solve the problems of complex synthesis steps and low selectivity and sensitivity of the conventional probe for separately identifying aluminum ions or gallium ions, and provides a bifunctional 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 the aluminum ions and the gallium ions is as follows:
the invention discloses a preparation method of a difunctional fluorescent probe for identifying aluminum ions and gallium ions, which comprises the following steps:
1. reacting 3-methoxysalicylaldehyde with 2-aminothiophenol to obtain a compound 1:
dissolving 3-methoxysalicylaldehyde in N, N-dimethylformamide, sequentially adding sodium metabisulfite and 2-aminothiophenol, stirring in an oil bath at the temperature of 110-120 ℃, reacting for 3-4 h, detecting the reaction by using a TCL (thermal conductive liquid chromatography) 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-methoxysalicylaldehyde to the 2-aminothiophenol is 1; the molar ratio of the 3-methoxy salicylaldehyde to the sodium pyrosulfite is (0.6-1.2) to 1;
2. reacting the compound 1 obtained in the step one with ethyl bromoacetate to obtain a compound 2:
adding compound 1, ethyl bromoacetate and K to acetonitrile 2 CO 3 Heating to 85-90 ℃, reacting for 2-3 h, cooling to room temperature after the reaction is stopped, 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 molar ratio of (1) - (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 at the temperature of 80-85 ℃, reacting for 6-7 h, detecting the reaction by using a TCL (thermal conductive liquid chromatography) plate, cooling to room temperature after the reaction is completed, filtering the precipitate, washing by using ethanol, and drying to obtain a compound 3; wherein the molar ratio of the compound 2 to the hydrazine hydrate is 1:1;
4. and (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 at the temperature of 80-85 ℃, reacting for 2-3 h, detecting the reaction by using a TCL (thermal conductive liquid chromatography) plate, cooling to room temperature after the reaction is completed, filtering the precipitate, washing by using 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.
further, 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. The glacial acetic acid acts as a catalyst, accelerating the reaction rate.
The invention relates to 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 probe is used for carrying out fluorescence imaging detection on aluminum ions and gallium ions in cells.
Optionally adding Na 2 EDTAnd A, realizing repeated detection of gallium ions.
The preparation reaction formula of the difunctional fluorescent probe for the aluminum ions and the gallium ions is as follows:
in the reaction formula, 1 is a compound 1,2 is a compound 2,3 is a compound 3, BMP is a difunctional fluorescent probe of aluminum ions and gallium ions. The invention has the beneficial effects that:
1) The synthesis of the probe can be completed by only four steps, the raw materials are economical, and the post-treatment process is relatively simple;
2) The invention realizes that the probe can identify the aluminum ions and can sense and detect the gallium ions, and has good selectivity, strong anti-interference capability of other metal ions and low detection limit. Aluminum ion: the fluorescence detection limit is 1.5162 multiplied by 10 -6 M, ultraviolet detection limit is 9.4011 × 10 -8 And M. Gallium ion: the fluorescence detection limit is 4.2816 multiplied by 10 -6 M, the ultraviolet detection limit is 3.2019 multiplied by 10 -8 M。
In addition, remarkable fluorescence color change can be observed under an ultraviolet lamp, aluminum ions and gallium ions can be distinguished through different fluorescence colors, and the fluorescent probe has a color generation sensing function. Compared with other fluorescent probes for quantitatively detecting metal ions only through a fluorescent spectrum, the probe can also perform ultraviolet ratio quantitative detection through an ultraviolet spectrum. Based on the specificity and obvious color change of the reagent, the reagent can be used as a specificity indicator for displaying the existence of aluminum ions or gallium ions in an aqueous solution, and can carry out real-time qualitative and quantitative visual colorimetric method detection. And more importantly, sensing of gallium ions can be accomplished by using Na 2 EDTA realizes rapid reversible repeated detection. In addition, the invention can also be applied to the fluorescence imaging identification of aluminum ions or gallium ions in cells. Therefore, the invention is a simple, rapid and sensitive aluminum ion and gallium ion double-function detection reagent, and has wide application prospect in the fields of water sample environment and life system.
Drawings
FIG. 1 shows the BMP probe (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 determination;
FIG. 3 is a graph showing the effect of coexisting ions on the determination of gallium ions;
FIG. 4 shows the BMP probe (concentration: 1X 10) -5 mol/L) in DMF/H 2 For different concentrations of Al under O 3+ A fluorescence spectral response map of (a);
FIG. 5 shows the probe BMP (concentration 1X 10) -5 mol/L) in DMF/H 2 For different concentrations of Al under O 3+ Ultraviolet spectral response diagram of (a);
FIG. 6 shows the probe BMP (concentration 1X 10) -5 mol/L) in DMF/H 2 For Ga of different concentrations under O 3+ A fluorescence spectral response map of (a);
FIG. 7 shows the probe BMP (concentration 1X 10) -5 mol/L) in DMF/H 2 For Ga of different concentrations under O 3+ Ultraviolet spectral response plot of (a);
FIG. 8 is a graph showing fluorescence emission of probe BMP after adding aluminum ions and gallium ions, respectively, under an ultraviolet lamp at 365 nm;
FIG. 9 is a graph showing reversible changes in recognition of gallium ions by a probe BMP;
FIG. 10 is a naked eye visual detection diagram of aluminum ions and gallium ions by means of test paper dip dyeing;
FIG. 11 is a fluorescent identification chart of aluminum ion and gallium ion in cells using probe BMP.
Detailed Description
The technical solution of the present invention is not limited to the following specific embodiments, but includes any combination of the specific embodiments.
The first embodiment is as follows: the structural formula of the bifunctional fluorescent probe for identifying aluminum ions and gallium ions in the embodiment is as follows:
the dual-functional fluorescent probe for detecting aluminum ions and gallium ions in the embodiment is marked as probe BMP, the probe itself has no fluorescence due to the isomerization of PET mechanism and C = N, and after the fluorescent probe BMP reacts with the aluminum ions and the gallium ions, the isomerization of the PET mechanism and C = N is inhibited, so that the fluorescence of the detection system is enhanced and the fluorescence color is changed.
The second embodiment is as follows: the preparation method of the difunctional fluorescent probe for identifying the aluminum ions and the gallium ions comprises the following steps:
1. reacting 3-methoxysalicylaldehyde with 2-aminothiophenol to obtain a compound 1:
dissolving 3-methoxysalicylaldehyde in N, N-dimethylformamide, sequentially adding sodium metabisulfite and 2-aminothiophenol, stirring in an oil bath at the temperature of 110-120 ℃, reacting for 3-4 h, detecting the reaction by using a TCL (thermal conductive liquid chromatography) 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-methoxysalicylaldehyde to the 2-aminothiophenol is 1; the molar ratio of the 3-methoxy salicylaldehyde to the sodium pyrosulfite is (0.6-1.2) to 1;
2. reacting the compound 1 obtained in the first step with ethyl bromoacetate to obtain a compound 2:
adding compound 1, ethyl bromoacetate and K to acetonitrile 2 CO 3 Heating to 85-90 ℃, reacting for 2-3 h, cooling to room temperature after the reaction is stopped, 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 molar ratio of (1) - (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 at the temperature of 80-85 ℃, reacting for 6-7 h, detecting the reaction by using a TCL (thermal conductive liquid chromatography) plate, cooling to room temperature after the reaction is completed, filtering the precipitate, washing by using ethanol, and drying to obtain a compound 3; wherein the molar ratio of the compound 2 to the hydrazine hydrate is 1:1;
4. and (3) 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 at the temperature of 80-85 ℃, reacting for 2-3 h, detecting the reaction by using a TCL (thermal conductive liquid chromatography) plate, cooling to room temperature after the reaction is completed, filtering the precipitate, washing by using 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.
the third concrete implementation mode: the second embodiment is different from the first embodiment in that: and step two, washing with deionized water for 5 times. The rest is the same as the second embodiment.
The fourth concrete implementation mode: the second or third embodiment is different from the first or second embodiment in that: and in the second step, separating and purifying by silica gel column chromatography by using ethyl acetate/petroleum ether as an eluent. The other is the same as the second or third embodiment.
The fifth concrete implementation mode: the difference between this embodiment and one of the second to fourth embodiments is: and in the third step and the fourth step, washing for 3-5 times by using ethanol. The other is the same as one of the second to fourth embodiments.
The sixth specific implementation mode: the difunctional fluorescent probe provided by the embodiment is applied to heavy metal ion detection.
The seventh concrete implementation mode: the sixth embodiment is different from the specific 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 rest is the same as the fourth embodiment.
The specific implementation mode is eight: the sixth or seventh embodiment is different 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 the sixth or seventh embodiments.
The naked eye visual detection of the aluminum ions and the gallium ions can be realized by using a test paper dip dyeing mode.
Detailed description of the inventionThe method is nine: this embodiment differs from one of the sixth to eighth embodiments in that: further adding Na 2 EDTA realizes repeated detection of gallium ions. The rest is the same as the sixth to eighth embodiments.
The detailed implementation mode is ten: the present embodiment differs from one of the sixth to ninth embodiments in that: the difunctional 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 are given to illustrate the present invention, and the following examples are carried out on the premise of the technical solution of the present invention, and give detailed embodiments and specific procedures, 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 comprises the following steps:
(1) Synthesis of Compound 1:
3-methoxy salicylaldehyde (0.85g, 5.60mmol) is dissolved in 15ml DMF, then sodium metabisulfite (1.28g, 6.72mmol) and 2-aminothiophenol (0.60mL, 5.60mmol) are added in sequence, and stirred in an oil bath at 110 ℃. And monitoring the reaction process by TLC, cooling the mixed solution to room temperature after the reaction is completed, pouring 20mL of deionized water with the temperature of 0 ℃ into the mixed solution to separate out a large amount of yellow solid, filtering and precipitating, washing the obtained filter cake for 5 times by using absolute ethyl alcohol, and drying to obtain the compound 1 which is light yellow solid and has the yield of 80.5%.
(2) Synthesis of Compound 2:
to a round bottom flask containing 25mL of acetonitrile was added Compound 1 (0.46g, 1.80mmol), followed by potassium carbonate (1.28g, 3.60mmol) and ethyl bromoacetate (0.20mL, 1.83mmol), and the mixture was heated under reflux to the end of the reaction (TLC monitoring) at a temperature of 90 ℃. After the reaction liquid is cooled, the reaction liquid is filtered, washed by deionized water to obtain a crude product, and the crude product is separated and purified by silica gel column chromatography by using ethyl acetate/petroleum ether as an eluent and dried to obtain a compound 2 which is a white solid with the yield of 76.0%.
(3) Synthesis of Compound 3:
compound 2 (0.41g, 1.20mmol) was dissolved in 20mL of anhydrous ethanol, and 1.20mmol of hydrazine hydrate was added thereto at room temperature, and the mixture was refluxed until the starting material spot disappeared (TLC tracing reaction) and the heating temperature was 80 ℃. Stopping reaction, standing for 30min to separate out a large amount of precipitate, filtering, washing the precipitate with absolute ethyl alcohol for three times, and drying to obtain a compound 3 which is a white solid with a yield of 91.1%.
(4) Synthesis of target compound:
adding compound 3 (164mg, 0.50mmol) and 5-methyl salicylaldehyde (68mg, 0.50mmol) into 15mL of absolute ethyl alcohol, dropwise adding two drops of glacial acetic acid into the absolute ethyl alcohol, heating and refluxing, heating to 80 ℃, reacting for 2.5h, detecting the reaction by using a TCL plate, cooling to room temperature after the reaction is completed, filtering a precipitate, washing for 5 times by using absolute ethyl alcohol, and drying to obtain the target compound BMP with the yield of 81.3%.
Example 2:
application of a bifunctional fluorescent probe BMP for identifying aluminum ions and gallium ions.
The fluorescent probe BMP for bifunctional recognition of aluminum ion and gallium ion synthesized in example 1 is dissolved in DMF, and the preparation concentration is 1 × 10 -5 mol/L of DMF/H 2 O (2/3, v/v), and detecting the fluorescence selectivity of the probe to different metal ions by using a spectrophotometer, wherein FIG. 1 is a fluorescence selectivity spectrogram, and can be seen in FIG. 1Almost no fluorescence emission is generated under the excitation of the wavelength of 370 nm; after adding different metal ions, detecting the change of the fluorescence intensity by using a fluorescence spectrophotometer, wherein the result is shown in figure 1, after adding aluminum ions, the maximum fluorescence emission wavelength is observed at 472nm, and the fluorescence intensity is obviously enhanced; after the gallium ions are added, the maximum fluorescence emission wavelength is 482nm, the fluorescence intensity is obviously enhanced, and the addition of other metal ions is almost unchanged.
To further confirm that the selectivity of the probe to aluminum ions and gallium ions is not affected in the presence of other metal ions, a competitive fluorescence experiment was performed, and as a result, as shown in fig. 2 and 3, the fluorescence spectrum analysis shows that the recognition of aluminum ions and gallium ions by the probe is not affected in the presence of other metal ions.
FIG. 2 shows the effect of coexisting ions on the measurement of aluminum ions, and FIG. 2 shows "Al 3+ "is 1.0X 10 -5 The fluorescence intensity of the system when the aluminum ions exist alone in mol/L, and the fluorescence intensity of the system when the aluminum ions with the same concentration and various metal ions with the same concentration times coexist in the rest. The black bars indicate the fluorescence intensity of the probe and the probe when each metal ion is added alone, and the gray diagonal bars indicate the fluorescence intensity of the system when aluminum ions with the same concentration and various metal ions with the same concentration multiple coexist. As can be seen, al is added 3+ The fluorescence of the rear probe is enhanced, and the detection result of the probe molecule on the aluminum ions is not obviously changed by the existence of the coexisting ions.
FIG. 3 shows the effect of coexisting ions on the measurement of gallium ions, and the symbol "Ga" in FIG. 3 3+ "is 1.0X 10 -5 The fluorescence intensity of the system when the gallium ions of mol/L exist alone, and the fluorescence intensity of the system when the gallium ions of the same concentration coexist with various metal ions of the same concentration times. The black bars represent the fluorescence intensity of the probe and the probe when various metal ions are added alone, and the gray diagonal bars represent the fluorescence intensity of the system when aluminum ions of the same concentration and various metal ions of the same concentration multiple coexist. As can be seen, ga is added 3+ The fluorescence of the rear probe is enhanced, and the detection result of the probe molecule for gallium ions is not obviously changed by the existence of the coexisting ions.
Adding aluminum ions with different concentrations into the solution, detecting the change of the fluorescence intensity and the ultraviolet absorption intensity, and as shown in FIG. 4 and FIG. 5, the fluorescence spectrum analysis shows that the concentration of the added aluminum ions is 0 to 5X 10 -5 In the mol/L range, the change of fluorescence intensity and ultraviolet absorption intensity respectively has good linear relation curves with the added concentration, thereby realizing the quantitative detection of aluminum ions.
FIG. 4 shows the probe BMP (concentration 1X 10) -5 mol/L) in DMF/H 2 For different concentrations of Al under O (2/3, v/v) 3+ Fluorescence spectral response plot of (a). In FIG. 4, the abscissa is the wavelength (nm), the ordinate is the 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 multiplied by 10 -6 M。
FIG. 5 shows the probe BMP (concentration 1X 10) -5 mol/L) in DMF/H 2 For different concentrations of Al under O (2/3, v/v) 3+ Ultraviolet spectral response diagram of (1). In fig. 5, the abscissa is the wavelength (nm) and the ordinate is the ultraviolet absorption intensity. The concentration of aluminum ions is from 0 to 5X 10 -5 mol/L, detection limit of 9.4011 × 10 -8 M。
Adding gallium ions with different concentrations into the solution, detecting the change of the fluorescence intensity and the ultraviolet absorption intensity, as shown in FIG. 6 and FIG. 7, the fluorescence spectrum analysis shows that the concentration of the added gallium ions is 0 to 1.5X 10 -4 In the mol/L range, the change of fluorescence intensity and ultraviolet absorption intensity respectively has good linear relation curves with the added concentration, thereby realizing the quantitative detection of gallium ions.
FIG. 6 shows the probe BMP (concentration 1X 10) -5 mol/L) in DMF/H 2 For Ga in different concentrations under O (2/3, v/v) 3+ Fluorescence spectral response plot of (a). In FIG. 6, the abscissa is the wavelength (nm), the ordinate is the fluorescence intensity, and the excitation wavelength is 370nm. The concentration of gallium ion is from 0 to 1.5 × 10 -4 mol/L, detection limit of 4.2816X 10 -6 M。
FIG. 7 shows the probe BMP (concentration 1X 10) -5 mol/L) in DMF/H 2 Ga (2/3, v/v) at different concentrations 3+ Ultraviolet spectral response diagram of (a). In FIG. 7, the abscissa is the wavelength (nm) and the ordinate is the ultraviolet absorption intensity. The concentration of gallium ion is from 0 to 1.5 × 10 -4 mol/L, detection limit is 3.2019 multiplied by 10 -8 M。
FIG. 8 is a graph showing fluorescence emission of probe BMP after adding aluminum ion and gallium ion, respectively, under an ultraviolet lamp at 365 nm. To 1X 10 -5 Adding 5X 10 mol/L probe solution -5 mol/L of aluminum ion and 5X 10 -5 After being placed under an ultraviolet lamp at 365nm, the gallium ions in mol/L change the fluorescence color (from non-fluorescence to blue and blue-green fluorescence respectively), so that the visual qualitative detection of the aluminum ions and the gallium ions is realized. As can be seen, after the aluminum ions are added, the solution can emit blue fluorescence; after the gallium ions are added, the solution can emit blue-green fluorescence.
FIG. 9 shows a view of a direction of 1X 10 -5 Adding 5X 10 mol/L probe solution -5 Adding 5X 10 of gallium ions after mol/L -5 mol/L Na 2 The reversibility change after EDTA can realize more than 3 times of cyclic detection on gallium ions. Reversible change of the probe BMP on gallium ion recognition is that after gallium ions are added into BMP solution, fluorescence is obviously increased, and then equivalent Na is added 2 The fluorescence is restored to a quenching state after EDTA, and the reversible recognition of the probe BMP to the gallium ions can be repeatedly cycled for at least 3 times.
FIG. 10 is a schematic diagram of naked eye visual detection of aluminum ions and gallium ions by test paper dip dyeing, in which BMP and 5 μ MAL are respectively arranged from left to right in the upper row 3+ 、10μMAl 3+ 、15μMAl 3+ 、20μMAl 3+ (ii) a The lower row is 10 mu MGa from left to right 3+ 、20μMGa 3 + 、40μMGa 3+ 、80μMGa 3+ . The 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), taking out the solution after dip dyeing for two hours, and drying the solution in the air. Placing the dried test paper under 365nm ultraviolet lamp, and adding Al 3+ Or Ga 3+ The test paper showed a visible color change from colorless to bright blue or colorless to cyan with increasing concentration. This phenomenon indicates that probe BMP can be loaded on test paper for Al 3+ Or Ga 3+ And (5) carrying out fluorescence colorimetric detection.
FIG. 11 shows the application of probe BMP to cellsIn the fluorescence identification of aluminum ions and gallium ions, BMP (100 mu M) and aluminum ions or gallium ions are respectively incubated with A549 cells, and the fluorescence emission in the cells can be observed by a laser confocal fluorescence microscope. A549 cells are selected as research objects. First use of cell with Al 3+ Or Ga 3+ After 2h (50. Mu.M) culture, cells were fixed by washing 3 times with serum-free medium and adding 4% paraformaldehyde. After 1h, the paraformaldehyde is washed away with PBS, and the sample is further incubated with probe BMP (10 μ M) for 2h, rinsed with PBS three times, and finally placed under laser confocal imaging. Fluorescence imaging results show that only when the probes BMP and Al 3+ Or Ga 3+ Fluorescence signals can be observed in the experimental group for co-incubation, which shows that the probe BMP can treat Al in cells 3+ Or Ga 3+ And performing fluorescence imaging identification.
Claims (10)
1. A bifunctional fluorescent probe for identifying aluminum ions and gallium ions is characterized in that the structural formula of the bifunctional fluorescent probe is as follows:
2. the method for preparing the bifunctional fluorescent probe for identifying aluminum ions and gallium ions in claim 1, which is characterized by comprising the following steps:
1. reacting 3-methoxy salicylaldehyde with 2-aminothiophenol to obtain a compound 1:
dissolving 3-methoxysalicylaldehyde in N, N-dimethylformamide, sequentially adding sodium metabisulfite and 2-aminothiophenol, stirring in an oil bath at the temperature of 110-120 ℃, reacting for 3-4 h, detecting the reaction by using a TCL (thermal conductive liquid chromatography) 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-methoxysalicylaldehyde to the 2-aminothiophenol is 1; the molar ratio of the 3-methoxy salicylaldehyde to the sodium pyrosulfite is (0.6-1.2) to 1;
2. reacting the compound 1 obtained in the step one with ethyl bromoacetate to obtain a compound 2:
adding compound 1, ethyl bromoacetate and K to acetonitrile 2 CO 3 Heating to 85-90 ℃, reacting for 2-3 h, cooling to room temperature after the reaction is stopped, 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 molar 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 at the temperature of 80-85 ℃, reacting for 6-7 h, detecting the reaction by using a TCL (thermal conductive liquid) plate, cooling to room temperature after the reaction is completed, filtering the precipitate, washing by using ethanol, and drying to obtain a compound 3; wherein the molar ratio of the compound 2 to the hydrazine hydrate is 1:1;
4. and (3) 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 at the temperature of 80-85 ℃, reacting for 2-3 h, detecting the reaction by using a TCL (thermal conductive liquid chromatography) plate, cooling to room temperature after the reaction is completed, filtering the precipitate, washing by using 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 capable of recognizing aluminum ions and gallium ions according to claim 2, wherein in step two, deionized water is used for washing 5 times.
4. The method for preparing a bifunctional fluorescent probe capable of recognizing aluminum ions and gallium ions according to claim 2, wherein the step two is performed with silica gel column chromatography using ethyl acetate/petroleum ether as eluent.
5. The method for preparing a bifunctional fluorescent probe capable of recognizing aluminum ions and gallium ions according to claim 2, wherein the steps three and four are washed with ethanol for 3-5 times.
6. The use of the bifunctional fluorescent probe of claim 1 for heavy metal ion detection.
7. The application of claim 6, wherein the bifunctional fluorescent probe is specifically used for sensing and detecting the content of aluminum ions and gallium ions in a water environment system.
8. The use of claim 7, wherein the sensory test comprises fluorescence, ultraviolet ratiometric, visual qualitative, gallium ion reversible, or dipstick tests.
9. Use according to claim 6, characterized in that Na is also added 2 EDTA realizes repeated detection of gallium ions.
10. The use according to claim 6, wherein the bifunctional fluorescent probe is used for fluorescence imaging detection of aluminum ions and gallium ions in cells.
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