CN107556305B - Fluorescent probe for detecting aluminum ions, preparation method and application - Google Patents
Fluorescent probe for detecting aluminum ions, preparation method and application Download PDFInfo
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- CN107556305B CN107556305B CN201710816511.4A CN201710816511A CN107556305B CN 107556305 B CN107556305 B CN 107556305B CN 201710816511 A CN201710816511 A CN 201710816511A CN 107556305 B CN107556305 B CN 107556305B
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Abstract
the invention discloses a fluorescent probe for detecting aluminum ions, which has the characteristics of high selectivity, high sensitivity and good water solubility. The invention relates to a fluorescent probe for detecting aluminum ions, which has a structure shown in a formula I: wherein R is H, CH3 or t-Bu.
Description
Technical Field
The invention relates to a fluorescent probe, a preparation method and application thereof, in particular to a fluorescent probe for detecting aluminum ions, a preparation method and application thereof.
Background
Aluminum, the third element in the earth's crust, second only to the elements oxygen and silicon, determines its widespread use in life. In addition, aluminum has been widely used in various fields of electronic materials, catalysts, medicines, sensors, etc. due to its unique physical and chemical properties. While the widespread use of aluminum has brought various conveniences to our lives, it has left many inevitable problems on the ever-evolving road. It is well known that the large number of activities of humans and the widespread use of aluminum cause aluminum to exist in nature in the form of aluminum ions rather than monomers. However, high levels of aluminum ions pose certain hazards to both the environment and the human body. According to the standard issued by the World Health Organization (WHO), the per-person intake of aluminum ions should be controlled to be 3-10mg, and the content of aluminum ions in daily drinking water cannot exceed 200 mug/L. The research result shows that when the content of aluminum ions in human bodies is too high, a plurality of diseases can be caused, including Alzheimer disease, Parkinson disease and dialysis encephalopathy. Therefore, it is important to be able to monitor the content of aluminum ions in environmental and biological samples in real time. Conventional methods for detecting aluminum ions include ion mass spectrometry, atomic absorption spectrometry, inductively coupled plasma atomic emission spectrometry, and electrochemical methods. However, most of these methods require long analysis time, expensive instruments and are not easy to operate. Compared with the methods, the fluorescent probe has the advantages of good selection specificity, high sensitivity, easy operation, instant detection, quick response and the like. These advantages make it have more extensive application in the subject field such as chemistry, biomedicine, especially in the biomedicine field, the fluorescent probe not only can be used for in vitro analysis but also can be used for the image study of the living body. In recent years, a large number of small-molecule fluorescent probes capable of specifically detecting aluminum ions have been reported, however, many of them have poor water solubility, low sensitivity, and large influence of pH change on detection effect; other probes have high biological toxicity and poor cell membrane permeability, and the defects greatly influence the application of the probes. Therefore, it is necessary to develop a novel fluorescent probe that can overcome these drawbacks.
Disclosure of Invention
The technical problem to be solved by the invention is as follows: the fluorescent probe for detecting the aluminum ions has the characteristics of high selectivity, high sensitivity and good water solubility.
The invention also provides a preparation method of the fluorescent probe, a single crystal structure and application of the fluorescent probe in aluminum ion detection.
The technical concept of the invention is as follows: according to research, the derivative probe based on the 2- (5-alkyl-4-aldehyde-2-hydroxyphenyl) benzothiazole can selectively react with aluminum ions and generate a blue shift phenomenon, and the ratio of the fluorescence intensity at 476nm to the fluorescence intensity at 568nm (I476nm/I568nm) to the aluminum ion concentration has a better linear relation in the range of 0-100 mu M aluminum ion concentration. The present inventors prepared 2- (5-alkyl-4-aldehyde-2-hydroxyphenyl) benzothiazole derivatives for the first time and used them for the selective detection of aluminum ions for the first time, thereby solving the above technical problems.
The technical scheme for solving the technical problems of the invention is as follows:
the invention relates to a fluorescent probe for detecting aluminum ions, which has a structure shown in a formula I:
Wherein R is H, CH3 or t-Bu.
The preparation method of the fluorescent probe for detecting aluminum ions comprises the following steps:
Reacting 2- (5-alkyl-4-aldehyde-2-hydroxyphenyl) benzothiazole with a 2-thiophene formhydrazide compound in a solvent to generate the fluorescent probe for detecting aluminum ions.
The preparation method of the fluorescent probe for detecting aluminum ions, provided by the invention, has the further technical scheme that the preparation method comprises the following steps of:
Adding 2- (5-alkyl-4-aldehyde-2-hydroxyphenyl) benzothiazole into a reactor, adding a solvent for dissolving, then adding 2-thiophenecarboxhydrazide, reacting for 12 hours or more at normal temperature to obtain yellow solid precipitate, and purifying to obtain the fluorescent probe for detecting aluminum ions.
According to the preparation method of the fluorescent probe for detecting aluminum ions, the further technical scheme is that the solvent is methanol, ethanol, acetonitrile, dichloromethane or chloroform.
the preparation method of the fluorescent probe for detecting aluminum ions, provided by the invention, further adopts the technical scheme that the purification steps are as follows: and (3) precipitating the yellow solid precipitate in a reaction solvent, carrying out suction filtration on the reaction solution to obtain a yellow solid crude product, carrying out cross washing on the yellow solid crude product by using methanol and dichloromethane for 3 times or more respectively, and finally drying in a vacuum drying oven to obtain the fluorescent probe for detecting aluminum ions.
According to a further technical scheme of the preparation method of the fluorescent probe for detecting aluminum ions, the dosage mass ratio of the 2- (5-alkyl-4-aldehyde-2-hydroxyphenyl) benzothiazole to the 2-thiophene formhydrazide is 1.26-1.89: 1.
The fluorescent probe for detecting aluminum ions can be applied to detecting aluminum ions.
The invention has the following beneficial effects:
1) The fluorescent probe is colorless and orange in a buffer solution with the pH value of 7.4, and shows light green after reacting with aluminum ions and emits strong blue fluorescence.
2) After the fluorescent probe is adopted, the detection sensitivity is high, and the detection limit of aluminum ions can reach 10-6 mol/L.
3) The fluorescent probe only performs a fluorescent reaction with aluminum ions, has no reaction to other ions, and has good selectivity and specificity. In addition, the detection performance can tolerate a large pH variation range and has a good ratio fluorescence emission property.
4) The preparation process of the fluorescent probe is simple and easy to implement and is easy for large-scale production.
Drawings
FIG. 1 is a fluorescence emission spectrum of a fluorescent probe reacting with various ions in example 2 of the present invention.
FIG. 2 is a graph showing the change in fluorescence of the fluorescent probe in reaction with various ions in example 2 of the present invention.
FIG. 3 is a graph showing the change in fluorescence of the reaction between the fluorescent probe and aluminum ions in example 3 of the present invention.
FIG. 4 is a graph showing the increment of I476nm/I568nm in the reaction of fluorescent probes with aluminum ions in example 3 of the present invention.
FIG. 5 is a graph showing the linear relationship between the fluorescent probe of example 3 of the present invention and the concentration of aluminum ions I476nm/I568nm of 0-100. mu.M.
FIG. 6 is a graph showing the change in fluorescence of fluorescent probes of example 4 of the present invention at different water volume percentages.
FIG. 7 is a graph showing the change in the ratio of fluorescence intensity (I/I0) at different water volume percentages for the fluorescent probe of example 4 of the present invention.
FIG. 8 is the fluorescence of the fluorescent probe and metal ion filter paper experiment in example 5 of the present invention.
FIG. 9 is a single crystal structure characterization diagram of the fluorescent probe of example 1 of the present invention.
FIG. 10 is a nuclear magnetic hydrogen spectrum characterization chart of the fluorescent probe of example 1 of the present invention.
FIG. 11 is a diagram of mass spectrum characterization of the fluorescent probe of example 1 of the present invention
Detailed Description
The invention is described in further detail below with reference to embodiments and with reference to the drawings.
EXAMPLE 1 preparation of aluminum ion fluorescent Probe
269mg of 2- (5-methyl-4-carboxaldehyde-2-hydroxyphenyl) benzothiazole and 156mg of 2-thiophenecarboxhydrazide are dissolved in 30mL of methanol, and the reaction is stirred at room temperature for 12 hours. After the reaction is finished, yellow solid is separated out from the reaction solution, the reaction solution is subjected to suction filtration to obtain yellow solid precipitate, the yellow solid precipitate is then alternately washed by methanol and dichloromethane for 3 times respectively, and the yellow solid precipitate is dried in a vacuum drying oven to obtain 320mg of yellow solid, namely the pure product of the aluminum ion fluorescent probe (the single crystal structure, the 1H-NMR chart and the high-resolution mass spectrogram are shown in figures 9, 10 and 11). The actual measurement molecular weight of the obtained pure fluorescent probe is 393.
the process route of the embodiment is as follows:
Example 2 spectral Properties of the aluminum ion fluorescent Probe prepared in example 2, which reacts with various ions
3.9mg of the aluminum ion fluorescent probe prepared in example 1 was weighed out and prepared into 10mL of DMF solution with a concentration of 1mM as a mother solution.
Fluorescence spectrum test: mu.L of the above mother liquor was added to an amount of 10mM HEPES buffer solution (pH 7.4), followed by addition of each metal ion: al3+, Zn2+, Cu2+, Fe2+, Fe3+, Hg2+, Ag +, Co2+, Ni2+, Cr3+, Ca2+, Cs +, Cd2+, Pb2+, Mn2+, Zr4+, K +, Mg2+, Li +, Na +, so that the final concentration of metal ions in the measurement system is 1mM, and the final concentration of the fluorescent probe is 10. mu.M. The fluorescence emission spectrum was immediately tested at the excitation wavelength of 380 nm. The slit width for excitation and emission light was 10nm/5 nm. The results obtained are shown in FIG. 1. The prepared solution was irradiated with 365nm ultraviolet light, and the change in fluorescence was observed, and the result was shown in FIG. 2.
The above results show that:
(1) Example 1 the fluorescent probe itself was colorless and orange in buffer solution, but with the addition of aluminum ions, the orange fluorescence gradually disappeared at 568nm and the blue fluorescence gradually increased at 476 nm.
(2) The fluorescent probe prepared in example 1 has high selectivity and specificity for aluminum ions, and can distinguish aluminum ions from common heavy metal ions such as Zn2+, Ag +, Cd2+, Pb2+, Cu2+, Cr3+, Hg2+, Mn2+ under the above conditions.
example 3 spectral Properties of reaction product of aluminum ion fluorescent Probe and aluminum ion
mu.L of the mother liquor obtained in example 2 was added to a quantity of 10mM HEPES buffer solution (pH 7.4) so that the final concentration of the fluorescent probe in the test system became 10. mu.M, and then different equivalents of aluminum ions were added to the above test system to make the final concentrations of the aluminum ions 0mM, 0.2mM, 0.4mM, 0.6mM, 0.8mM, 1mM, 1.2mM, 1.4mM, 1.6mM, 1.8mM, and 2mM, respectively. After the ion addition, the fluorescence emission spectrum was measured instantaneously. Excitation at 380nm for fluorescence emission spectrometry; the slit width for excitation and emission light was 10nm/5 nm. The resulting incremental plot of fluorescence intensity ratios I476nm/I568nm is shown in FIG. 3; a working curve was prepared from the data of I476nm/I568nm, and the results are shown in FIG. 4.
The experimental results show that the fluorescence intensity ratio I476nm/I568nm increases with the increase of the aluminum ion concentration as the reaction proceeds, and the fluorescence intensity ratio I476nm/I568nm has a better linear relationship with the aluminum ion concentration in the range of 0-100 μ M, and can be used for quantitative analysis and detection of the aluminum ion content, and the linear relationship between I476nm/I568nm and the aluminum ion concentration in the range of 0-100 μ M is shown in a graph of FIG. 5.
Example 4 fluorescence Spectroscopy Properties of aluminum ion fluorescent Probe prepared in different Water volume percents
The total volume of tetrahydrofuran and deionized water is maintained to be constant, the volume percentage of water is changed (0-95%), and the change of the fluorescence spectrum of the aluminum ion fluorescent probe under different volume percentages of water is detected. The results show that in the range of 0-90%, the fluorescence intensity of the aluminum ion fluorescent probe and the ratio of the fluorescence intensity (I/I0) increase along with the increase of the volume percentage of water; when the volume percentage of the water exceeds 90%, the ratio (I/I0) of the fluorescence intensity of the aluminum ion fluorescent probe is reduced, and the experimental results show that the aluminum ion fluorescent probe has the effect of aggregation-induced luminescence. The fluorescence spectra of the aluminum ion fluorescent probe at different water volume percentages are shown in fig. 6 and fig. 7.
Example 5 fluorescence Spectrum Properties of aluminum ion fluorescent Probe and Metal ion Filter paper experiment
The prepared circular filter paper sheet was placed in a beaker, and then 1.5mL of the mother liquor of example 2 was added to the beaker so that the circular filter paper sheet was completely submerged. And after the filter paper sheet is soaked for 12 hours, taking out all the filter paper sheet, and drying the filter paper sheet at normal temperature for 12 hours. At this time, the filter paper exhibits red fluorescence under 365nm ultraviolet excitation. Al3+, Zn2+, Cu2+, Fe2+, Fe3+, Hg2+, Ag +, Co2+, Ni2+, Cr3+, Ca2+, Cs +, Cd2+, Pb2+, Mn2+, Zr4+, K +, Mg2+, Li +, Na + each 10. mu.L were pipetted in the center of the dried filter paper and allowed to diffuse freely. After complete reaction, the change in fluorescence on each filter paper was examined. The results show that under 365nm ultraviolet excitation irradiation, the fluorescence of the filter paper part added with metal ions Hg2+, Ni2+, Co2+, Cu2+, Fe3+ and Fe2+ is completely quenched; other metal ions such as: the fluorescence of the filter paper parts of Zn2+, Ag +, Cr3+, Ca2+, Cs +, Cd2+, Pb2+, Mn2+, Zr4+, K +, Mg2+, Li + and Na + is not changed; whereas the fluorescence of only the filter paper portion to which Al3+ was added changed from red to strong blue fluorescence. The fluorescence image of the aluminum ion fluorescent probe and the metal ion filter paper experiment is shown in FIG. 8.
In addition to the above embodiments, the present invention may have other embodiments. All technical solutions formed by adopting equivalent substitutions or equivalent transformations fall within the protection scope of the claims of the present invention.
Claims (7)
1. A fluorescent probe for detecting aluminum ions is characterized in that the probe has a structure shown as a formula I:
Wherein R is H, CH3 or t-Bu.
2. The method for preparing the fluorescent probe for detecting aluminum ions according to claim 1, comprising the steps of: reacting 2- (5-alkyl-4-aldehyde-2-hydroxyphenyl) benzothiazole with a 2-thiophene formhydrazide compound in a solvent to generate the fluorescent probe for detecting aluminum ions.
3. The method of claim 2, comprising the steps of:
Adding 2- (5-alkyl-4-aldehyde-2-hydroxyphenyl) benzothiazole into a reactor, adding a solvent for dissolving, then adding 2-thiophenecarboxhydrazide, reacting for more than 12 hours at normal temperature to obtain yellow solid precipitate, and purifying to obtain the fluorescent probe for detecting aluminum ions.
4. The method according to claim 2 or 3, wherein the solvent is methanol, ethanol, acetonitrile, dichloromethane or chloroform.
5. the method according to claim 4, wherein the purification step comprises: and (3) precipitating the yellow solid precipitate in a reaction solvent, carrying out suction filtration on the reaction solution to obtain a yellow solid crude product, carrying out cross washing on the yellow solid crude product by using methanol and dichloromethane for more than 3 times respectively, and finally drying in a vacuum drying oven to obtain the fluorescent probe for detecting aluminum ions.
6. The preparation method according to claim 2 or 3, wherein the mass ratio of the 2- (5-alkyl-4-aldehyde-2-hydroxyphenyl) benzothiazole to the 2-thiophenecarboxhydrazide is 1.26-1.89: 1.
7. Use of the fluorescent probe for detecting aluminum ions according to claim 1 for detecting aluminum ions.
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| 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 |
| CN113004220B (en) * | 2021-03-12 | 2022-03-11 | 南京工业大学 | Esterase detection fluorescent probe, preparation method and application |
| CN114907336B (en) * | 2022-07-01 | 2023-08-29 | 廊坊师范学院 | Zinc ion fluorescent probe based on benzothiazole and preparation method and application thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105294539A (en) * | 2015-11-20 | 2016-02-03 | 齐鲁工业大学 | Aluminum ion fluorescent probe compound and preparation method thereof |
| CN105802608A (en) * | 2016-03-08 | 2016-07-27 | 温州医科大学 | Preparation method of fluorescent probe and application of fluorescent probe in aluminum ion detection |
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105294539A (en) * | 2015-11-20 | 2016-02-03 | 齐鲁工业大学 | Aluminum ion fluorescent probe compound and preparation method thereof |
| CN105802608A (en) * | 2016-03-08 | 2016-07-27 | 温州医科大学 | Preparation method of fluorescent probe and application of fluorescent probe in aluminum ion detection |
Non-Patent Citations (2)
| Title |
|---|
| "A highly sensitive and selective fluorescent sensor for Al3+ ions based on thiophene-2-carboxylic acid hydrazide Schiff base";Karishma Tiwari，等;《RSC Adv.》;20130430;第3卷;第12124-12132页 * |
| "一个高度灵敏和高选择性铝离子比率探针的合成及应用";刘传涛，等;《影像科学与光化学》;20170531;第35卷(第3期);第281-289页 * |
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