CN109438386B - Difunctional fluorescent probe for identifying aluminum ions and zinc ions as well as preparation method and application thereof - Google Patents
Difunctional fluorescent probe for identifying aluminum ions and zinc ions as well as preparation method and application thereof Download PDFInfo
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- PTFCDOFLOPIGGS-UHFFFAOYSA-N Zinc dication Chemical compound [Zn+2] PTFCDOFLOPIGGS-UHFFFAOYSA-N 0.000 title claims abstract description 66
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- -1 aluminum ions Chemical class 0.000 title claims abstract description 52
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- 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
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- 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
- G01N21/17—Systems in which incident light is modified in accordance with the properties of the material investigated
- G01N21/25—Colour; Spectral properties, i.e. comparison of effect of material on the light at two or more different wavelengths or wavelength bands
- G01N21/31—Investigating relative effect of material at wavelengths characteristic of specific elements or molecules, e.g. atomic absorption spectrometry
- G01N21/33—Investigating relative effect of material at wavelengths characteristic of specific elements or molecules, e.g. atomic absorption spectrometry using ultraviolet light
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
- G01N21/62—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light
- G01N21/63—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light optically excited
- G01N21/64—Fluorescence; Phosphorescence
- G01N21/6428—Measuring fluorescence of fluorescent products of reactions or of fluorochrome labelled reactive substances, e.g. measuring quenching effects, using measuring "optrodes"
- G01N21/643—Measuring fluorescence of fluorescent products of reactions or of fluorochrome labelled reactive substances, e.g. measuring quenching effects, using measuring "optrodes" non-biological material
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
- G01N21/62—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light
- G01N21/63—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light optically excited
- G01N21/64—Fluorescence; Phosphorescence
- G01N21/6447—Fluorescence; Phosphorescence by visual observation
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
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- 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
Abstract
A difunctional fluorescent probe for identifying aluminum ions and zinc ions and a preparation method and application thereof relate to a difunctional fluorescent probe and a preparation method and application thereof. The method aims to solve the problems of complicated synthesis steps and low selectivity and sensitivity of the conventional probe for separately identifying aluminum ions or zinc ions. The bifunctional fluorescent probe is a covalent combination of 2- (2-hydroxyphenyl) benzothiazole and salicylhydrazide. The method comprises the following steps: firstly, 5-methyl salicylaldehyde reacts with o-aminothiophenol to obtain a compound 1; secondly, reacting the compound 1 with urotropine to obtain a compound 2; and thirdly, reacting the compound 2 with salicylhydrazine to obtain the target compound Z. The synthesis of the probe can be completed only by three steps, and the post-treatment process is relatively simple; the probe can identify the aluminum ions and can sense and detect the zinc ions, and the detection method has the advantages of good selectivity, strong anti-interference capability 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
It is known that aluminum is the second most abundant metal element in the earth crust, and its compound is widely used in water treatment, food additives, medicines, light alloys, etc. The widespread use of aluminum as an unnecessary element in the human body causes excessive intake of aluminum, which accumulates in various tissues and organs of the human body, thereby causing various diseases such as hypopigmentation anemia of small cells, diseases related to aluminum bones, encephalopathy, myopathy, dementia, and alzheimer's disease. In addition, the trivalent aluminum ion is widely present in many plant and animal tissues and in the water system of the nature. Excessive aluminum ions pose a danger of extinction of some fish in the water. In acid soils, an excess of aluminium ions results in a substantial reduction in the yield of agricultural products. Under acidic conditions, the solubility of aluminum-containing minerals becomes greater, which will be more harmful to the mildly acidic aquatic life. The zinc ion is the second most abundant transition metal in the organism, and the zinc ion has very important significance and effect in the organism. Zinc can control the gene expression mechanism, and can affect the chromatin structure, the function of DNA template, the activity of transcription factor and RNA polymerase, etc. Because of the importance of aluminum ions and zinc ions to life, the determination of the content of the aluminum ions and the zinc ions in an environmental system and a life system has important significance.
At present, the means widely used for metal ion detection include atomic absorption spectrometry, inductively coupled plasma mass spectrometry, electrochemical analysis and the like, but these methods require expensive and complex instruments and skilled operating professionals in the process of detecting metal ions, and the defects of the analysis methods are that the analysis process is complicated, the detection and analysis time is long, the analysis cost is high and the like, which obviously does not meet the requirement of rapid on-site evaluation required by modern environmental monitoring. In recent years, fluorescence detection and analysis methods based on chemical sensors attract special attention of people, and the fluorescence detection and analysis methods are simple and convenient to operate, high in selectivity and sensitivity, quick in analysis time, free of sample damage and capable of conducting convenient visual qualitative identification.
In recent years, many probes for separately recognizing aluminum ions or zinc ions have been reported, but the synthetic procedures of these probes are complicated, and the selectivity and sensitivity are low, resulting in a decrease in the applicability of the probes.
Disclosure of Invention
The invention aims to solve the problems of complicated synthesis steps and low selectivity and sensitivity of the conventional probe for independently identifying aluminum ions or zinc ions, and provides a bifunctional fluorescent probe for identifying aluminum ions and zinc ions, and a preparation method and application thereof.
The bifunctional fluorescent probe for identifying aluminum ions and zinc ions is a covalent combination of 2- (2-hydroxyphenyl) benzothiazole and salicyloyl hydrazide, and the structural formula of the bifunctional fluorescent probe is as follows:
the preparation method of the difunctional fluorescent probe for identifying the aluminum ions and the zinc ions comprises the following steps:
reacting the primary, 5-methyl salicylaldehyde and o-aminothiophenol to obtain a compound 1:
dissolving 5-methyl salicylaldehyde and o-aminothiophenol in N, N-Dimethylformamide (DMF), adding sodium pyrosulfite, heating and refluxing 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 separate out a light yellow precipitate, filtering the precipitate, washing with the deionized water for 5-6 times, and drying to obtain a compound 1;
wherein the molar ratio of the 5-methyl salicylaldehyde to the o-aminothiophenol is 1: 1;
secondly, reacting the compound 1 obtained in the first step with urotropine to obtain a compound 2:
dissolving the compound 1 and urotropine in trifluoroacetic acid, heating and refluxing, wherein the heating temperature is 70-75 ℃, reacting for 7-8 h, detecting and reacting by using a TCL (thermal conductive liquid chromatography) plate, after the reaction is completed, adding deionized water into the solution, continuing to react for 10-20 min, separating out a large amount of precipitate, filtering the precipitate, washing with deionized water for 5-6 times, and drying to obtain a compound 2;
wherein the molar ratio of the compound 1 to the urotropine is 1 (2-5);
thirdly, reacting the compound 2 obtained in the second step with salicylhydrazine to obtain a target compound Z:
adding the compound 2 and salicyloyl hydrazine into ethanol, heating and refluxing at 80-85 ℃, reacting for 4-5 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 for 5-6 times by using ethanol, and drying to obtain a target compound Z; wherein the molar ratio of the compound 2 to the salicylhydrazide is 1: 1.
Further, in the third step, after the compound 2 and the salicylhydrazine are added into the ethanol, glacial acetic acid is also added until the pH value of the reaction system is 4-6. The glacial acetic acid acts as a catalyst, accelerating the reaction rate.
The invention discloses application of a bifunctional fluorescent probe in heavy metal ion detection. The method is used for sensing and detecting the content of aluminum ions and zinc ions in a water environment system; the sensing detection is fluorescence detection, ultraviolet ratio detection, visual qualitative detection or zinc ion reversible detection.
Optionally adding Na2EDTA realizes repeated detection of zinc ions and is used as an important means for distinguishing aluminum ions from zinc ions.
The preparation reaction formula of the difunctional fluorescent probe is as follows:
the invention has the beneficial effects that:
1) the synthesis of the probe can be completed only by three steps, the raw materials are economical and easy to obtain, 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 zinc ions, and has good selectivity, strong anti-interference capability to other metal ions and low detection limit. Aluminum ion: the fluorescence detection limit is 1.4209 multiplied by 10-7M, ultraviolet detection limit of 3.9953 multiplied by 10-8And M. Zinc ion: the fluorescence detection limit is 1.2676 multiplied by 10-7M, ultraviolet detection limit of 3.3180 multiplied by 10-8M。
In addition, the color change of the solution can be observed by naked eyes under sunlight, and the color change of fluorescence can also be observed under an ultraviolet lamp, so that 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 zinc ions in an aqueous solution, and can carry out real-time qualitative and quantitative visual colorimetric method detection. And more importantly, the sensing detection of zinc ions can be realized by using Na2EDTA realizes rapid reversible repeated detection, and Na is added for sensing detection of aluminum ions2EDTA is irreversible, which also realizes that the probe detects the aluminum ionsThe important means for distinguishing the zinc ion from the proton in the process. Therefore, the invention is a simple, rapid and sensitive aluminum ion and zinc ion double-function detection reagent, and has wide application prospect in the field of water sample environment detection.
Drawings
FIG. 1 shows probe Z (concentration: 1X 10)-5mol/L) in DMF/H2Selectivity 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 zinc ion determination;
FIG. 4 shows probe Z (concentration: 1X 10)-5mol/L) in DMF/H2For different concentrations of Al under O3+A fluorescence spectral response map of (a);
FIG. 5 shows probe Z (concentration: 1X 10)-5mol/L) in DMF/H2For different concentrations of Al under O3+Ultraviolet spectral response diagram of (a);
FIG. 6 shows probe Z (concentration: 1X 10)-5mol/L) in DMF/H2For different concentrations of Zn under O2+A fluorescence spectral response map of (a);
FIG. 7 shows probe Z (concentration: 1X 10)-5mol/L) in DMF/H2For different concentrations of Zn under O2+Ultraviolet spectral response diagram of (a);
FIG. 8 is a graph showing fluorescence emission of probe Z under 365nm with an ultraviolet lamp after adding aluminum ions and zinc ions, respectively;
FIG. 9 is a diagram showing the change of the appearance color of the probe Z in sunlight after the probe Z is added with aluminum ions and zinc ions, respectively;
FIG. 10 is a graph showing reversible changes in recognition of zinc ions by the probe Z.
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 bifunctional fluorescent probe for identifying aluminum ions and zinc ions in the embodiment is a covalent combination of 2- (2-hydroxyphenyl) benzothiazole and salicyloyl hydrazide, and the structural formula of the bifunctional fluorescent probe is as follows:
the second embodiment is as follows: the preparation method of the bifunctional fluorescent probe for identifying aluminum ions and zinc ions comprises the following steps:
reacting the primary, 5-methyl salicylaldehyde and o-aminothiophenol to obtain a compound 1:
dissolving 5-methyl salicylaldehyde and o-aminothiophenol in N, N-Dimethylformamide (DMF), adding sodium pyrosulfite, heating and refluxing 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 separate out a light yellow precipitate, filtering the precipitate, washing with the deionized water for 5-6 times, and drying to obtain a compound 1;
wherein the molar ratio of the 5-methyl salicylaldehyde to the o-aminothiophenol is 1: 1;
secondly, reacting the compound 1 obtained in the first step with urotropine to obtain a compound 2:
dissolving the compound 1 and urotropine in trifluoroacetic acid, heating and refluxing, wherein the heating temperature is 70-75 ℃, reacting for 7-8 h, detecting and reacting by using a TCL (thermal conductive liquid chromatography) plate, after the reaction is completed, adding deionized water into the solution, continuing to react for 10-20 min, separating out a large amount of precipitate, filtering the precipitate, washing with deionized water for 5-6 times, and drying to obtain a compound 2;
wherein the molar ratio of the compound 1 to the urotropine is 1 (2-5);
thirdly, reacting the compound 2 obtained in the second step with salicylhydrazine to obtain a target compound Z:
adding the compound 2 and salicyloyl hydrazine into ethanol, heating and refluxing at 80-85 ℃, reacting for 4-5 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 for 5-6 times by using ethanol, and drying to obtain a target compound Z; wherein the molar ratio of the compound 2 to the salicylhydrazide is 1: 1.
The third concrete implementation mode: the second embodiment is different from the first embodiment in that: in the third step, after the compound 2 and the salicylhydrazine are added into the ethanol, glacial acetic acid is also added until the pH value of the reaction system is 4-6. The rest is the same as the second embodiment.
The fourth concrete implementation mode: the application of the bifunctional fluorescent probe in the detection of heavy metal ions is provided.
The fifth concrete implementation mode: the fourth difference between this embodiment and the specific embodiment is that: the dual-function fluorescent probe is particularly used for sensing and detecting the content of aluminum ions and zinc ions in a water environment system. The rest is the same as the fourth embodiment.
The sixth specific implementation mode: the fifth embodiment is different from the fifth embodiment in that: the sensing detection is fluorescence detection, ultraviolet ratio detection, visual qualitative detection or zinc ion reversible detection. The rest is the same as the fifth embodiment.
The seventh embodiment: the fourth difference between this embodiment and the specific embodiment is that: further adding Na2EDTA realizes repeated detection of zinc ions and distinguishes aluminum ions from zinc ions. The rest is the same as the fourth embodiment.
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:
(1) synthesis of Compound 1:
dissolving 5-methyl salicylaldehyde (4.66g, 37.22mmol) and o-aminothiophenol (5.1g, 37.46mmol) in 50ml of N, N-Dimethylformamide (DMF), adding sodium metabisulfite (6g, 31.56mmol), heating and refluxing at 110 ℃, reacting for 3h, detecting the reaction by using a TCL plate, cooling to room temperature after the reaction is completed, adding 50ml of deionized water into the solution to precipitate a light yellow precipitate, filtering the precipitate, washing with deionized water for 5 times, and drying to obtain the compound 1 with the yield of 93.56%.
(2) Synthesis of Compound 2:
dissolving compound 1(500mg, 2.07mmol) and urotropine (581mg, 4.14mmol) in 10ml of trifluoroacetic acid, heating and refluxing at 70 ℃, reacting for 7h, detecting the reaction by using a TCL plate, after the reaction is completed, adding 20ml of deionized water into the solution, continuing the reaction for 10min to separate out a large amount of precipitate, filtering the precipitate, washing the precipitate with deionized water for 5 times, and drying to obtain compound 2 with the yield of 92.13%.
(3) Synthesis of target compound:
adding the compound 2(99.5mg, 0.37mmol) and salicyloyl hydrazine (58mg,0.38mmol) into 20ml of ethanol, dropwise adding two drops of glacial acetic acid into the ethanol, heating and refluxing at the heating temperature of 80 ℃, reacting for 4h, detecting the reaction by using a TCL plate, cooling to room temperature after the reaction is completed, filtering the precipitate, washing with ethanol for 5 times, and drying to obtain the target compound Z with the yield of 83.24%.
Example 2:
application of aluminum ion and zinc ion dual-function fluorescent probe Z
The aluminum ion and zinc ion bifunctional fluorescent probe Z synthesized in example 1 is dissolved in DMF, and the preparation concentration is 1X 10-5mol/L of DMF/H2O (1/1, v/v,0.01M HEPES, pH 6), detecting its fluorescence selectivity to different metal ions, fig. 1 is a fluorescence selectivity spectrogram, and it can be seen in fig. 1 that the probe itself has a maximum emission wavelength of 500nm, a Stokes shift of 80nm, and weak yellow fluorescence under the excitation of 420nm wavelength; after adding different metal ions, the fluorescence intensity change is detected by a fluorescence spectrophotometer, the result is shown in figure 1, and the maximum fluorescence emission wavelength is blue-shifted to494nm, the fluorescence intensity is obviously enhanced; after zinc ions are added, the maximum fluorescence emission wavelength is red-shifted to 508nm, and the fluorescence intensity is obviously enhanced; and Cd2 +，Pb2+Although the addition of (A) enhances the fluorescence, the increase is smaller than that of aluminum ions and zinc ions, the change of the fluorescence color is not obvious, and the addition of other metal ions hardly changes.
To further confirm that the selectivity of aluminum ion and zinc ion is not affected by the coexistence of other metal ions, competitive fluorescence experiments were performed, and the results are shown in FIG. 2 and FIG. 3 (black in FIGS. 2 and 3 represents the fluorescence intensity of a probe added with a certain metal ion alone, and the oblique line represents the fluorescence intensity of a probe added with another metal ion species after the addition of aluminum ion or zinc ion), FIG. 2 represents the effect of the coexisting ions on the measurement of aluminum ion, and "Al" is marked in FIG. 23+"is 1.0X 10-5The 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 the various metal ions with the same concentration multiple coexist in the rest. As can be seen, the presence of the coexisting ions did not significantly change the detection result of the probe molecules for aluminum ions. FIG. 3 shows the effect of coexisting ions on the determination of zinc ion, and the symbol "Zn" in FIG. 32+"is 1.0X 10-5The fluorescence intensity of the system when the zinc ions exist alone in mol/L, and the fluorescence intensity of the system when the zinc ions with the same concentration and the various metal ions with the same concentration multiple coexist in the rest. As can be seen, the presence of the coexisting ions does not significantly change the detection result of the probe molecules for zinc ions.
Fluorescence spectrum analysis shows that the recognition of the aluminum ions and the zinc ions by the probe is not influenced under the condition of coexisting with other metal 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 figure 4 and figure 5, the figure 4 is the probe Z (the concentration is 1X 10)-5mol/L) in DMF/H2Different concentrations of Al in O (1/1, v/v,0.01M HEPES, pH 6)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 420And (5) nm. The concentration of aluminum ions is from 0 to 5X 10-6mol/L. FIG. 5 shows probe Z (concentration: 1X 10)-5mol/L) in DMF/H2Different concentrations of Al in O (1/1, v/v,0.01M HEPES, pH 6)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 10-6mol/L. After adding aluminum ions with the concentration of 0 to 5X 10-6In 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.
Zinc ions of different concentrations were added to the solution and the change in fluorescence intensity and UV absorption intensity was detected, and FIG. 6 shows probe Z (concentration: 1X 10)-5mol/L) in DMF/H2O (1/1, v/v,0.01M HEPES, pH 6) for different concentrations of Zn2+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 420 nm. The concentration of zinc ion is from 0 to 1X 10-5mol/L. FIG. 7 shows probe Z (concentration: 1X 10)-5mol/L) in DMF/H2O (1/1, v/v,0.01M HEPES, pH 6) for different concentrations of Zn2+Ultraviolet spectral response diagram of (1). In fig. 7, the abscissa is the wavelength (nm) and the ordinate is the ultraviolet absorption intensity. The concentration of zinc ion is from 0 to 1X 10-5mol/L。
As shown in FIGS. 6 and 7, the fluorescence spectrum analysis showed that the concentration of zinc ions was 0 to 1X 10-5In 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 zinc ions.
FIG. 8 and FIG. 9 show the direction of 1X 10-5Adding 5X 10 mol/L probe solution-6mol/L of aluminum ion and 1X 10- 5The color change (from colorless to yellow) under sunlight after mol/L of zinc ions and the color change (from yellow fluorescence to bluish and turquoise) under 365nm irradiation of an ultraviolet lamp realize visual qualitative detection of aluminum ions and zinc ions.
FIG. 10 shows the direction of 1X 10-5Adding 1X 10 to mol/L probe solution-5After mol/L of zinc ionsThen adding 1X 10-5mol/LNa2The reversible change after the EDTA is formed,
in FIG. 10, the upper half is that after adding zinc ion under sunlight, the same amount of Na is added2Color change after EDTA, the lower half of FIG. 10 is that after zinc ion is added under 365nm UV lamp, the same amount of Na is added2The fluorescent color changes after EDTA, and the reversible recognition of the zinc ions by the probe Z can be repeatedly cycled for at least 5 times. Na is not available for the binding of the probe and aluminum ions2EDTA undergoes a reversible change and thus can be used to further distinguish zinc ions from aluminum ions.
Claims (6)
1. A bifunctional fluorescent probe for identifying aluminum ions and zinc ions is characterized in that the bifunctional fluorescent probe for identifying the aluminum ions and the zinc ions is a covalent combination of 2- (2-hydroxyphenyl) benzothiazole and salicyloyl hydrazide, and 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 zinc ions as claimed in claim 1, which comprises the steps of:
reacting the primary, 5-methyl salicylaldehyde and o-aminothiophenol to obtain a compound 1:
dissolving 5-methyl salicylaldehyde and o-aminothiophenol in N, N-Dimethylformamide (DMF), adding sodium pyrosulfite, heating and refluxing 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 separate out a faint yellow precipitate, filtering the precipitate, washing with deionized water for 5-6 times, and drying to obtain a compound 1, wherein the structural formula of the compound 1 is as shown in formula (I):
wherein the molar ratio of the 5-methyl salicylaldehyde to the o-aminothiophenol is 1: 1;
secondly, reacting the compound 1 obtained in the first step with urotropine to obtain a compound 2:
dissolving the compound 1 and urotropine in trifluoroacetic acid, heating and refluxing, wherein the heating temperature is 70-75 ℃, reacting for 7-8 h, detecting and reacting by using a TCL (thermal conductive liquid chromatography) plate, after the reaction is completed, adding deionized water into the solution, continuing to react for 10-20 min, separating out a large amount of precipitate, filtering the precipitate, washing the precipitate for 5-6 times by using the deionized water, and drying to obtain a compound 2, wherein the structural formula of the compound 2 is shown as the formula (II):
wherein the molar ratio of the compound 1 to the urotropine is 1 (2-5);
thirdly, reacting the compound 2 obtained in the second step with salicylhydrazine to obtain a target compound Z:
adding the compound 2 and salicylhydrazine into ethanol, heating and refluxing, wherein the heating temperature is 80-85 ℃, reacting for 4-5 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 for 5-6 times by using ethanol, and drying to obtain a target compound Z, wherein the structural formula of the compound Z is shown as a formula (III); wherein the molar ratio of the compound 2 to the salicylhydrazine is 1: 1;
3. the method for preparing the bifunctional fluorescent probe capable of recognizing aluminum ions and zinc ions according to claim 2, wherein glacial acetic acid is further added to the reaction system until the pH value of the reaction system is 4-6 after the compound 2 and the salicyloyl hydrazine are added to the ethanol in the third step.
4. The application of the bifunctional fluorescent probe of claim 1 in heavy metal ion detection, characterized in that the bifunctional fluorescent probe is used for sensing and detecting the content of aluminum ions and zinc ions in a water environment system.
5. The use according to claim 4, wherein said sensing is fluorescence detection, UV ratiometric detection, visual qualitative detection or reversible detection of zinc ions.
6. Use according to claim 4, characterized in that Na is also added2EDTA realizes repeated detection of zinc ions and distinguishes aluminum ions from zinc ions.
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