CN113200930A - Fluorescent probe for copper ion detection and preparation method and application thereof - Google Patents
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Abstract
The invention relates to a fluorescent probe for detecting copper ions, a preparation method and application thereof, wherein the synthesis method of the fluorescent probe comprises the following steps: 1, 2-phenylenediamine is used as a raw material to react, the solvent is evaporated under reduced pressure after the reaction is finished, the residue is separated by column chromatography to obtain benzotriazole, and then the benzotriazole is reacted with RX (CH)3I. BnCl and BnBr) under the alkaline condition to generate benzotriazole derivatives 3a, 2- (2H-1,2, 3-benzotriazole-2-yl) -N-benzylaniline, 3b, 2- (2H-1,2, 3-benzotriazole-2-yl) -N-methylaniline and 3c, 2- (2H-1,2, 3-benzotriazole-2-yl) -N, N-dibenzylaniline. The synthesis method is simple and efficient, and a catalyst is not needed in the amino derivatization reaction process, so that the economic cost is greatly saved. The finally synthesized benzotriazole derivatives can be used forThe method has the advantages of rapid detection of the bivalent copper ions, good selectivity and strong anti-interference capability, and can be widely used for detecting the bivalent copper ions.
Description
Technical Field
The invention relates to a fluorescent probe for detecting copper ions, a preparation method and application research thereof.
Background
Most heavy metal ions are generated in the industrial production process, and if the heavy metal ions are not treated, the heavy metal ions are discharged to the nature to cause heavy metal pollution, so that the removal of the heavy metal ions is an important link. Copper is a heavy metal and is a necessary trace element for human beings, animals and plants, but when the amount of copper is accumulated to a certain degree, a series of diseases can be caused, and even the health is damaged. The currently commonly used methods for detecting copper ions include ion chromatography, spectrophotometry, atomic absorption method, electrochemical method, fluorescence spectroscopy and the like, wherein the fluorescence spectroscopy has the characteristics of high speed, high efficiency, sensitive response and the like, and is currently applied to scientific research. Therefore, the development of the fluorescent probe capable of detecting the copper ions has wide application prospect.
The invention provides a fluorescent probe for detecting copper ions, a preparation method and application thereof, the derivatization reaction can be completed without the participation of a catalyst, a series of benzotriazole derivatives capable of detecting copper ions are successfully synthesized, and the fluorescent probe has good selectivity and strong anti-interference capability.
Disclosure of Invention
The invention mainly aims to provide a fluorescent probe for detecting copper ions, and a preparation method and application research thereof.
The technical scheme of the invention is as follows:
the fluorescent probe for detecting copper ions and the preparation method and the application thereof, wherein the chemical structural formula of the compound is as follows:
in the structure, a substituent R comprises an electron-donating group of any one of methyl and benzyl, and the position of the substituent R is fixed on an amino; wherein, the monosubstituted products 3a and 3b have ESIPT effect, and the structural formula of the benzotriazole derivative comprises:
according to the compound, the invention also provides a preparation method of the benzotriazole derivative, which comprises the following steps:
dissolving compound 1 in solvent, adding compound 2RX, performing oil bath reaction under alkaline condition, detecting by TLC, evaporating under reduced pressure to remove solvent, and separating residue by column chromatography to obtain product, wherein R is methyl or benzyl, and X is halogen (RX: CH)3I. BnCl, or BnBr.
The feeding molar ratio of the compound 1 to the compound 2 to the alkali is 0.15-0.6: 0.3-3.6: 0.45-7.2.
In the reaction process, the alkali is potassium carbonate, and the solvent is acetonitrile.
During the oil bath reaction, the reaction temperature is 30-130 ℃.
During the reaction of compound 1 with BnCl or BnBr under the above reaction conditions, the temperature increase and/or the increase in the charge ratio of compound 2 will make the reaction more prone to the formation of disubstituted product 3 c. If the temperature is raised to be more than 100 ℃, the product comprises a disubstituted product 3 c; if the feeding molar ratio of the compound 1 to the compound 2 is 1: 2-6, the product comprises disubstituted product 3 c.
The technical scheme of the invention is to apply the compound to a fluorescent probe for detecting copper ions, and the fluorescent probe is used for detecting divalent copper ions.
The invention has the following beneficial effects:
the invention discloses an amino derivatization reaction of benzotriazole for detecting copper ions for the first time. In the amino derivatization reaction process of benzotriazole, the synthesis method is simple and efficient, the reaction speed is high, the reaction can be stably carried out at high temperature, and no catalyst is needed, so that the economic cost is greatly saved. The method successfully synthesizes a series of benzotriazole derivatives. It is noted that the temperature during the reaction and the charge ratio of compound 2 are increased to make the amino derivatization more prone to generate the disubstituted product 3c, wherein the monosubstituted products 3a and 3b have the ESIPT characteristic, and are an ESIPT type fluorescent probe capable of detecting divalent copper ions.
Drawings
FIG. 1: nuclear magnetic resonance hydrogen spectrum of 2- (2H-1,2, 3-benzotriazol-2-yl) -N-benzylaniline (3a) (2H-1,2, 3-benzotriazol-2-yl) -N-benzylaniline1H NMR) graph.
FIG. 2: nuclear magnetic resonance carbon spectrum of 2- (2H-1,2, 3-benzotriazol-2-yl) -N-benzylaniline (3a) (2H-1,2, 3-benzotriazol-2-yl) -N-benzylaniline13C NMR) graph.
FIG. 3: nuclear magnetic resonance hydrogen spectrum of 2- (2H-1,2, 3-benzotriazol-2-yl) -N-methylaniline (3b) ((1H NMR) graph.
FIG. 4: nuclear magnetic resonance carbon spectrum of 2- (2H-1,2, 3-benzotriazol-2-yl) -N-methylaniline (3b) ((13C NMR) graph.
FIG. 5: nuclear magnetic resonance hydrogen spectrum of 2- (2H-1,2, 3-benzotriazol-2-yl) -N, N-dibenzylaniline (3c) ((1H NMR) graph.
FIG. 6: nuclear magnetic resonance carbon spectrum of 2- (2H-1,2, 3-benzotriazol-2-yl) -N, N-dibenzylaniline (3c) ((13C NMR) graph.
FIG. 7: fluorescence spectra of the fluorescent probe 3a in the presence of different concentrations of copper ions.
FIG. 8: fluorescence spectra of fluorescent probe 3b in the presence of different concentrations of copper ions.
FIG. 9: fluorescence spectra of fluorescent probe 3c in the presence of different concentrations of copper ions.
FIG. 10: fluorescent probes 3a are respectively attached to Cu2+And other ions (Blank, Ca)2+、Co2+、Zn2+、Fe3+、Cs+、K+、Mg2+、Ni2+、NH4 +、Al3+、Na+) Fluorescence spectrum after the action.
FIG. 11: fluorescent probes 3b are each in contact with Cu2+And other ions (Blank, Ca)2+、Co2+、Zn2+、Fe3+、Cs+、K+、Mg2+、Ni2+、NH4 +、Al3+、Na+) Fluorescence spectrum after the action.
FIG. 12: fluorescent probes 3c are attached to Cu, respectively2+And other ions (Blank, Ca)2+、Co2+、Zn2+、Fe3+、Cs+、K+、Mg2+、Ni2+、NH4 +、Al3+、Na+) Fluorescence spectrum after the action.
Detailed Description
The invention is further illustrated by the following examples, but the scope of the invention as claimed is not limited to the scope of the examples.
Instruments and reagents:
SHZ-E type circulating water vacuum pump (shanghai rongyan chemical instrumentation plant); model DZE-6120 vacuum drying oven (Shanghai Hengtian scientific instruments manufacturing Co.); EB2005A electronic balance; ZF-I type three-purpose ultraviolet analyzer; DE-102J heat collection type constant temperature heating magnetic stirrer (Wanfa chemical instruments factory, Hiroshi city); DFX-5L/30 low-temperature constant-temperature reaction bath (Wuchuan instrument factory in Wuxi city); a 2YZ-4A rotary vane type vacuum oil pump (Winhao vacuum equipment factory in Linhai city). Toluene (AR), potassium tert-butoxide (AR), copper oxide (AR), o-phenylenediamine (AR), potassium carbonate (AR), Acetonitrile (AR), petroleum ether (AR), ethyl Acetate (AR).
1H NMR and13c NMR was measured using a Varian Mercury 400 model 400MHz NMR spectrometer or a Varian Mercury 600 model 600MHz NMR spectrometer using deuterated chloroform (CDCl)3) Solvent and TMS as internal standard; the reagent is chemically pure or analytically pure.
Example 1
A process for the preparation of 2- (2H-1,2, 3-benzotriazol-2-yl) -N-benzylaniline (3a) from BnCl comprising the following experimental steps:
benzotriazole (0.6mmol, 0.1261g) is weighed and dissolved in 6mL acetonitrile solvent, stirred at room temperature until the benzotriazole is fully dissolved, potassium carbonate (1.8mmol, 0.2488g) and benzyl chloride (1.2mmol, 0.1519g) are sequentially added into the solution, the solution is placed in an oil bath kettle at 100 ℃ under alkaline conditions for reaction for 4 hours, and then TLC is carried out to detect the product points 3a and 3c, wherein the main product point is 3 a. Then, the solvent was distilled off under reduced pressure, and the residue was separated by column chromatography to give the product 3a with a yield of 64%.
Hydrogen spectrum:
1H NMR(400MHz,CDCl3)δ(ppm)8.24-8.21(m,1H),8.05-8.02(t,J＝12Hz,1H),7.94-7.92(m,2H),7.44-7.42(m,3H),7.40(s,1H),7.37-7.33(t,J＝16Hz,2H),7.29-7.25(t,J＝16Hz,2H),6.84-6.80(m,2H),4.59-4.58(d,J＝4Hz,2H).
carbon spectrum:
13C NMR(101MHz,CDCl3)δ143.64,140.80,138.99,130.11,128.66,127.10,126.89,126.85,124.11,117.84,116.32,113.11,77.32,77.00,76.68,47.34.
example 2
A process for the preparation of 2- (2H-1,2, 3-benzotriazol-2-yl) -N, N-dibenzylaniline (3c) from BnCl comprising the following experimental steps:
benzotriazole (0.6mmol, 0.1261g) is weighed and dissolved in 6mL acetonitrile solvent, stirred at room temperature until the benzotriazole is fully dissolved, potassium carbonate (7.2mmol, 0.9951g) and benzyl chloride (3.6mmol, 0.4557g) are sequentially added into the solution, the solution is placed in an oil bath kettle at 120 ℃ under alkaline condition for reaction for 4 hours, and the reaction is detected to have product points 3a and 3c through TLC, wherein the main product point is 3 c. Then, the solvent was distilled off under reduced pressure, and the residue was separated by column chromatography to give the product 3c with a yield of 59%.
Hydrogen spectrum:
1H NMR(400MHz,CDCl3)δ(ppm)7.99-7.96(m,2H),7.57-7.55(d,J＝8Hz,1H),7.45-7.42(m,2H),7.36-7.32(t,J＝16Hz,1H),7.25,7.22-7.14(m,10H),7.12-7.05(m,2H),3.90(s,4H).
carbon spectrum:
13C NMR(101MHz,CDCl3)δ146.31,144.92,137.53,134.81,130.36,128.35,128.09,126.91,126.74,122.97,122.25,118.40,77.32,77.00,76.68,55.62.
example 3
By CH3I Process for the preparation of 2- (2H-1,2, 3-benzotriazol-2-yl) -N-methylaniline (3b) comprising the following experimental steps:
benzotriazole (0.6mmol, 0.1261g) is weighed and dissolved in 6mL acetonitrile solvent, the mixture is stirred at room temperature until the benzotriazole and the acetonitrile solvent are fully dissolved, potassium carbonate (4.2mmol, 0.5805g) and methyl iodide (3.6mmol, 0.5110g) are sequentially added into the solution, the solution is placed in an oil bath kettle at 30 ℃ under alkaline condition for reaction for 4 hours, after the reaction is detected by TLC, the solvent is evaporated under reduced pressure, and the residue is separated by column chromatography to obtain the product 3b, wherein the yield is 55%.
Hydrogen spectrum:
1H NMR(400MHz,CDCl3)δ(ppm)8.12-8.10(d,J＝8Hz,1H),7.87-7.83(m,2H),7.37-7.32(m,3H),7.29-7.25(t,J＝16Hz,1H),6.81-6.79(d,J＝8Hz,1H),6.76-6.72(t,J＝16Hz,1H),2.93-2.92(d,J＝4Hz,3H).
carbon spectrum:
13C NMR(101MHz,CDCl3)δ143.60,141.91,130.18,126.78,124.01,117.77,115.82,112.06,77.32,77.00,76.68,30.04.
example 4
A process for the preparation of 2- (2H-1,2, 3-benzotriazol-2-yl) -N-benzylaniline (3a) from BnBr comprising the following experimental steps:
benzotriazole (0.6mmol, 0.1261g) is weighed and dissolved in 6mL acetonitrile solvent, stirred at room temperature until the benzotriazole is fully dissolved, potassium carbonate (1.8mmol, 0.2488g) and benzyl bromide (1.2mmol, 0.2052g) are sequentially added into the solution, the solution is placed in an oil bath kettle at 100 ℃ under alkaline conditions for reaction for 4 hours, and the reaction products of points 3a and 3c are detected by TLC, wherein the main product point is 3 a. Then, the solvent was distilled off under reduced pressure, and the residue was separated by column chromatography to give the product 3a with a yield of 73%.
Hydrogen spectrum:
1H NMR(400MHz,CDCl3)δ(ppm)8.24-8.21(m,1H),8.05-8.02(t,J＝12Hz,1H),7.94-7.92(m,2H),7.44-7.42(m,3H),7.40(s,1H),7.37-7.33(t,J＝16Hz,2H),7.29-7.25(t,J＝16Hz,2H),6.84-6.80(m,2H),4.59-4.58(d,J＝4Hz,2H).
carbon spectrum:
13C NMR(101MHz,CDCl3)δ143.64,140.80,138.99,130.11,128.66,127.10,126.89,126.85,124.11,117.84,116.32,113.11,77.32,77.00,76.68,47.34.
example 5
A process for the preparation of 2- (2H-1,2, 3-benzotriazol-2-yl) -N, N-dibenzylaniline (3c) from BnBr, comprising the following experimental steps:
benzotriazole (0.6mmol, 0.1261g) is weighed and dissolved in 6mL acetonitrile solvent, stirred at room temperature until the benzotriazole is fully dissolved, potassium carbonate (7.2mmol, 0.9951g) and benzyl bromide (3.6mmol, 0.6157g) are sequentially added into the solution, the solution is placed in an oil bath kettle at 120 ℃ under alkaline conditions for reaction for 4 hours, and the reaction is detected to have product points 3a and 3c through TLC, wherein the main product point is 3 c. Then, the solvent was distilled off under reduced pressure, and the residue was separated by column chromatography to give the product 3c in 69% yield.
Hydrogen spectrum:
1H NMR(400MHz,CDCl3)δ(ppm)7.99-7.96(m,2H),7.57-7.55(d,J＝8Hz,1H),7.45-7.42(m,2H),7.36-7.32(t,J＝16Hz,1H),7.25,7.22-7.14(m,10H),7.12-7.05(m,2H),3.90(s,4H).
carbon spectrum:
13C NMR(101MHz,CDCl3)δ146.31,144.92,137.53,134.81,130.36,128.35,128.09,126.91,126.74,122.97,122.25,118.40,77.32,77.00,76.68,55.62.
example 6: detecting copper ions with different concentrations by using a 2- (2H-1,2, 3-benzotriazole-2-yl) -N-benzylaniline (3a) fluorescent probe, dissolving the prepared 2- (2H-1,2, 3-benzotriazole-2-yl) -N-benzylaniline (3a) fluorescent probe into a DMSO solution, and preparing a 500 mu M probe mother solution; then, 30. mu.L of the probe stock solution was taken out with a pipette and added to 3ml of a mixed solution of DMF: HEPES buffer (0.01mM, pH 7.4) ═ 4: 6, and then copper ions (1mM) were added to the system at different concentrations (0. mu.M, 2. mu.M, 4. mu.M, 6. mu.M, 8. mu.M, 10. mu.M, 12. mu.M, 14. mu.M, 16. mu.M, 18. mu.M, 20. mu.M, 22. mu.M, 24. mu.M, 26. mu.M, 28. mu.M), and after 10 minutes of reaction, the fluorescence emission was gradually reduced at 502nm as shown in FIG. 7 and as seen in FIG. 7, with the addition of the copper ion solution.
Example 7: detecting copper ions with different concentrations by using a 2- (2H-1,2, 3-benzotriazole-2-yl) -N-methylaniline (3b) fluorescent probe, dissolving the prepared 2- (2H-1,2, 3-benzotriazole-2-yl) -N-methylaniline (3b) fluorescent probe into a DMSO solution, and preparing a 500 mu M probe mother solution; then, 30. mu.L of the probe stock solution was taken out with a pipette and added to 3ml of a mixed solution of DMF: HEPES buffer (0.01mM, pH 7.4) ═ 4: 6, and then copper ions (1mM) were added to the system at different concentrations (0. mu.M, 2. mu.M, 4. mu.M, 6. mu.M, 8. mu.M, 10. mu.M, 12. mu.M, 14. mu.M, 16. mu.M, 18. mu.M, 20. mu.M, 22. mu.M, 24. mu.M, 26. mu.M, 28. mu.M), and after 10 minutes of reaction, the fluorescence emission was gradually reduced at 512nm as shown in FIG. 8 and as seen in FIG. 8.
Example 8: detection of copper ions with different concentrations by 2- (2H-1,2, 3-benzotriazole-2-yl) -N, N-dibenzylaniline (3c) fluorescent probe
Dissolving the prepared 2- (2H-1,2, 3-benzotriazole-2-yl) -N, N-dibenzylaniline (3c) fluorescent probe into a DMSO solution to prepare a 500 mu M probe mother solution; then, 30. mu.L of the probe stock solution was taken out with a pipette and added to 3ml of a mixed solution of DMF: HEPES buffer (0.01mM, pH 7.4) ═ 4: 6, and then copper ions (1mM) were added to the system at different concentrations (0. mu.M, 2. mu.M, 4. mu.M, 6. mu.M, 8. mu.M, 10. mu.M, 12. mu.M, 14. mu.M, 16. mu.M, 18. mu.M, 20. mu.M, 22. mu.M, 24. mu.M, 26. mu.M, 28. mu.M), and after 10 minutes of reaction, the fluorescence emission was gradually decreased at 514nm as shown in FIG. 9 and as shown in FIG. 9.
Example 9: selective detection of copper and other ions by 2- (2H-1,2, 3-benzotriazol-2-yl) -N-benzylaniline (3a) fluorescent probe to 3ml dmdmmf containing 30 μ L of probe stock: HEPES buffer (0.01mM, pH 7.4) ═ 4: 6, different ions (Blank, Cu) with the same concentration are respectively added into the solution2+、Ca2+、Co2+、Zn2+、Fe3+、Cs+、K+、Mg2+、Ni2+、NH4 +、Al3+、Na+) The fluorescence spectrum change detected after 10 minutes is shown in fig. 10, and it can be seen from fig. 10 that the addition of copper ions compared with other ions causes a significant fluorescence response. This result indicates that the probe has a divalent copper ionBetter fluorescence selectivity.
Example 10: selective detection of copper and other ions by 2- (2H-1,2, 3-benzotriazol-2-yl) -N-methylaniline (3b) fluorescent probe to 3ml dmdmmf containing 30 μ L of probe stock: HEPES buffer (0.01mM, pH 7.4) ═ 4: 6, different ions (Blank, Cu) with the same concentration are respectively added into the solution2+、Ca2+、Co2+、Zn2+、Fe3+、Cs+、K+、Mg2 +、Ni2+、NH4 +、Al3+、Na+) The fluorescence spectrum change detected after 10 minutes is shown in fig. 11, and it can be seen from fig. 11 that the addition of copper ions compared with other ions causes a significant fluorescence response. This result indicates that the probe has better fluorescence selectivity for divalent copper ions.
Example 11: selective detection of copper and other ions by 2- (2H-1,2, 3-benzotriazol-2-yl) -N, N-dibenzylaniline (3c) fluorescent probe to 3ml dmdm containing 30 μ L of probe stock: HEPES buffer (0.01mM, pH 7.4) ═ 4: 6, different ions (Blank, Cu) with the same concentration are respectively added into the solution2+、Ca2+、Co2+、Zn2+、Fe3+、Cs+、K+、Mg2+、Ni2+、NH4 +、Al3+、Na+) The fluorescence spectrum change detected after 10 minutes is shown in fig. 12, and it can be seen from fig. 12 that the addition of copper ions compared with other ions causes a significant fluorescence response. This result indicates that the probe has better fluorescence selectivity for divalent copper ions.
Claims (7)
1. Benzotriazole derivatives are characterized in that the structural formula is as follows:
2. According to claim1, wherein the structural formula of the benzotriazole derivative comprises:
3. the process for the preparation of benzotriazole derivatives according to claim 1 or 2, wherein the process is carried out by the steps of:
dissolving the compound 1 in a solvent, adding a compound 2RX to perform oil bath reaction under an alkaline condition, performing TLC detection reaction, evaporating the solvent under reduced pressure, and performing column chromatography separation on residues to obtain a product, wherein R is methyl or benzyl, and X is halogen.
4. The benzotriazole derivative according to claim 3, wherein the molar ratio of compound 1 to compound 2 to the base is 0.15-0.6: 0.3-3.6: 0.45-7.2.
5. The benzotriazole derivative of claim 3 wherein the base is potassium carbonate and the solvent is acetonitrile during the reaction.
6. The benzotriazole derivative according to claim 3, wherein the reaction temperature during the oil bath reaction is 30 to 130 ℃.
7. Use of a fluorescent probe for copper ion detection according to claim 1 or 2, characterized in that the fluorescent probe is used for detection of divalent copper ions.
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| CN114573519A (en) * | 2021-04-14 | 2022-06-03 | 三峡大学 | Fluorescent probe for copper ion detection and preparation method and application thereof |
| CN114573519B (en) * | 2021-04-14 | 2023-11-21 | 三峡大学 | Fluorescent probe for copper ion detection and preparation method and application thereof |
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| CN114573519B (en) | 2023-11-21 |
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