CN113214108B - Fluorescent probe for detecting cyanide ions and preparation method and application thereof - Google Patents
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Abstract
The invention relates to a fluorescent probe for detecting cyanide ions and a preparation method and application thereof, wherein the preparation method of the fluorescent probe comprises the following steps: (1) Synthesizing 2-cyano-2- (9, 10-dioxo-9, 10-dihydroanthracene-1-yl) acetic ether; (2) And (3) synthesizing a fluorescent probe, wherein the fluorescent probe is applied to detecting cyanide ions in an aqueous solution. Compared with the prior art, the method has the advantages of high sensitivity, capability of circularly identifying anions, capability of detecting cyanide ions in aqueous solution and the like.
Description
Technical Field
The invention relates to the field of fluorescent probes, in particular to a fluorescent probe for detecting cyanide ions and a preparation method and application thereof.
Background
Anion recognition is of widespread interest because of its important role in a variety of chemical, biological and environmental processes, is highly toxic to humans, and affects many normal functions of the physiological system, such as the vascular, visual, central nervous, cardiac, endocrine and metabolic systems. Cyanide is used in the gold ore and electroplating industries and causes irreparable damage to the environment.
In recent years, a large number of cyanide salts have been widely used in industrial production fields such as metallurgy, electroplating and synthesis of herbicides. However, as we know, cyanide anion is also one of the most notorious anions in biologically relevant aspects and constitutes a great threat to human health by binding to the active site of cytochrome c oxidase, leading to the destruction of the electron transport chain from the central nervous system to the endocrine system. In view of the highly toxic effect of cyanide even at sub-micromolar concentrations, scientists have been without the burden of developing efficient methods and novel fluorescent materials to meet the real-time detection of cyanide ions.
However, the reported cyanide ion detection method is relatively time consuming, time consuming and requires expensive equipment; for example, atomic Absorption Spectroscopy (AAS), atomic Fluorescence Spectroscopy (AFS), photoluminescence, surface enhanced raman scattering techniques, inductively coupled plasma atomic emission spectroscopy, and gas chromatography-mass spectrometry, among others. At present, many anion fluorescent probes with potential application values are designed and synthesized, but most of the probes are complex to synthesize, high in cost and incapable of being identified repeatedly, and anions are difficult to identify in an aqueous solution.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provide a fluorescent probe which has high sensitivity, can circularly identify anions and can detect cyanide ions in an aqueous solution, and a preparation method and application thereof.
The purpose of the invention can be realized by the following technical scheme:
the inventor knows that 1-chloroanthraquinone is an excellent fluorophore, and the fluorophore has the advantages of stable structure, easy synthesis, excellent optical characteristics, such as absorption and emission wavelength in a visible light region, larger Stokes red shift, higher light stability and the like, and has typical ESIPT photoelectric characteristics in a molecular structure, extremely high sensitivity under micro-environmental conditions and the like. Therefore, the fluorescent probe can be used as a potential fluorescent chromophore to be applied to the design of probes for identifying anions, and can also be applied to the industrial fields of medicine, fluorescence, dyes, pigments and the like, so that the following scheme is obtained:
a fluorescent probe for detecting cyanide ions, the chemical name of the fluorescent probe is 2-imino-7-oxo-2, 7-dihydrodibenzo [ de, h ] chromene-3-carboxylic acid ethyl ester, and the structural formula of the fluorescent probe is as follows:
the fluorescent probe takes 1-chloroanthraquinone as a fluorophore and an-NH group as a recognition site, an ultraviolet absorption peak is formed at 300nm under the condition that acetonitrile is used as a solvent, after cyanide ions are added, the absorption peak at 300nm is reduced, and a new peak is formed at 517 nm. And when other anions are added, the ultraviolet absorption spectrum of the fluorescent probe is not obviously changed. In a fluorescence spectrum, the maximum emission wavelength of the fluorescent probe is 477nm, the fluorescent probe has weak blue fluorescence, and the fluorescence intensity at 477nm is obviously reduced after CN < - >. Under 365nm UV light, fluorescence quenching was observed after CN-, while the other anions were unchanged. Under the interference of other ions, a new absorption peak still appears at 528nm after CN < - > is added, and the interference of other ions is hardly caused.
A preparation method of the fluorescent probe for detecting cyanide ions comprises the following steps:
(1) Synthesis of ethyl 2-cyano-2- (9, 10-dioxo-9, 10-dihydroanthracen-1-yl) acetate:
adding 1-chloroanthraquinone, adding ethyl cyanoacetate, cesium carbonate and a first solvent, heating to about 110-130 ℃, refluxing (the reflux temperature is the boiling point of the mixed liquid), recovering to room temperature, and separating and purifying to obtain yellow powdery 2-cyano-2- (9, 10-dioxo-9, 10-dihydroanthracene-1-yl) ethyl acetate;
(2) Synthesis of ethyl 2-imino-7-oxo-2, 7-dihydrodibenzo [ de, h ] chromene-3-carboxylate:
dissolving 2-cyano-2- (9, 10-dioxo-9, 10-dihydroanthracene-1-yl) ethyl acetate in a second solvent, adding 2-aminopyridine, and heating to reflux state; and after the reaction is completed, the reaction is returned to the room temperature, and yellow solid 2-imino-7-oxo-2, 7-dihydrodibenzo [ de, h ] chromene-3-carboxylic acid ethyl ester is obtained by separation and purification, namely the fluorescent probe for detecting cyanide ions.
Further, the mol ratio of the 1-chloroanthraquinone to the ethyl cyanoacetate to the cesium carbonate in the step (1) is (20-25) mmol, (40-50) mmol.
Further, the molar volume ratio of the 1-chloroanthraquinone to the ethyl cyanoacetate to the cesium carbonate to the first solvent is (20-25) mmol, (40-50) mmol, (150-250) ml.
Further, the molar ratio of ethyl 2-cyano-2- (9, 10-dioxo-9, 10-dihydroanthracen-1-yl) acetate and 2-aminopyridine described in step (2) was (2-4) mmol, (12-14) mmol.
Further, the molar volume ratio of the ethyl 2-cyano-2- (9, 10-dioxo-9, 10-dihydroanthracene-1-yl) acetate to the 2-aminopyridine to the second solvent is (2-4) (12-14) (35-40) ml.
Further, the first solvent comprises dimethyl sulfoxide; the second solvent comprises dimethylformamide.
Further, the refluxing time in the step (1) is 1-2h; the reaction time in the step (2) is 6-8h.
Further, the separation and purification mode comprises acidification, washing, reduced pressure distillation, column chromatography or column chromatography purification.
The application of the fluorescent probe for detecting cyanide ions is to detect cyanide ions in an aqueous solution.
Further, the aqueous solution also comprises interfering ions, particularly Cl - 、Br - 、I - 、HSO 4 - 、NO 3 - 、BF 4 - 、ClO 4 - 、SCN - Or S 2 - One or more of (a).
Further, in the detection, a fluorescent probe was dissolved in acetonitrile, and cyanide ions were tested.
Compared with the prior art, the invention has the following advantages:
(1) Compared with the traditional series release reaction, the technology has the advantages that the fluorescence signal of the nitrogen-containing negative ions is released by means of the influence of cyanide ions on the deprotonation of NH, and the mechanism is novel and unique and is not reported;
(2) The probe has good specificity, and mainly has the advantage that only cyanide ions can cut off nitrogen-hydrogen bonds, thereby causing optical signal change.
Drawings
FIG. 1 is a diagram showing the UV absorption spectra of the fluorescent probe of example 1 when different anions are added to the acetonitrile solution;
FIG. 2 is a photograph of the fluorescent probe of example 1 irradiated with visible light when different anions are added to the acetonitrile solution;
FIG. 3 shows the fluorescence probes of example 1 in acetonitrile with different CN - Ultraviolet absorption spectrum at concentration;
FIG. 4 shows A-590nm and CN in example 1 - A concentration relation curve;
FIG. 5 shows the fluorescence probes of example 1 in acetonitrile with different CN - Fluorescence emission spectra at concentration;
FIG. 6 shows I-477nm and CN in example 1 - A concentration relation curve;
FIG. 7 shows the fluorescent probe in example 1 for CN in the presence of other anions - The response is a bar graph of the change of ultraviolet absorption at 528nm, which shows that the response of other anions to cyanide ions is not interfered;
FIG. 8 is a graph showing the fluorescence intensity and CN in the detection of the fluorescent probe in example 1 - Concentration relation curve.
Detailed Description
The invention is described in detail below with reference to the figures and specific embodiments.
A preparation method of a fluorescent probe for detecting cyanide ions comprises the following steps:
(1) Synthesis of ethyl 2-cyano-2- (9, 10-dioxo-9, 10-dihydroanthracen-1-yl) acetate:
adding 1-chloroanthraquinone into a single-neck flask, adding magnetons, keeping a sample with a bullet, adding ethyl cyanoacetate, cesium carbonate and a first solvent dimethyl sulfoxide into the flask by using an injector, heating the flask, refluxing the flask for 1 to 2 hours, and recovering the flask to room temperature to perform post-treatment to obtain yellow powdery 2-cyano-2- (9, 10-dioxo-9, 10-dihydroanthracene-1-yl) ethyl acetate; wherein the mol volume ratio of the 1-chloroanthraquinone to the ethyl cyanoacetate to the first solvent is (20-25) mmol, (40-50) mmol, and 200ml
(2) Synthesis of ethyl 2-imino-7-oxo-2, 7-dihydrodibenzo [ de, h ] chromene-3-carboxylate:
dissolving ethyl 2-cyano-2- (9, 10-dioxo-9, 10-dihydroanthracene-1-yl) acetate in a second solvent, adding 2-aminopyridine, and heating to reflux, wherein the molar volume ratio of the ethyl 2-cyano-2- (9, 10-dioxo-9, 10-dihydroanthracene-1-yl) acetate, the 2-aminopyridine and the second solvent is (2-4) mmol, (12-14) mmol, (35-40) ml; and after reacting for 6-8h, recovering to room temperature, acidifying, washing, drying, distilling under reduced pressure, and collecting a yellow solid 2-imino-7-oxo-2, 7-dihydrodibenzo [ de, h ] chromene-3-carboxylic acid ethyl ester after column chromatography, namely the fluorescent probe for detecting cyanide ions.
The names, specifications and manufacturer information of the raw materials used in the examples are shown in Table 1.
TABLE 1
| Name of raw material | Manufacturer information |
| 1-chloroanthraquinone | SHANGHAI TITAN TECHNOLOGY Co.,Ltd. |
| Cesium carbonate | SHANGHAI TITAN TECHNOLOGY Co.,Ltd. |
| 2-aminopyridines | SHANGHAI TITAN TECHNOLOGY Co.,Ltd. |
| Cyanoacetic acid ethyl ester | SHANGHAI TITAN TECHNOLOGY Co.,Ltd. |
| Acetic acid ethyl ester | SHANGHAI TITAN TECHNOLOGY Co.,Ltd. |
| Dimethyl sulfoxide | SHANGHAI TITAN TECHNOLOGY Co.,Ltd. |
| Dimethyl formamide | SHANGHAI TITAN TECHNOLOGY Co.,Ltd. |
The type and manufacturer of the silica gel column used in each example was a silica gel column having a length of 45cm and a diameter of 45mm, manufactured by Beijing Union glass instruments, inc.
Example 1
The synthesis of fluorescent probe molecule for detecting cyanide ion is carried out by taking 1-chloroanthraquinone, 2-aminopyridine and ethyl cyanoacetate as raw materials, amidating and nucleophilic substituting
(1) Synthesis of ethyl 2-cyano-2- (9, 10-dioxo-9, 10-dihydroanthracen-1-yl) acetate:
a mixture of 1-chloroanthraquinone (5.00g, 20.60mmol), ethyl cyanoacetate (4.66g, 41.20mmol) and cesium carbonate (13.43g, 41.22mmol) in dimethyl sulfoxide (200 ml) was stirred at 130 ℃ for 1.5 hours. After completion of the reaction (monitored by thin layer chromatography), the reaction mixture was cooled to room temperature, and then insoluble components were removed by suction filtration using a buchner funnel. The filtrate was extracted with ethyl acetate, washed with an appropriate amount of saturated brine, and dried over anhydrous NaSO 4. Finally, the dried solution was concentrated and purified by column chromatography (polyethylene: ethyl acetate =12: 1) to give a pale yellow solid (5.95g, 90.4% yield); the yellowish solid powder obtained above was measured by means of a nuclear magnetic resonance instrument (Bruker AVANCE III 500 MHz) and the data are as follows:
1 H NMR(500MHz,CDCl 3 )δ[ppm]:8.43(d,J＝7.5Hz, 1 H),8.23–8.20(m, 2 H),7.93(d,J＝5.5Hz, 1 H),7.85(t,J＝7.5Hz, 1 H),7.80-7.70(m, 2 H),6.03(s, 1 H),4.32(q,J＝7.0Hz, 2 H),1.35(t,J＝7.0Hz, 3 H). 13 C NMR(125MHz,CDCl 3 )δ[ppm]:184.93,182.59,164.66,136.81,135.61,134.80,134.76,134.60,134.07,132.78,131.96,130.62,129.56,127.90,127.27,115.83,63.63,42.61,14.33.HRMS-ESI Calcd.For C 19 H 13 NO 4 [M + H] + :320.0923；Found:320.0917 .
the result of the nuclear magnetic resonance spectrum data analysis of the pale yellow solid powder product obtained above shows that the pale yellow solid powder product obtained above is 2-ethoxyethyl 2-cyano-2- (9, 10-dioxo-9, 10-dihydroanthracene-1-yl) acetate.
(2) Synthesis of ethyl 2-imino-7-oxo-2, 7-dihydrodibenzo [ de, h ] chromene-3-carboxylate:
a mixture of ethyl 2-cyano-2- (9, 10-dioxo-9, 10-dihydroanthracen-1-yl) acetate (1.00g, 3.13mmol) and 2-aminopyridine (1.18g, 12.54mmol) in dimethylformamide (35 ml) was stirred at 120 ℃ for 6 hours. After cooling to room temperature, the reaction was quenched with deionized water. Then, the solution was extracted with ethyl acetate, washed with an appropriate amount of saturated brine, and dried over anhydrous sodium sulfate. Finally, the dried solution was concentrated and purified by column chromatography (PE: EA =12 1) to give a yellow solid (0.35g, 35.0% yield) and a pale yellow solid (0.10g, 13.0% yield); the yellow solid powder product obtained above was measured by means of a nuclear magnetic resonance instrument (Bruker AVANCE III 500 MHz) and the data are as follows:
1 H NMR(500MHz,CDCl 3 )δ[ppm]:12.88(s, 1 H),9.06(d,J＝9Hz, 1 H),8.90(d,J＝8Hz, 1 H),8.41(d,J＝7Hz, 1 H),8.35(d,J＝7.5Hz, 1 H),7.86(t,J＝8Hz, 1 H),7.80(t,J＝7.5Hz, 1 H),7.70(t,J＝7.5Hz, 1 H),4.65(q,J＝7.0Hz, 2 H),1.59(t,J＝7.0Hz, 3 H). 13 C NMR(125MHz,CDCl 3 )δ[ppm]:183.41,171.85,166.18,154.45,136.25,135.40,134.47,132.94,132.80,132.36,131.54,129.82,127.75,127.26,127.24,119.96,98.78,63.36,14.69.HRMS-ESI Calcd.For C 19 H 13 NO 4 [M + Na] + :342.0742；Found:342.0738. 1 H NMR(500MHz,CDCl 3 )δ[ppm]:8.42(d,J＝8Hz, 1 H),8.28(d,J＝8.5Hz, 2 H),7.94(d,J＝7.5Hz, 1 H),7.85-7.70(m, 3 H),4.48(s, 2 H). 13 C NMR(125MHz,CDCl 3 )δ[ppm]:185.08,182.95,136.28,135.70,134.85,134.62,134.49,134.43,132.94,132.92,130.69,128.72,127.86,127.33,117.82,24.61.HRMS-ESI Calcd.For C 16 H 10 NO 2 [M + H] + :248.0712；Found,248.0709.
the result of the nuclear magnetic resonance spectrum data analysis of the yellow solid powder product obtained in the above way shows that the yellow solid powder product obtained in the above way is 2-imino-7-oxo-2, 7-dihydrodibenzo [ de, h ] chromene-3-carboxylic acid ethyl ester.
Identification performance of fluorescent probe for detecting cyanide ions on anions
1. Selective study of fluorescent probes for cyanide ions
The fluorescent probe is prepared into 20 mu mol.L -1 Acetonitrile (2): water = 3; separately prepare CN - ,F - ,H 2 PO 4 - ,AcO - ,Cl - ,Br - ,I - ,HSO 4 - ,NO 3 - ,BF 4 - ,ClO 4 - ,SCN - ,S 2 - 5000. Mu. Mol. L of -1 Acetonitrile: for a solution of water =3 -1 Fluorescent probe solution, with acetonitrile: water =3, 1 volume is adjusted to 100mL to prepare 20 μmol · L -1 Of (2)The solution was divided into 13 groups (5 mL each), and 180 equivalents (180.0. Mu.L, 5000. Mu. Mol. L) were added to each group -1 ) The response of the fluorescent probe to various anions is observed through ultraviolet absorption spectrum.
The results show that the fluorescent probe has an ultraviolet absorption peak at 300nm under the condition of acetonitrile as a solvent, and CN is added as shown in figure 1 - After that, the absorption peak at 300nm appeared to decrease, and a new peak at 517nm appeared. And when other anions are added, the ultraviolet absorption spectrum of the fluorescent probe is not obviously changed. Therefore, the fluorescent probe can specifically detect the cyanide ions.
2. Interference test study on fluoride ions in the Presence of other anions
The prepared CN - ,F - ,H 2 PO 4 - ,AcO - ,Cl - ,Br - ,I - ,HSO 4 - ,NO 3 - ,BF 4 - ,ClO 4 - ,SCN - ,S 2 - The 13 solutions were observed by UV absorption spectroscopy, and then added with 180 equivalents (180.0. Mu.L, 5000. Mu. Mol. L) respectively -1 ) The response of the fluorescent probe to the cyanide ion under the interference of various anions is observed through ultraviolet absorption spectrum.
The results show that the right bars of the fluorescent probes in acetonitrile as solvent respectively show the presence of Cl alone, as shown in FIG. 7 - ,Br - ,I - ,HSO 4 - ,NO 3 - ,BF 4 - ,ClO 4 - ,SCN - ,S 2 - Emission at 528nm for the anion. The left bar indicates the change that occurs when 180 equivalents of cyanide ion are subsequently added. To give in Cl - ,Br - ,I - ,HSO 4 - ,NO 3 - ,BF 4 - ,ClO 4 - ,SCN - ,S 2 - In the presence of anions, the interference on detection of cyanide ions by a fluorescent probe in an acetonitrile solution is small, and the influence is almost avoided.
3. Cyanid ion fluorescence probe titration experiment
Dissolving the fluorescent probe in acetonitrile to prepare 5000 mu mol.L -1 Stock solution of (2), preparing CN in acetonitrile - Stock solution with a concentration of 50000. Mu. Mol. L -1 . 100. Mu.L of 5000. Mu. Mol/L was measured -1 The fluorescent probe solution is put into a 25mL volumetric flask, the volume is adjusted to 25mL by acetonitrile solution to prepare 25mL,20 mu mol.L -1 Acetonitrile solvent (b) of the fluorescent probe solution of (a).
(1) High concentration titration experiment: 25mL, 20. Mu. Mol. L -1 The probe solution of acetonitrile solvent (2) was poured into a 250mL wide-mouth flask, and 10.0. Mu.L of 5000. Mu. Mol. L each time was added dropwise -1 (10.0 equiv.) of CN - The solution is shaken evenly and then the ultraviolet absorption spectrum of the solution is detected, and the operation is repeated until 180.0 equivalents of cyanide ion solution is added.
(2) Low concentration titration experiment: 25mL, 20. Mu. Mol. L -1 The probe solution of acetonitrile solvent (2) was poured into a 100mL wide-necked flask, and 1.0. Mu.L, 50000. Mu. Mol. L, was added dropwise thereto -1 (0.1 equivalent) of CN - The solution was shaken well and the UV absorption spectrum was measured and the procedure was repeated until 2.5 equivalents of fluoride ion solution were added.
The results show that, as shown in FIGS. 3-4, the ultraviolet absorption spectrum of the fluorescent probe is influenced by the concentration of cyanide ions, and the absorption peak of the fluorescent probe at 590nm gradually increases with the gradual addition of cyanide ions until 3600. Mu. Mol.L is added -1 CN (C) - Equilibrium is reached.
Then measuring the fluorescence emission spectrum, as shown in FIGS. 5-6, the fluorescence intensity of the fluorescent probe is very strong at 477nm, and gradually decreases with the addition of cyanide ions until 28. Mu. Mol. L is added -1 CN (C) - Equilibrium is reached.
From the titration experiment, as shown in fig. 8, the detection limit LOD =0.61 μ M, and the lower detection limit indicates that the probe has high sensitivity for detecting cyanide ions.
Example 2
A preparation method of a fluorescent probe for detecting cyanide ions comprises the following steps:
(1) Synthesizing 2-cyano-2- (9, 10-dioxo-9, 10-dihydroanthracene-1-yl) ethyl acetate;
a mixture of 1-chloroanthraquinone (5.00g, 20.60mmol), ethyl cyanoacetate (4.66g, 41.20mmol) and cesium carbonate (13.43 g,41.22 mmol) in dimethyl sulfoxide (200 mL) was stirred at 130 ℃ for 1 hour. After completion of the reaction (monitored by thin layer chromatography), the reaction mixture was cooled to room temperature, and then insoluble components were removed by suction filtration using a buchner funnel. The filtrate was extracted with ethyl acetate, washed with an appropriate amount of saturated brine, and dried over anhydrous NaSO 4. Finally, the dried solution was concentrated and purified by column chromatography (polyethylene: ethyl acetate =12: 1) to give 2 (5.95g, 90.4% yield) as light yellow solid ethyl 2-cyano-2- (9, 10-dioxo-9, 10-dihydroanthracen-1-yl) acetate.
(2) Synthesis of ethyl 2-imino-7-oxo-2, 7-dihydrodibenzo [ de, h ] chromene-3-carboxylate:
a mixture of ethyl 2-cyano-2- (9, 10-dioxo-9, 10-dihydroanthracen-1-yl) acetate (1.00g, 3.13mmol) and 2-aminopyridine (1.18 g,12.54 mmol) in a second solvent (35 ml) was stirred at 120 ℃ for 6 h. After cooling to room temperature, the reaction was quenched with deionized water. Then, the solution was extracted with ethyl acetate, washed with an appropriate amount of saturated brine, and dried over anhydrous sodium sulfate. Finally, the dried solution was concentrated and purified by column chromatography (PE: EA =12: 1) to give 3 (0.35g, 35.0% yield) yellow solid and 4 (0.10 g,13.0% yield) pale yellow solid ethyl 2-imino-7-oxo-2, 7-dihydrodibenzo [ de, h ] chromene-3-carboxylate; the second solvent is dimethylformamide;
the fluorescent probe for detecting cyanide ions is applied to detecting cyanide ions in an aqueous solution, and during detection, the fluorescent probe is dissolved in acetonitrile to test the cyanide ions.
Example 3
A preparation method of a fluorescent probe for detecting cyanide ions comprises the following steps:
(1) Synthesis of ethyl 2-cyano-2- (9, 10-dioxo-9, 10-dihydroanthracen-1-yl) acetate: a mixture of 1-chloroanthraquinone (5.00g, 20.60mmol), ethyl cyanoacetate (4.66g, 41.20mmol) and cesium carbonate (13.43 g,41.22 mmol) in a first solvent (200 mL) was stirred at 130 ℃ for 2 hours. After completion of the reaction (monitored by thin layer chromatography), the reaction mixture was cooled to room temperature, and then insoluble components were removed by suction filtration using a buchner funnel. The filtrate was extracted with ethyl acetate, washed with an appropriate amount of saturated brine, and dried over anhydrous NaSO 4. Finally, the dried solution was concentrated and purified by column chromatography (polyethylene: ethyl acetate =12: 1) to give ethyl 2-cyano-2- (9, 10-dioxo-9, 10-dihydroanthracen-1-yl) acetate (5.95g, 90.4% yield) as a pale yellow solid; the first solvent is dimethyl sulfoxide;
(2) Synthesis of ethyl 2-imino-7-oxo-2, 7-dihydrodibenzo [ de, h ] chromene-3-carboxylate: a mixture of ethyl 2-cyano-2- (9, 10-dioxo-9, 10-dihydroanthracen-1-yl) acetate (1.00g, 3.13mmol) and 2-aminopyridine (1.18 g,12.54 mmol) in a second solvent (35 ml) was stirred at 120 ℃ for 6 h. After cooling to room temperature, the reaction was quenched with deionized water. Then, the solution was extracted with ethyl acetate, washed with an appropriate amount of saturated brine, and dried over anhydrous sodium sulfate. Finally, the dried solution was concentrated and purified by column chromatography (PE: EA =12: 1) to give 3 (0.35g, 35.0% yield) yellow solid and 4 (0.10 g,13.0% yield) pale yellow solid ethyl 2-imino-7-oxo-2, 7-dihydrodibenzo [ de, h ] chromene-3-carboxylate; the second solvent is dimethylformamide;
the fluorescent probe for detecting cyanide ions is applied to detecting cyanide ions in an aqueous solution, and during detection, the fluorescent probe is dissolved in pyridine acetonitrile to test the cyanide ions.
The foregoing is directed to preferred embodiments of the present invention, other and further embodiments of the invention may be devised without departing from the basic scope thereof, and the scope thereof is determined by the claims that follow. However, any simple modification, equivalent change and modification of the above embodiments according to the technical essence of the present invention are within the protection scope of the technical solution of the present invention.
Claims (10)
1. A fluorescent probe for detecting cyanide ions is characterized in that the chemical name of the fluorescent probe is 2-imino-7-oxo-2, 7-dihydrodibenzo [ de, h ] chromene-3-carboxylic acid ethyl ester, and the structural formula of the fluorescent probe is as follows:
2. a method for preparing a fluorescent probe for detecting cyanide ions according to claim 1, comprising the steps of:
(1) Synthesis of ethyl 2-cyano-2- (9, 10-dioxo-9, 10-dihydroanthracen-1-yl) acetate:
adding 1-chloroanthraquinone, adding ethyl cyanoacetate, cesium carbonate and a first solvent, heating, refluxing, recovering to room temperature, separating and purifying to obtain yellow powdery 2-cyano-2- (9, 10-dioxo-9, 10-dihydroanthracene-1-yl) ethyl acetate;
(2) Synthesis of ethyl 2-imino-7-oxo-2, 7-dihydrodibenzo [ de, h ] chromene-3-carboxylate:
dissolving ethyl 2-cyano-2- (9, 10-dioxo-9, 10-dihydroanthracene-1-yl) acetate in a second solvent, adding 2-aminopyridine, and heating to reflux state; and after the reaction is completed, the reaction is returned to the room temperature, and yellow solid 2-imino-7-oxo-2, 7-dihydrodibenzo [ de, h ] chromene-3-carboxylic acid ethyl ester is obtained by separation and purification, namely the fluorescent probe for detecting cyanide ions.
3. The method for preparing a fluorescent probe for detecting cyanide ions according to claim 2, wherein the molar ratio of 1-chloroanthraquinone, ethyl cyanoacetate and cesium carbonate in step (1) is (20-25) mmol, (40-50) mmol.
4. The method for preparing a fluorescent probe for detecting cyanide ions according to claim 2, wherein the molar ratio of ethyl 2-cyano-2- (9, 10-dioxo-9, 10-dihydroanthracen-1-yl) acetate to 2-aminopyridine in step (2) is (2-4) mmol, (12-14) mmol.
5. The method for preparing a fluorescent probe for detecting cyanide ions according to claim 2, wherein the first solvent comprises dimethyl sulfoxide; the second solvent comprises dimethylformamide.
6. The method for preparing a fluorescent probe for detecting cyanide ions according to claim 2, wherein the refluxing time in step (1) is 1-2h; the reaction time in the step (2) is 6-8h.
7. The method for preparing a fluorescent probe for detecting cyanide ions according to claim 2, wherein the separation and purification comprises acidification, washing, reduced pressure distillation, column chromatography or column chromatography.
8. Use of a fluorescent probe for detection of cyanide ions according to claim 1 for detection of cyanide ions in aqueous solutions.
9. The use of the fluorescent probe for detecting cyanide ions according to claim 8, wherein the aqueous solution further comprises interfering ions, particularly Cl - 、Br - 、I - 、HSO 4 - 、NO 3 - 、BF 4 - 、ClO 4 - 、SCN - Or S 2 - One or more of (a).
10. The use of the fluorescent probe for detecting cyanide ions according to claim 8, wherein the cyanide ions are detected by dissolving the fluorescent probe in acetonitrile.
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