CN113105387A - Cyanite ion fluorescent probe and preparation method and application thereof - Google Patents

Cyanite ion fluorescent probe and preparation method and application thereof Download PDF

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CN113105387A
CN113105387A CN202110414709.6A CN202110414709A CN113105387A CN 113105387 A CN113105387 A CN 113105387A CN 202110414709 A CN202110414709 A CN 202110414709A CN 113105387 A CN113105387 A CN 113105387A
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fluorescent probe
thiocyanate
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张奇龙
漆爱明
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Guangdong Institute For Drug Control (guangdong Institute For Drug Quality
Guizhou Medical University
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Guizhou Medical University
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Abstract

The invention provides a thiocyanate ion fluorescent probe with a molecular formula of C57H75N4Br3Also provides a preparation method: adding tris (4-bromo) aniline, 4-pyridineboronic acid, potassium carbonate and palladium tetratriphenylphosphine into an aqueous solution of 1, 4-dioxane, under N2Under protection, adding distilled water a after reaction at 100 ℃, extracting with dichloromethane, washing, dissolving in ethanol water solution, adding distilled water b, performing suction filtration, water washing and petroleum ether washing, then recrystallizing with ethanol, adding N, N-dimethylformamide for dissolving, adding 1-bromooctane, reacting at 100 ℃, filtering, washing with acetone and petroleum ether, and drying to obtain the thiocyanate ion fluorescent probe. Also provided is an application for identifying thiocyanate ions. The synthetic method of the thiocyanate ion fluorescent probe is simple and easy to operateAs a result, the fluorescent probe for the thiocyanate ions has strong selectivity to the thiocyanate ions, specificity, real-time performance and high sensitivity, and has great practical significance for detecting the content of the thiocyanate ions in the ecological environment.

Description

Cyanite ion fluorescent probe and preparation method and application thereof
Technical Field
The invention belongs to the technical field of fluorescent probes, and particularly relates to a thiocyanate ion fluorescent probe as well as a preparation method and application thereof.
Background
Thiocyanide is used as an important chemical raw material and widely used in the fields of textile printing and dyeing, fine chemical industry, pharmaceutical industry and the like. In the process of preparing industrial products, the adding proportion is excessive and can not completely react, so that a large amount of thiocyanate enters a waste water system. According to related researches, thiocyanate ions have poor stability, SCN-in the wastewater is easy to react with oxidants such as chlorine and the like to generate a highly toxic substance cyanogen chloride or be oxidized into cyanide, so that the toxicity of the wastewater is increased; simultaneous SCN-The product has toxicity, and excessive intake of thiocyanate can prevent the use of iodine element by human body and cause acute poisoning of human body. SCN-Has strong coordination and is easy to react with Fe in water3+、Cu2+The metal ions are subjected to a complex reaction to generate a metal complex, so that the chromaticity of the wastewater is increased. The large amount of the waste water containing the thiocyanide enters the water body, which causes pollution to the environment and poses serious threats to the health of human beings and the life of livestock and fishes.
The traditional method for detecting thiocyanate ions comprises a cathodic stripping voltammetry method, a GC-MS method and an ion chromatography method, but most of the methods are complex, time-consuming and high in analysis cost. The design and synthesis of the fluorescent probe with selectivity to thiocyanate radical can realize the visual detection of thiocyanate radical, so that the high-efficiency and accurate detection method has important significance in the fields of environment, medicine and biology.
Disclosure of Invention
The technical problem to be solved by the invention is to provide a thiocyanate ion fluorescent probe and a preparation method and application thereof aiming at the defects of the prior art, the method for synthesizing the thiocyanate ion fluorescent probe has the advantages of simplicity, easy operation and few reaction steps, the thiocyanate ion fluorescent probe has strong selectivity to thiocyanate ions, specificity and high sensitivity, is not easily interfered by other anions, has real-time performance and high sensitivity, can instantly detect the thiocyanate ions in a water solution to be detected, and has great practical significance for detecting the content of the thiocyanate ions in an ecological environment.
In order to solve the technical problems, the invention adopts the technical scheme that: a thiocyanate ion fluorescent probe has a molecular formula as follows: c57H75N4Br3The structural formula of the thiocyanate ion fluorescent probe is as follows:
Figure BDA0003025366850000021
the invention also provides a method for preparing the cyanamide ion fluorescent probe, which comprises the following steps:
s1, adding tri (4-bromo) aniline, 4-pyridine boric acid, potassium carbonate and palladium tetratriphenylphosphine into 66 mass percent of 1, 4-dioxane aqueous solution, and adding the mixture into N2Under the protection of (1), reacting for 24h at the temperature of 100 ℃ to obtain a substance A, and then adding the substance A into distilled water a to obtain an extract liquid to be extracted;
s2, extracting the extraction liquid obtained in the S1 with dichloromethane for 3 times, washing the obtained organic phase with distilled water for 3 times, and then washing with a saturated sodium chloride aqueous solution for 3 times to obtain a substance B;
s3, dissolving the substance B obtained in the step S2 in absolute ethyl alcohol, and then adding distilled water B to obtain a substance C;
s4, sequentially carrying out suction filtration, water washing and petroleum ether washing on the substance C obtained in the step S3, and then recrystallizing with ethanol to obtain a substance D; the molecular formula of the substance D is C33H24N4(ii) a The structural formula of the substance D is as follows:
Figure BDA0003025366850000031
s5, adding the substance D obtained in the S4 into N, N-dimethylformamide to dissolve, adding 1-bromooctane, reacting for 24 hours at the temperature of 100 ℃, filtering, washing the obtained precipitate with acetone for 3 times, washing with petroleum ether for 3 times, and drying for 5 hours at the temperature of 100 ℃ to obtain the thiocyanate ion fluorescent probe.
Preferably, the using ratio of the tris (4-bromo) aniline, the 4-pyridineboronic acid, the potassium carbonate, the tetratriphenylphosphine palladium, the 1, 4-dioxane aqueous solution and the distilled water a in S1 is 390.43 mg: 358.93 mg: 325 mg: 93.5 mg: 15mL of: 100 mL.
Preferably, the amount ratio of the substance B, the absolute ethyl alcohol and the distilled water B in S3 is 300 mg: 10mL of: 100 mL.
Preferably, the substance D, N, N-dimethylformamide and 1-bromooctane in S5 are used in a ratio of 476 mg: 10mL of: 2 mL.
The invention also provides an application of the cyanamide ion fluorescent probe, the cyanamide ion fluorescent probe is used for identifying the cyanamide ion, and the method for identifying the cyanamide ion comprises the following steps:
dissolving a thiocyanate ion fluorescent probe in dimethyl sulfoxide, adding distilled water to obtain a stock solution of the thiocyanate ion fluorescent probe, dropwise adding a to-be-detected aqueous solution to the stock solution of the thiocyanate ion fluorescent probe to obtain a mixed solution, and carrying out fluorescence excitation.
Preferably, the concentration of the thiocyanate ion fluorescent probe in the mixed solution is 1 × 10-5mol/L。
Preferably, the wavelength of fluorescence excitation is 340nm, and the wavelength of the cyanamide ion fluorescent probe when the cyanamide ion is identified is 595 nm.
Preferably, the minimum detection limit of the cyanamide ion fluorescent probe for identifying the cyanamide ion is 6.79 multiplied by 10- 6mol/L。
Compared with the prior art, the invention has the following advantages:
the method for synthesizing the thiocyanogen ion fluorescent probe has the advantages of simplicity, easy operation and few reaction steps, and the thiocyanogen ion fluorescent probe has strong selectivity to thiocyanogen ions, specificity, high sensitivity and real-time performance, is not easily interfered by other anions, and can be used for preparing a fluorescent probe for the thiocyanogen ionsThe method has great practical significance for detecting the content of the thiocyanate ions in the ecological environment by instantly detecting the thiocyanate ions in the aqueous solution to be detected, and the minimum detection limit of the thiocyanate ions is 6.79 multiplied by 10-6And the mol/L can meet the detection requirement under a lower concentration of the thiocyanate ions.
The present invention will be described in further detail with reference to the accompanying drawings and examples.
Drawings
FIG. 1 is the nuclear magnetic resonance hydrogen spectrum of the thiocyanate ion fluorescent probe of the present invention.
FIG. 2 is a graph showing fluorescence intensities of different anions detected by the fluorescent probe for thiocyanate ions in example 3 of the present invention.
FIG. 3 is a graph showing the change in fluorescence intensity with respect to a thiocyanate ion (identification wavelength 595nm) in the fluorescent probe for a thiocyanate ion of example 4 of the present invention.
FIG. 4 is an anti-interference diagram of the fluorescent probe for thiocyanate ions in example 5 of the present invention in identifying thiocyanate ions.
Detailed Description
Example 1
In the thiocyanate ion fluorescent probe of the embodiment, the molecular formula of the thiocyanate ion fluorescent probe is as follows: c57H75N4Br3The structural formula of the thiocyanate ion fluorescent probe is as follows:
Figure BDA0003025366850000051
the embodiment also provides a method for preparing the above-mentioned thiocyanate ion fluorescent probe, which comprises the following steps:
s1, adding tri (4-bromo) aniline, 4-pyridine boric acid, potassium carbonate and palladium tetratriphenylphosphine into 66 mass percent of 1, 4-dioxane aqueous solution, and adding the mixture into N2Under the protection of (1), reacting for 24h at the temperature of 100 ℃ to obtain a substance A, and then adding the substance A into distilled water a to obtain an extract liquid to be extracted; the dosage ratio of the tri (4-bromine) aniline, the 4-pyridine boric acid, the potassium carbonate, the tetratriphenylphosphine palladium, the 1, 4-dioxane aqueous solution and the distilled water a390.43 mg: 358.93 mg: 325 mg: 93.5 mg: 15mL of: 100 mL;
s2, extracting the extraction liquid obtained in the S1 with dichloromethane for 3 times, washing the obtained organic phase with distilled water for 3 times, and then washing with a saturated sodium chloride aqueous solution for 3 times to obtain a substance B;
s3, dissolving the substance B obtained in the step S2 in absolute ethyl alcohol, and then adding distilled water B to obtain a substance C; the dosage ratio of the substance B, the absolute ethyl alcohol and the distilled water B is 300 mg: 10mL of: 100 mL;
s4, sequentially carrying out suction filtration, water washing and petroleum ether washing on the substance C obtained in the step S3, and then recrystallizing with ethanol to obtain a substance D; the molecular formula of the substance D is C33H24N4(ii) a The structural formula of the substance D is
Figure BDA0003025366850000061
The mass D, N, N-dimethylformamide and 1-bromooctane were used in a ratio of 476 mg: 10mL of: 2 mL;
s5, adding the substance D obtained in the S4 into N, N-dimethylformamide to dissolve, adding 1-bromooctane, reacting for 24 hours at the temperature of 100 ℃, filtering, washing the obtained precipitate with acetone for 3 times, washing with petroleum ether for 3 times, and drying for 5 hours at the temperature of 100 ℃ to obtain the thiocyanate ion fluorescent probe.
Performing structure detection on the prepared cyanamide ion fluorescent probe, and characterizing the probe by a nuclear magnetic resonance apparatus, wherein a nuclear magnetic resonance hydrogen spectrogram is shown in figure 1, and the analysis of the nuclear magnetic resonance hydrogen spectrogram shows that the cyanamide ion fluorescent probe is C57H75N4Br3The structure is exactly as described above.
Example 2
The embodiment also provides an application of the cyanamide ion fluorescent probe prepared in embodiment 1, wherein the cyanamide ion fluorescent probe is used for identifying the cyanamide ion, and the method for identifying the cyanamide ion comprises the following steps:
dissolving the fluorescent probe of the thiocyanate ion in dimethyl sulfoxide, and adding distilled water to obtain the fluorescent probe of the thiocyanate ionThe concentration of the needles is 1X 10-4Dropwise adding a to-be-detected aqueous solution into the stock solution of the thiocyanate ion fluorescent probe to obtain a stock solution of the thiocyanate ion fluorescent probe with the concentration of 1 × 10-5The mixed solution of mol/L is subjected to fluorescence excitation under the wavelength of 340nm, the thiocyanate ion fluorescent probe has real-time performance, and can instantly identify the thiocyanate ions in the aqueous solution to be detected.
Example 3
This example is the selectivity of the fluorescent probe for thiocyanate ions prepared in example 1:
concentration of thiocyanato ion fluorescent probe is 1X 10-4Stock solution (1X 10) of mol/L thiocyanate ion fluorescent probe-4mol/L) preparation:
dissolving the fluorescent probe in dimethyl sulfoxide, adding distilled water to obtain fluorescent probe with concentration of 1 × 10-4Stock solution of thiocyanate ion fluorescent probe (100mL) in mol/L.
② 18 anions concentration is 1.0X 10-3Anion stock solution (1.0X 10) in mol/L-3mol/L) preparation:
dissolving 18 anion sodium salts in distilled water respectively to obtain 18 anions with concentration of 1.0 × 10-3Anion stock solutions in mol/L (all 100 mL); the anions of the 18 anion stock solutions are SCN-、F-、Cl-、Br-、I-、OH、ClO4 -、CO3 2-、HCO3 -、HSO3 -、HSO4 -、NO3 -、Ac-、S2-、P2O7 2-、H2PO4 -、HPO4 2-、SO4 2-。
③ 18 Cyanite ion fluorescent probes with the concentration of 1 multiplied by 10-5Preparing a mixed solution of mol/L:
1mL of thiocyanate ion fluorescent probe is sequentially added into a 10mL volumetric flaskHas a concentration of 1X 10-4mol/L stock solution of thiocyanate ion fluorescent probe and 1mL of single anion with concentration of 1.0 × 10-3The mol/L anion stock solution is fixed to the scale by distilled water, shaken up and placed for 1h to obtain 18 thiocyanate ion fluorescent probes with the concentration of 1 multiplied by 10- 5A mixed solution of mol/L.
And respectively transferring the 18 mixed solutions into a 1cm quartz cuvette for ultraviolet visible absorption and fluorescence spectrometry, wherein the excitation wavelength of the fluorescence spectrometry is 340nm, and the emission wavelength of the fluorescence spectrometry is 595 nm. As shown in FIG. 2, curve a in the figure is that the fluorescent probe for detecting SCN by using thiocyanate ions-The other curves (b) represent: cyanite ion fluorescent probe detection F-、Cl-、Br-、I-、OH、ClO4 -、CO3 2-、HCO3 -、HSO3 -、HSO4 -、NO3 -、Ac-、S2-、P2O7 2-、H2PO4 -、HPO4 2-、SO4 2-. As can be seen, SCN-The fluorescence intensity of the cyanamide ion fluorescent probe at 595nm is obviously enhanced, other anions have little influence on the fluorescence spectrum of the probe, and no obvious response signal is generated when other anions are added, so that the cyanamide ion fluorescent probe has good selectivity on the cyanamide ion and can be used for identifying the cyanamide ion.
Example 4
This example is the effect of the concentration of the thiocyanate ion on the fluorescence intensity when the thiocyanate ion fluorescent probe prepared in example 1 is used for identifying the thiocyanate ion:
the fluorescent probe for thiocyanate ions prepared in example 1 was dissolved in dimethyl sulfoxide, and distilled water was added thereto to obtain a fluorescent probe for thiocyanate ions having a concentration of 1X 10-4Adding the stock solution of the thiocyanate ion fluorescent probe with the concentration of 1 multiplied by 10 into the stock solution of the thiocyanate ion fluorescent probe with mol/L-4mol/L～50×10-4The mol/L stock solution of 17 thiocyanate ions is obtained to obtain 17Mixing the solution; the concentration of the thiocyanate ion fluorescent probes in the 17 mixed solutions is 1 multiplied by 10-5mol/L, concentration of thiocyanato ion is 1X 10-5mol/L～50×10-5mol/L, the mixed solution was fluorescence excited at 340nm, as shown in FIG. 3, the intensity of fluorescence at 595nm of the fluorescent probe increases gradually with the increase of the concentration of thiocyanato ions, but when SCN is used-Increased to 1X 10-5After mol/L, the increase in fluorescence of the fluorescent probe becomes small.
Further, SCN was measured at room temperature in an aqueous solution at an excitation wavelength of 340nm and an emission wavelength of 595nm-Ion pair concentration of 1X 10-5Calibration curve of fluorescence enhancement of mol/L thiocyanate ion fluorescent probe, y is 1.91x +147.253, and correlation coefficient R20.9935(n is 17), detection limit is 6.79 × 10-6mol/L。
Example 5
This example is an anti-interference test of the fluorescent probe for identifying a thiocyanate ion prepared in example 1:
(1) test a:
concentration of thiocyanato ion fluorescent probe is 1X 10-4Stock solution (1X 10) of mol/L thiocyanate ion fluorescent probe-4mol/L) preparation:
dissolving the fluorescent probe in dimethyl sulfoxide, adding distilled water to obtain fluorescent probe with concentration of 1 × 10-4And (3) preparing a mol/L stock solution of the thiocyanate ion fluorescent probe.
② 17 SCN-free-All anion concentrations of (A) are 1.0X 10-3Anion stock solution (1.0X 10) in mol/L- 3mol/L) preparation:
17 of the cells not containing SCN-Respectively dissolving the anion sodium salt in distilled water to obtain 17 anions with the concentration of 1.0 × 10-3mol/L of anionic stock solution (17 of said solutions not containing SCN)-The anion of the anion stock solution is F-、Cl-、Br-、I-、OH、ClO4 -、CO3 2-、HCO3 -、HSO3 -、HSO4 -、NO3 -、Ac-、S2-、P2O7 2-、H2PO4 -、HPO4 2-、SO4 2-)
③ concentration of 1.0X 10-4Preparing mol/L thiocyanate ion stock solution:
dissolving sodium thiocyanide in distilled water to obtain SCN-The concentration is 1.0 × 10-4A mol/L stock solution of thiocyanate ions.
③ 18 Cyanite ion fluorescent probes with the concentration of 1 multiplied by 10-5Preparing a mixed solution of mol/L:
1mL of a thiocyanate ion fluorescent probe was sequentially added to a 10mL measuring flask in a concentration of 1X 10-4mol/L stock solution of thiocyanate ion fluorescent probe and 1mL of single anion with concentration of 1.0 × 10-3mol/L SCN-free-Anion stock solution of (anion is sequentially F)-、Cl-、Br-、I-、OH、ClO4 -、CO3 2-、HCO3 -、HSO3 -、HSO4 -、NO3 -、Ac-、S2-、P2O7 2-、H2PO4 -、HPO4 2-、SO4 2-) Adding distilled water to constant volume to scale, shaking, standing for 1h to obtain 17 thiocyanate ion fluorescent probes with concentration of 1 × 10-5mol/L mixture (mixture B-mixture R in that order, without SCN)-)。
1mL of a thiocyanate ion fluorescent probe was sequentially added to a 10mL measuring flask in a concentration of 1X 10-4mol/L stock solution of thiocyanate ion fluorescent probe and 1mL of SCN-The concentration is 1.0 × 10-4Fixing the volume of the mol/L stock solution of the thiocyanate ion to a scale with distilled water, shaking uniformly, and standing for 1h to obtain the thiocyanate ion fluorescent probe with the concentration of 1 × 10-5mixing of mol/LCompound solution A (containing SCN)-)。
After distilled water is used for fixing the volume to the scale, the mixture is shaken up and placed for 1h to obtain 18 thiocyanate ion fluorescent probes with the concentration of 1 multiplied by 10-5The obtained mixed solution is named as mixed solution A-mixed solution Q (corresponding to A-Q from left to right in the front row in the stereogram of FIG. 4), 18 mixed solutions are subjected to fluorescence spectrum measurement under the excitation wavelength of 340nm and the emission wavelength of 595nm, and as can be seen from FIG. 4, a thiocyanate ion fluorescence probe pair F-、Cl-、Br-、I-、OH、ClO4 -、CO3 2-、HCO3 -、HSO3 -、HSO4 -、NO3 -、Ac-、S2-、P2O7 2-、H2PO4 -、HPO4 2-、SO4 2-There was little apparent response (mix B-mix R), while SCN was added-When the fluorescent probe is used (mixed solution A), the fluorescent probe can be induced to generate strong and stable fluorescence emission.
(2) Test b:
concentration of thiocyanato ion fluorescent probe is 1X 10-4Preparing mol/L stock solution of a thiocyanate ion fluorescent probe:
dissolving the fluorescent probe in dimethyl sulfoxide, adding distilled water to obtain fluorescent probe with concentration of 1 × 10-4And (3) preparing a mol/L stock solution of the thiocyanate ion fluorescent probe.
Concentration of 1.0X 10-4Preparing mol/L thiocyanate ion stock solution:
dissolving sodium thiocyanide in distilled water to obtain SCN-The concentration is 1.0 × 10-4A mol/L stock solution of thiocyanate ions.
③ Cyanium sulfide radical ion fluorescent probe-SCN-Preparation of solution system:
1mL of a thiocyanate ion fluorescent probe was sequentially added to a 10mL measuring flask in a concentration of 1X 10-4Stock solution of mol/L thiocyanate ion fluorescent probe and 1mL thiocyanate ion fluorescent probeHas a concentration of 1X 10-4Fixing the volume of the stock solution of the mol/L thiocyanate ion fluorescent probe to a scale with distilled water, shaking uniformly and standing for 1h to obtain the thiocyanate ion fluorescent probe-SCN-Solution system of said thiocyanate ion fluorescent probe-SCN-SCN in solution System-The concentration is 1.0 × 10-5mol/L, the concentration of the thiocyanato ion fluorescent probe is 1.0 multiplied by 10-5mol/L (corresponding to solution A in test a);
fourthly, 17 SCN-free products are prepared-All anion concentrations of (A) are 1.0X 10-3Anion stock solution (1.0X 10) in mol/L-3mol/L) preparation:
17 of the cells not containing SCN-Respectively dissolving the anion sodium salt in distilled water to obtain 17 anions with the concentration of 1.0 × 10-3mol/L of anionic stock solution (17 of said solutions not containing SCN)-The anion of the anion stock solution is F-、Cl-、Br-、I-、OH、ClO4 -、CO3 2-、HCO3 -、HSO3 -、HSO4 -、NO3 -、Ac-、S2-、P2O7 2-、H2PO4 -、HPO4 2-、SO4 2-)
To each thiocyanate ion fluorescent probe-SCN-Adding 17 SCN-free solutions into the solution system respectively-All anion concentrations of (A) are 1.0X 10-3mol/L of anionic stock solution (17 of said solutions not containing SCN)-The anion of the anion stock solution is F-、Cl-、Br-、I-、OH、ClO4 -、CO3 2-、HCO3 -、HSO3 -、HSO4 -、NO3 -、Ac-、S2-、P2O7 2-、H2PO4 -、HPO4 2-、SO4 2-) To obtain a mixed solution b-a mixed solution r (corresponding to the rear part of the perspective view of FIG. 4)B-r from left to right in the row) concentration of the anion stock solution (1.0X 10) despite the addition of other anions-3mol/L) is far larger than the fluorescent probe-SCN of the thiocyanate ion-SCN in solution System-Concentration of (1.0X 10)-5mol/L) of the cyanogen sulfide ion fluorescence probe, but the fluorescence of the solution added with other anion stock solutions at 595nm is not quenched, which shows that the cyanogen sulfide ion fluorescence probe prepared in example 1 has stronger anti-interference capability.
Example 6
This example is a time test of the interaction of the fluorescent probe for thiocyanate ions prepared in example 1 with the thiocyanate ions:
the response of the thiocyanate ion fluorescent probe to the thiocyanate ions is fast, the fluorescence is enhanced immediately after the probe is added, and the probe is almost instantaneous and has good sensitivity and real-time performance, so the probe has great practical significance for detecting the content of the thiocyanate ions in the ecological environment.
The above description is only for the preferred embodiment of the present invention, and is not intended to limit the present invention in any way. Any simple modification, change and equivalent changes of the above embodiments according to the technical essence of the invention are still within the protection scope of the technical solution of the invention.

Claims (9)

1. The thiocyanate ion fluorescent probe is characterized in that the molecular formula of the thiocyanate ion fluorescent probe is as follows: c57H75N4Br3The structural formula of the thiocyanate ion fluorescent probe is as follows:
Figure FDA0003025366840000011
2. a method for preparing the thiocyanate ion fluorescent probe of claim 1, which comprises:
s1, adding tri (4-bromo) aniline, 4-pyridine boric acid, potassium carbonate and palladium tetratriphenylphosphine into 66 mass percent of 1, 4-dioxane aqueous solution, and then adding the mixture into a reactorN2Under the protection of (1), reacting for 24h at the temperature of 100 ℃ to obtain a substance A, and then adding the substance A into distilled water a to obtain an extract liquid to be extracted;
s2, extracting the extraction liquid obtained in the S1 with dichloromethane for 3 times, washing the obtained organic phase with distilled water for 3 times, and then washing with a saturated sodium chloride aqueous solution for 3 times to obtain a substance B;
s3, dissolving the substance B obtained in the step S2 in absolute ethyl alcohol, and then adding distilled water B to obtain a substance C;
s4, sequentially carrying out suction filtration, water washing and petroleum ether washing on the substance C obtained in the step S3, and then recrystallizing with ethanol to obtain a substance D; the molecular formula of the substance D is C33H24N4(ii) a The structural formula of the substance D is as follows:
Figure FDA0003025366840000021
s5, adding the substance D obtained in the S4 into N, N-dimethylformamide to dissolve, adding 1-bromooctane, reacting for 24 hours at the temperature of 100 ℃, filtering, washing the obtained precipitate with acetone for 3 times, washing with petroleum ether for 3 times, and drying for 5 hours at the temperature of 100 ℃ to obtain the thiocyanate ion fluorescent probe.
3. The method according to claim 2, wherein the tris (4-bromo) aniline, 4-pyridineboronic acid, potassium carbonate, palladium tetratriphenylphosphine, 1, 4-dioxane aqueous solution and distilled water a in S1 are used in an amount ratio of 390.43 mg: 358.93 mg: 325 mg: 93.5 mg: 15mL of: 100 mL.
4. The method according to claim 2, wherein the substance B, the absolute ethanol and the distilled water B are used in a ratio of 300mg in S3: 10mL of: 100 mL.
5. The method as claimed in claim 2, wherein the substance D, N, N-dimethylformamide and 1-bromooctane are used in S5 in a ratio of 476 mg: 10mL of: 2 mL.
6. The application of the fluorescent probe for the thiocyanate ions according to claim 1, wherein the fluorescent probe for the thiocyanate ions is used for identifying the thiocyanate ions, and the method for identifying the thiocyanate ions comprises the following steps:
dissolving a thiocyanate ion fluorescent probe in dimethyl sulfoxide, adding distilled water to obtain a stock solution of the thiocyanate ion fluorescent probe, dropwise adding a to-be-detected aqueous solution to the stock solution of the thiocyanate ion fluorescent probe to obtain a mixed solution, and carrying out fluorescence excitation.
7. The use of claim 6, wherein the concentration of the Cyania ion fluorescent Probe in the mixture is 1x 10-5mol/L。
8. The use of claim 6, wherein the wavelength of fluorescence excitation is 340nm and the wavelength of the cyanamide ion when recognized by the cyanamide ion fluorescent probe is 595 nm.
9. The use of claim 6, wherein the minimum detection limit of the fluorescent probe for identifying the thiocyanate ions is 6.79 x 10-6mol/L。
CN202110414709.6A 2021-04-17 2021-04-17 Cyanite ion fluorescent probe and preparation method and application thereof Pending CN113105387A (en)

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Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20190062629A1 (en) * 2016-05-23 2019-02-28 Shaanxi Normal University Preparation method and application of fluorescent compound having sensing ability to aniline and o-toluidine gas, and fluorescent film with the same
CN110423609A (en) * 2019-07-29 2019-11-08 贵州大学 A kind of fluorescence probe identifying thiocyanate radical and its preparation and recognition methods

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20190062629A1 (en) * 2016-05-23 2019-02-28 Shaanxi Normal University Preparation method and application of fluorescent compound having sensing ability to aniline and o-toluidine gas, and fluorescent film with the same
CN110423609A (en) * 2019-07-29 2019-11-08 贵州大学 A kind of fluorescence probe identifying thiocyanate radical and its preparation and recognition methods

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