CN112321817B - Preparation of terbium ion coordination polymer fluorescent nano probe and K thereof+Detection of - Google Patents

Preparation of terbium ion coordination polymer fluorescent nano probe and K thereof+Detection of Download PDF

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CN112321817B
CN112321817B CN202011277096.8A CN202011277096A CN112321817B CN 112321817 B CN112321817 B CN 112321817B CN 202011277096 A CN202011277096 A CN 202011277096A CN 112321817 B CN112321817 B CN 112321817B
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ether nitrile
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arylene ether
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CN112321817A (en
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贾坤
谢俊妮
刘孝波
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University of Electronic Science and Technology of China
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    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
    • C08G65/34—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from hydroxy compounds or their metallic derivatives
    • C08G65/38—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from hydroxy compounds or their metallic derivatives derived from phenols
    • C08G65/40—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from hydroxy compounds or their metallic derivatives derived from phenols from phenols (I) and other compounds (II), e.g. OH-Ar-OH + X-Ar-X, where X is halogen atom, i.e. leaving group
    • C08G65/4012—Other compound (II) containing a ketone group, e.g. X-Ar-C(=O)-Ar-X for polyetherketones
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Abstract

Preparation of terbium ion coordination poly (arylene ether nitrile) fluorescent nano probe and K thereof+Detection, belonging to the field of metal ion coordination polymers. The invention takes the block poly (arylene ether nitrile) copolymer with side chain containing carboxyl and sulfonic group as raw material, and reacts with Tb by a solvent displacement method3+And adsorbing rhodamine B dye after crosslinking to obtain the fluorescent nano probe. With Tb in the aqueous phase3+Adding into poly (arylene ether nitrile) in DMF phase, wherein poly (arylene ether nitrile) containing a large amount of carboxyl sulfonic group replaces water molecule and Tb3+Tb sensitised by coordination and the presence of a large number of aromatic rings3+To obtain Tb3+Coordinating poly (arylene ether nitrile) nanoparticles. Meanwhile, due to an interpenetrating network formed by coordination, the structure has a large specific surface area and is convenient for adsorbing rhodamine B with red light emission. By K+The specific enhanced response to the luminous intensity of the fluorescent probe constructs a ratio type fluorescent nano probe, and realizes the aim of comparing the water phase K+And detecting residual potassium ions in the polyaryl ether nitrile powder produced industrially.

Description

Preparation of terbium ion coordination polymer fluorescent nano probe and K thereof+Detection of
Technical Field
The invention belongs to the field of metal ion coordination polymers, and particularly relates to a preparation method of a terbium ion coordination poly (arylene ether nitrile) fluorescent nano probe and application thereof in K+Application in detection.
Background
The special engineering plastic has a series of excellent performances such as good heat resistance, high strength, corrosion resistance, good insulativity, wear resistance, radiation resistance and the like, and plays an increasingly important role in the fields of electronics, aerospace, military and the like. Polyarylether is a typical special engineering plastic, and the polyarylether special engineering plastic represented by polyetheretherketone, polyethersulfone, polyarylethernitrile and the like is prepared by nucleophilic substitution polycondensation. Because excessive K is often used in the polymerization of special engineering plastics of polyarylether2CO3As a catalyst, a certain amount of K is generated in the reaction product+Residual, and polymer excess residual K2CO3The processing performance and the electrical performance of the product are seriously influenced, and further the subsequent engineering application is greatly limited. Therefore, the residual K in the special polymer of the polyarylether is developed+The simple analysis method for detection has important application value.
At present, commonly used potassium ion detection methods include flame photometry, spectrophotometry, ion chromatography, microwave drying method, inductively coupled plasma atomic emission spectrometry (ICP-AES), and although the methods can achieve specific high-sensitivity detection of potassium ions, the methods generally have the defects of expensive instruments, complex operation, time-consuming analysis and the like, and are only used in central laboratories. Therefore, the potassium ion sensor with low development cost, simple operation, high sensitivity and strong selectivity has strong practical value. In recent years, researchers have developed a series of novel potassium ion sensors based on detection mechanisms such as electrochemical methods, fluorescence methods, colorimetric methods, and Surface Enhanced Raman Scattering (SERS). In a plurality of K+In the detection method, K is based on electrochemical method and fluorescence method+Sensors are favored by more researchers because of their versatility. Although the electrochemical method generally has higher sensitivity, the electrochemical method has the problems of fine and tedious electrode preparation, poor signal stability and the like. The fluorescence method has the characteristics of high signal-to-noise ratio, less required detection sample amount, simple and easy operation and the like, and has more obvious advantages.
In constructing fluorescent sensors, there are a number of reports using crown ethers or specific DNA aptamers as the pair K+Specific recognition probe, and then combining the probe with different matrixes with fluorescence emission to construct K+A responsive fluorescence sensor. By K+Changes in interaction with crown ethers and DNA aptamers, in turn, affect the fluorescence properties of the matrix to which they are bound. Although the novel potassium ion fluorescence sensor is successfully applied to potassium ion detection in plasma, water phase or soil samples, the novel potassium ion fluorescence sensor can be used for detecting residual K in special polymers produced in industrial scale+Content tests are not reported, and mainly because the synthesis process of the special polymer is complex, residual micromolecule monomers, intermediate products or reaction solvents in products can interfere detection signals, so that the detection efficiency is influenced.
Because of the advantages of narrow emission wavelength, high quantum yield, long fluorescence life and the like of rare earth ions, a great number of rare earth ion fluorescence sensors based on organic micromolecule coordination are used forTemperature, pH, metal ions, etc. Because the luminous efficiency of the rare earth ions is not high, the rare earth ions need to be sensitized by means of the antenna effect of the organic ligand, so that the luminous performance of the rare earth ions is greatly improved, and the development of a novel organic ligand is very important. Compared with most of traditional micromolecule organic ligands with aromatic rings, the polymer has excellent physical and chemical stability, easy processing and other performances, the intrinsic fluorescent polymer rich in conjugated aromatic rings has the advantages of natural sensitized rare earth ions, and the rare earth coordination polymer prepared by coordinating the intrinsic fluorescent polymer with the rare earth ions has wide application prospect. Based on the background, a novel method which has good stability and high sensitivity and can detect residual K in the polyaryl ether nitrile powder in industrial production is sought+The fluorescence sensor of concentration has good application value.
Disclosure of Invention
The invention aims to provide a preparation method of a novel rare earth ion coordination polymer fluorescent nano probe and application of the novel rare earth ion coordination polymer fluorescent nano probe to residual K in polyarylene ether nitrile powder produced industrially, aiming at defects and potential requirements in the background art+The detection application of (1). The invention takes the block poly (arylene ether nitrile) copolymer with side chain containing carboxyl and sulfonic group as raw material, and reacts with Tb by a solvent displacement method3+And adsorbing rhodamine B dye after crosslinking to prepare the fluorescent nano probe. With Tb in the aqueous phase3+Adding into poly (arylene ether nitrile) in DMF phase, wherein poly (arylene ether nitrile) containing a large amount of carboxyl sulfonic group replaces water molecule and Tb3+Coordinate and sensitize Tb due to the presence of a large number of aromatic rings3+Thereby obtaining Tb with green emission3+Nanoparticles of a coordinated polyarylene ether nitrile. Meanwhile, due to an interpenetrating network formed by coordination, the structure has a large specific surface area and is convenient for adsorbing rhodamine B dye with red light emission. By K+Different stimulus sensitivities to the prepared fluorescent probe can construct a ratio type fluorescent nano probe to realize the K of the water phase+The method can accurately detect the residual potassium ions in the polyaryl ether nitrile powder produced industrially.
In order to achieve the purpose, the technical scheme adopted by the invention is as follows:
a novel poly (arylene ether nitrile) copolymer, wherein the poly (arylene ether nitrile) copolymer is obtained by polycondensation reaction between a hydroxy-terminated sulfonic acid-containing poly (arylene ether nitrile) oligomer and a fluoro-terminated carboxylic acid-containing poly (arylene ether nitrile) oligomer, and the structural formula is as follows:
Figure BDA0002779443670000021
wherein m is 30-60, and n is 50-90.
A novel method for preparing a poly (arylene ether nitrile) copolymer is characterized by comprising the following steps:
step 1, adding 10.3-10.6 parts (mol) of potassium 2, 5-dihydroxybenzenesulfonate, 10 parts (mol) of difluorobenzonitrile, 13-16 parts (mol) of potassium carbonate, 1.9-2.0 parts (mol) of toluene and 6.5-6.6 parts (mol) of N-methylpyrrolidone into a reaction bottle, and uniformly mixing;
step 2, stirring and refluxing the mixed solution obtained in the step 1 at the temperature of 140-150 ℃ for 2-4 h to obtain a mixed solution A;
step 3, sequentially adding 10.3-10.6 parts by mole of difluorobenzonitrile, 10 parts by mole of 4, 4-bis (4-hydroxyphenyl) pentanoic acid, 19.5-22.5 parts by mole of potassium carbonate, 1.9-2.0 parts by mole of toluene and 6.5-6.6 parts by mole of N-methylpyrrolidone into another reaction bottle, and uniformly mixing;
step 4, stirring and refluxing the mixed solution obtained in the step 3 at the temperature of 140-150 ℃ for 2-4 h to obtain a mixed solution B;
step 5, mixing the mixed solution A obtained in the step 2 with the mixed solution B obtained in the step 4, heating to 175-185 ℃ at the speed of 30 ℃/min, and stirring and refluxing for 2-4 h to obtain a polymer solution;
and 6, injecting the polymer solution obtained in the step 5 into ethanol for cooling, and purifying to obtain the novel poly (arylene ether nitrile) copolymer powder.
A method for preparing a terbium ion coordination high-molecular fluorescent nano probe based on the novel poly (arylene ether nitrile) copolymer is characterized by comprising the following steps:
step 1, sequentially adding 0.0002-0.0005 parts (mol) of the novel poly (arylene ether nitrile) copolymer powder and 0.027-0.028 parts (mol) of N, N-dimethylformamide into a reaction bottle, and fully dissolving under magnetic stirring to obtain a mixed solution C;
step 2, adding 0.001-0.002 parts (mol) of NaOH, 9.3-11.5 parts of deionized water and 0.0005-0.0006 part (mol) of Tb (NO) into another reaction bottle in sequence3)3·6H2O, obtaining a mixed solution D;
step 3, under magnetic stirring, dropwise adding the mixed solution D obtained in the step 2 into the mixed solution C obtained in the step 1, and reacting for 10-30 min;
and 4, adding 0.000005-0.000006 parts (mol) of rhodamine B into the reaction solution obtained in the step 3, centrifuging to obtain a lower-layer precipitate, and cleaning an obtained product to obtain the terbium ion coordination polymer fluorescent nano-probe.
Further, the magnetic stirring speed in the step 3 is 800-1500 rpm.
The invention also provides application of the fluorescent nano probe in detecting the concentration of residual potassium ions in the industrially produced polyarylether nitrile powder, and the specific detection process is as follows:
step 1, firstly, preparing potassium ion aqueous solutions with different concentrations; adding the fluorescent nano probe powder into deionized water to prepare a fluorescent probe reaction solution, adding the fluorescent probe reaction solution into a fluorescent cuvette, adding potassium ion aqueous solutions with the same volume (1% of the volume of the fluorescent probe reaction solution) and different concentrations into the fluorescent cuvette to detect the fluorescence intensity, and obtaining a relation curve of the potassium ion concentration and the fluorescence intensity, namely a standard curve;
step 2, placing the poly (arylene ether nitrile) powder to be tested for industrial production in a crucible, heating to 490 ℃ at the speed of 2 ℃/min in the air atmosphere, and keeping the temperature for 2h to obtain a sintered product; adding the sintered product into deionized water, soaking for 12h, and centrifuging to obtain supernatant;
step 3, putting the fluorescent probe reaction solution with the same volume as that in the step 1 into a fluorescent cuvette, adding the supernatant obtained in the step 2 with the same volume (1% of the volume of the fluorescent probe reaction solution) as that of the potassium ion aqueous solution in the step 1, and detecting the fluorescence intensity; and (3) according to the fluorescence intensity of the sample to be detected obtained by detection, obtaining the concentration of potassium ions in the sample to be detected through the relation curve of the concentration of potassium ions in the standard curve obtained in the step (1) and the fluorescence intensity.
The fluorescent nano probe with green light and red light emission provided by the invention uses a block poly (arylene ether nitrile) copolymer with side chains containing carboxyl and sulfonic group as a raw material, and is subjected to solvent displacement method and Tb3+And adsorbing rhodamine B dye after crosslinking. With Tb in the aqueous phase3+Adding the polyarylether nitrile into the polyarylether nitrile in the DMF phase, wherein the polyarylether nitrile replaces water and Tb3+Coordinate and sensitize Tb due to the presence of a large number of aromatic rings3+Thereby obtaining Tb with green emission3+Nanostructures of coordinated polyarylene ether nitriles. Meanwhile, due to an interpenetrating network formed by coordination, the structure has a large specific surface area and is convenient for adsorbing rhodamine B dye. The fluorescence emission intensity of the sample also shows different concentrations of K in the aqueous phase+So that it can be used as a new type of detection K+The fluorescent nanoprobe of (1).
The invention has the beneficial effects that:
1. according to the invention, the sulfonic acid-containing hydrophilic poly (arylene ether nitrile) oligomer and the carboxylic acid-containing hydrophilic poly (arylene ether nitrile) oligomer are subjected to polycondensation reaction to obtain the novel hydrophilic poly (arylene ether nitrile) block copolymer with coordination capacity, on one hand, the abundant coordination functional groups of the novel hydrophilic poly (arylene ether nitrile) block copolymer endow the possibility of crosslinking with rare earth ions, and on the other hand, the existence of a large amount of aromatic rings provides the capacity of sensitizing the rare earth ions. The novel poly (arylene ether nitrile) has simple synthesis method, is easy for mass production, is expected to realize industrialization, and is a novel rare earth ion macromolecular organic ligand.
2. The invention utilizes the novel poly (arylene ether nitrile) to react with rare earth Tb by a simple solvent replacement method3+The coordination preparation obtains the rare earth ion crosslinking polymer nanostructure with green light emission, and the method has simple steps, easy operation and easy mass production.
3. The prepared rare earth ion crosslinked poly (arylene ether nitrile) nano structure emitted by green light has larger specific surface area, is easy to adsorb rhodamine B dye emitted by red light, can construct a ratio type fluorescent nano probe, and reduces test errors.
4. Tb prepared by the invention3+The ratio-type fluorescence nano probe of the crosslinked poly (arylene ether nitrile) has obvious fluorescence enhancement positive response to potassium ions, and the fluorescence changes from yellow to green along with the increase of the concentration of the potassium ions, so that the ratio-type fluorescence nano probe has the characteristic of visualization. The fluorescence linear detection range is 0.05 mM-7.41 mM, meets the detection requirement on the content of the residual potassium carbonate in the special engineering plastic, and has wide application prospect.
Drawings
FIG. 1 is an infrared spectrum (a) and a hydrogen nuclear magnetic resonance spectrum (b) of the polyarylene ether nitrile block copolymer obtained in example 1;
FIG. 2 shows Tb provided in embodiment 2 of the present invention3+Fluorescence emission spectrum (a) corresponding to the coordinated poly (arylene ether nitrile) nanostructure and SEM picture (b) of the surface;
FIG. 3 shows Tb provided in embodiment 3 of the present invention3+K of coordinated polyarylene ether nitriles+A fluorescence emission spectrum (a) and a surface SEM photograph (b) corresponding to the ratiometric fluorescent probe;
FIG. 4 shows Tb provided in example 4 of the present invention3+K of coordinated polyarylene ether nitriles+Ratiometric fluorescent probes at the same concentration (7.5X 10)-5mol/L) change value of 545nm fluorescence intensity under the action of different kinds of metal ions;
FIG. 5 shows fluorescence emission spectra (a) of a standard aqueous solution of potassium ions, and fluorescence intensity ratios at 545nm and 585nm, respectively, according to example 5 of the present invention
Figure BDA0002779443670000051
A fitted relation curve (b) with potassium ion concentration;
FIG. 6 shows K provided in example 3 after pretreatment of the blank, purified sample, and unpurified plant sample provided in example 6+Fluorescence emission spectra of ratiometric fluorescent probe tests;
Detailed Description
The present invention is further described by the following description of the specific embodiments, but the present invention is not limited thereto, and those skilled in the art can make various modifications based on the basic idea of the present invention within the scope of the present invention without departing from the basic idea of the present invention.
Example 1
A preparation method of a novel poly (arylene ether nitrile) copolymer specifically comprises the following steps:
step 1, sequentially adding 50 mmol of potassium 2, 5-dihydroxybenzenesulfonate, 47.5 mmol of difluorobenzonitrile, 75 mmol of potassium carbonate, 10ml of toluene and 30 ml of N-methylpyrrolidone into a reaction bottle, and uniformly mixing;
step 2, stirring and refluxing the mixed solution obtained in the step 1 at 150 ℃ for 3 hours to obtain a mixed solution A;
step 3, adding 50 mmol of difluorobenzonitrile, 47.5 mmol of 4, 4-bis (4-hydroxyphenyl) pentanoic acid, 106.9 mmol of potassium carbonate, 10ml of toluene and 30 ml of N-methylpyrrolidone into another reaction bottle in sequence, and mixing uniformly;
step 4, stirring and refluxing the mixed solution obtained in the step 3 at 150 ℃ for 3 hours to obtain a mixed solution B;
step 5, mixing the mixed solution A obtained in the step 2 with the mixed solution B obtained in the step 4, heating to 180 ℃ at the speed of 30 ℃/min, and stirring and refluxing for 3 hours;
and 6, injecting the polymer solution obtained in the step 5 into ethanol for cooling, and purifying to obtain the novel poly (arylene ether nitrile) copolymer powder.
The polyarylene ether nitrile block copolymer synthesized in example 1 was characterized by infrared (FITR) and nuclear magnetic resonance hydrogen spectroscopy (1H-NMR), and the results are shown in FIGS. 1(a) and 1 (b). As shown in FIG. 1(a), the polyarylene ether nitrile was found to be present at 2231cm-1Is located at 1714cm and is a cyano vibration peak-1Is a carboxyl vibration peak of 1084cm-1The peak is a sulfonic acid group vibration peak. As is clear from FIG. 1(b), the corresponding peaks of carboxyl group and hydroxyl group hydrogen on the polyarylene ether nitrile were detected at 10.41ppm, indicating that this example succeeded in producing a polyarylene ether nitrile containing a carboxyl group and a sulfonic acid group.
Example 2
Tb3+The preparation method of the coordination poly (arylene ether nitrile) nano structure specifically comprises the following steps:
step 1, adding 10mg of the novel poly (arylene ether nitrile) copolymer obtained in example 1 and 1mL of N, N-dimethylformamide into a reaction bottle in sequence, and fully dissolving the poly (arylene ether nitrile) copolymer and the N, N-dimethylformamide under magnetic stirring to obtain a mixed solution C;
step 2, adding 50 mu L of NaOH aqueous solution with the concentration of 1mol/L, 8.86mL of deionized water and 90 mu L of Tb (NO) with the concentration of 0.5mol/L into another reaction bottle in sequence3)3·6H2O, obtaining a mixed solution D;
and 3, dropwise adding the mixed solution D obtained in the step 2 into the mixed solution C obtained in the step 1 under the magnetic stirring at the rotating speed of 1500rpm, and reacting for 10min to obtain Tb3+Coordinating poly (arylene ether nitrile) nanostructures;
setting the wavelength of emitted light to 545nm, the width of a slit to 10nm, the voltage of a PMT to 700V, the response time to 0.1s, and obtaining Tb by wavelength scanning3+Excitation spectrum of the coordinated poly (arylene ether nitrile) nanostructure; the wavelength of the excitation light is set to 332nm, the width of the slit is set to 10nm, the voltage of the PMT is set to 700V, the response time is set to 0.1s, and the fluorescence emission spectrum under the excitation of 332nm is obtained through wavelength scanning.
As shown in fig. 2, Tb provided for embodiment 2 of the present invention3+Fluorescence emission spectra (a) and SEM (b) corresponding to the coordinated poly (arylene ether nitrile) nanostructure; from the spectrum (a), Tb after ligand substitution can be seen3+Tb was present at 490nm, 545nm and 586nm under excitation at an excitation wavelength of 332nm3+Wherein the characteristic peak at 545nm is strongest, which indicates that the polyarylether nitrile containing abundant benzene rings can successfully sensitize Tb by' antenna effect3+Thus showing Tb3+The coordination poly (arylene ether nitrile) nano structure can emit green light under the excitation of the wavelength of 332 nm. From the graph (b), it can be seen that the morphology is aggregated nanosized spherical particles.
Example 3
Tb3+K of coordinated polyarylene ether nitriles+The preparation method of the ratio type fluorescent probe specifically comprises the following steps:
to implementAdding 200 mu L of rhodamine B solution with the concentration of 60mg/L into the reaction solution obtained in the step 3 in the example 2, centrifuging, washing the obtained product for 3 times by using deionized water to obtain a lower-layer precipitate, and adding the lower-layer precipitate into 30 ml of deionized water to obtain the Tb3+K of coordinated polyarylene ether nitriles+Reaction solution for ratiometric fluorescent probe.
Setting the wavelength of emitted light to 545nm, the width of a slit to 10nm, the voltage of a PMT to 700V, the response time to 0.1s, and obtaining Tb by wavelength scanning3+K of coordinated polyarylene ether nitriles+Excitation spectra of ratiometric fluorescent probes; the wavelength of the excitation light is set to 332nm, the width of the slit is set to 10nm, the voltage of the PMT is set to 700V, the response time is set to 0.1s, and the fluorescence emission spectrum under the excitation of 332nm is obtained through wavelength scanning.
As shown in fig. 3, Tb provided for embodiment 3 of the present invention3+K of coordinated polyarylene ether nitriles+Fluorescence emission spectra (a) and sem (b) for ratiometric fluorescent probes; tb after adsorbing rhodamine B can be seen from the spectrum3+Coordinated polyarylene ether nitrile metal complexes (i.e., Tb)3+K of coordinated polyarylene ether nitriles+Ratiometric fluorescent probe) is excited by excitation wavelength of 332nm to adsorb Tb of rhodamine B less3+The emission characteristic peak of the coordination poly (arylene ether nitrile) metal complex at 585nm is obviously enhanced, which shows that Tb3+The coordination poly (arylene ether nitrile) metal complex successfully adsorbs rhodamine B, emits 545nm and 585nm yellow light under the excitation of 332nm wavelength, and can be used as a ratio type fluorescent probe. It can be seen from the graph (B) that after rhodamine B is introduced, the morphology is similar to Tb in example 23+The nano structure of the coordination poly (arylene ether nitrile) is not greatly changed.
Example 4
Tb3+K of coordinated polyarylene ether nitriles+The specific evaluation of the ratio-type fluorescent nano probe on different metal ions specifically comprises the following steps:
step 1, preparing the same concentration (7.5 multiplied by 10) in different reaction bottles respectively-5mol/L) of lead nitrate, nickel chloride, chlorinated polyethylene, aluminum chloride, calcium chloride, barium chloride, potassium chloride, lithium chloride, magnesium sulfate and sodium chloride aqueous solution;
step 2, taking 2.0mL of the fluorescent probe reaction solution obtained in the embodiment 3, adding 0.02mL of different metal ion aqueous solutions with the same concentration to be detected into a fluorescent cuvette; setting the wavelength of emitted light to 545nm, the width of a slit to 10nm, the voltage of a PMT to 700V, the response time to 0.1s, and obtaining Tb by wavelength scanning3+K of coordinated polyarylene ether nitriles+Excitation spectra of ratiometric fluorescent probes; the wavelength of the excitation light is set to 332nm, the width of the slit is set to 10nm, the voltage of the PMT is set to 700V, the response time is set to 0.1s, and the fluorescence emission spectrum under the excitation of 332nm is obtained through wavelength scanning.
And 3, calculating the change of the intensity of a fluorescence emission peak at 545nm of the nano probe reaction solution under the action of different metal ions relative to a blank sample (the nano probe reaction solution without any metal ions) according to the fluorescence emission spectrum obtained by the test in the step 2 to obtain a response mode of the fluorescent nano probe to different metal ions, wherein potassium ions can specifically enhance the fluorescence intensity of the nano probe reaction solution at 545nm as shown in fig. 4.
Example 5
Tb3+K of coordinated polyarylene ether nitriles+The determination of the linear test range of the ratio type fluorescent nano probe specifically comprises the following steps:
step 1, preparing potassium carbonate aqueous solutions with the concentrations of 10.00mM, 8.33mM, 7.41mM, 6.67 mM, 5.88mM, 5.00mM, 3.33mM, 2.50mM, 1.66mM, 1.00mM, 0.50mM and 0.05mM in different reaction bottles;
step 2, taking 2.0mL of the fluorescent probe reaction solution obtained in the embodiment 3, adding 0.02mL of the standard potassium ion aqueous solution with different concentrations into a fluorescent cuvette to be detected; obtaining a relation graph of potassium ion concentration and fluorescence intensity of the fluorescent probe;
setting the wavelength of emitted light to 545nm, the width of a slit to 10nm, the voltage of a PMT to 700V, the response time to 0.1s, and obtaining Tb by wavelength scanning3+K of coordinated polyarylene ether nitriles+Excitation spectra of ratiometric fluorescent probes; the wavelength of the excitation light is set to 332nm, the width of the slit is set to 10nm, the voltage of the PMT is set to 700V, the response time is set to 0.1s, and the fluorescence emission spectrum under the excitation of 332nm is obtained through wavelength scanning.
Example 6
Tb3+K of crosslinked polyarylene ether nitriles+The ratiometric fluorescent probe is used for detecting the residual quantity of potassium ions in the industrial production of poly (arylene ether nitrile) (factory samples), and specifically comprises the following steps:
step 1, 50g of factory sample (polyaryl ether nitrile powder produced in industry) is dissolved in 500ml of N-methyl pyrrolidone, precipitated in deionized water, and washed with deionized water for 10 times after being crushed to obtain a purified sample. Respectively weighing 5g of factory sample and the purified sample in two crucibles, heating to 490 ℃ at the speed of 2 ℃/min under the air atmosphere, and keeping the temperature for 2h to obtain a sintered product. Adding 10ml of deionized water into the product, soaking for 12 hours, and centrifuging to obtain a factory sample and a purified sample supernatant for later use;
step 2, taking 2.0mL of the fluorescent probe reaction solution obtained in the embodiment 3, adding 0.02mL of deionized water, 0.02mL of the plant sample supernatant obtained in the step 1 and 0.02mL of the purified sample supernatant obtained in the step 1 into a fluorescent cuvette to be detected, and respectively obtaining fluorescent spectrums corresponding to a blank sample, a plant sample and a purified sample; the potassium ion concentrations in different samples can be obtained by the graph of the relationship between the potassium ion concentration and the fluorescence intensity of the fluorescent probe obtained in example 5.
Setting the wavelength of emitted light to 545nm, the width of a slit to 10nm, the voltage of a PMT to 700V, the response time to 0.1s, and obtaining Tb by wavelength scanning3+K of coordinated polyarylene ether nitriles+Excitation spectra of ratiometric fluorescent probes; the wavelength of the excitation light is set to 332nm, the width of the slit is set to 10nm, the voltage of the PMT is set to 700V, the response time is set to 0.1s, and the fluorescence emission spectrum under the excitation of 332nm is obtained through wavelength scanning.
As shown in FIG. 5, the fluorescence emission spectrum (a) corresponding to the standard aqueous potassium ion solution provided in example 5 of the present invention and the fluorescence intensity ratio at the wavelength of 545nm to 585nm were obtained
Figure BDA0002779443670000091
And (b) a curve fitted with the potassium ion concentration. It can be seen from the spectrum of FIG. 5(a) that as the concentration of potassium ions increases, the fluorescence of the fluorescent probe increases and then remains substantially unchanged,and the fluorescence amplification at 545nm is obviously higher than that at 585nm, namely the change of the fluorescence of the sensor from yellow light to green light occurs. It can be seen from FIG. 5(b) that as the concentration of potassium ions gradually increases, the fluorescence intensities at the wavelengths of 545nm and 585nm gradually increase and then remain substantially unchanged, and the ratio of the concentration of potassium ions in the range of 0.05mM to 7.41mM to the fluorescence intensities at 545nm and 585nm
Figure BDA0002779443670000092
Has good linear correlation degree, and the linear correlation coefficient is as high as 0.9911. FIG. 6 shows K provided in example 3 after pretreatment of blanks, purified samples and unpurified plant samples provided in example 6+Fluorescence emission spectra of ratiometric fluorescent probe tests; as shown in fig. 6, the fluorescence of the purified plant sample is substantially identical to that of the blank sample, which indicates that the response of the fluorescent nanoprobe to potassium ions is not affected by the sample pretreatment method, and the fluorescence of the unpurified plant sample is significantly enhanced. According to FIG. 5(b), fluorescence intensity ratio at 545nm to 585nm wavelength
Figure BDA0002779443670000093
The potassium ion concentration in the unpurified plant sample was 125.23mmol/L as calculated from a curve fitted to the potassium ion concentration, and the residual potassium ion content in the unpurified plant sample was 9767ppm as calculated.

Claims (5)

1. The poly (arylene ether nitrile) copolymer is characterized by being obtained by polycondensation reaction between hydroxyl-terminated sulfonic acid-containing poly (arylene ether nitrile) oligomer and fluorine-terminated carboxylic acid-containing poly (arylene ether nitrile) oligomer, and the structural formula of the poly (arylene ether nitrile) copolymer is as follows:
Figure FDA0003207178930000011
wherein m is 30-60, and n is 50-90.
2. A method for preparing a poly (arylene ether nitrile) copolymer, which is characterized by comprising the following steps:
step 1, adding 10.3-10.6 molar parts of potassium 2, 5-dihydroxybenzenesulfonate, 10 molar parts of difluorobenzonitrile, 13-16 molar parts of potassium carbonate, 1.9-2.0 molar parts of toluene and 6.5-6.6 molar parts of N-methylpyrrolidone into a reaction bottle, and uniformly mixing;
step 2, stirring and refluxing the mixed solution obtained in the step 1 at the temperature of 140-150 ℃ for 2-4 h to obtain a mixed solution A;
step 3, sequentially adding 10.3-10.6 molar parts of difluorobenzonitrile, 10 molar parts of 4, 4-bis (4-hydroxyphenyl) pentanoic acid, 19.5-22.5 molar parts of potassium carbonate, 1.9-2.0 molar parts of toluene and 6.5-6.6 molar parts of N-methylpyrrolidone into another reaction bottle, and uniformly mixing;
step 4, stirring and refluxing the mixed solution obtained in the step 3 at the temperature of 140-150 ℃ for 2-4 h to obtain a mixed solution B;
step 5, mixing the mixed solution A obtained in the step 2 with the mixed solution B obtained in the step 4, heating to 175-185 ℃, stirring and refluxing for 2-4 hours to obtain a polymer solution;
and 6, injecting the polymer solution obtained in the step 5 into ethanol for cooling, and purifying to obtain the poly (arylene ether nitrile) copolymer powder.
3. A method for preparing terbium ion coordination polymer fluorescent nanoprobe by the polyaryl ether nitrile copolymer prepared by the method of claim 2 is characterized by comprising the following steps:
step 1, adding 0.0002 to 0.0005 molar parts of the polyaryl ether nitrile copolymer powder obtained in the claim 2 and 0.027 to 0.028 molar parts of N, N-dimethylformamide into a reaction bottle in sequence, and fully dissolving under magnetic stirring to obtain a mixed solution C;
step 2, adding 0.001-0.002 molar parts of NaOH, 9.3-11.5 molar parts of deionized water and 0.0005-0.0006 molar part of Tb (NO) into another reaction bottle in sequence3)3·6H2O, obtaining a mixed solution D;
step 3, under magnetic stirring, dropwise adding the mixed solution D obtained in the step 2 into the mixed solution C obtained in the step 1, and reacting for 10-30 min;
and 4, adding 0.000005-0.000006 mol part of rhodamine B into the reaction solution obtained in the step 3, centrifuging to obtain a lower-layer precipitate, and cleaning the obtained product to obtain the terbium ion coordination polymer fluorescent nano probe.
4. The use of the terbium ion-coordinated polymeric fluorescent nanoprobe prepared by the method of claim 3 in detecting the concentration of residual potassium ions in the polyaryl ether nitrile powder produced industrially.
5. A method for detecting the concentration of residual potassium ions in industrially produced polyarylether nitrile powder is characterized by comprising the following steps:
step 1, firstly, preparing potassium ion aqueous solutions with different concentrations; adding the fluorescent nano probe powder obtained in the claim 3 into deionized water to prepare a fluorescent probe reaction solution, adding the fluorescent probe reaction solution into a fluorescent cuvette, and adding potassium ion aqueous solutions with the same volume and different concentrations into the fluorescent cuvette to detect the fluorescence intensity to obtain a relation curve of the potassium ion concentration and the fluorescence intensity;
step 2, placing the poly (arylene ether nitrile) powder to be measured for industrial production in a crucible, heating to 490 ℃ in air atmosphere, and keeping the temperature for 2 hours to obtain a sintered product; adding the sintered product into deionized water, soaking for 12h, and centrifuging to obtain supernatant;
step 3, taking the fluorescent probe reaction liquid with the same volume as that in the step 1 into a fluorescent cuvette, adding the supernatant obtained in the step 2 with the same volume as that of the potassium ion aqueous solution in the step 1, and detecting the fluorescence intensity; and (3) according to the fluorescence intensity of the sample to be detected obtained by detection, obtaining the concentration of potassium ions in the sample to be detected through the relation curve of the concentration of potassium ions and the fluorescence intensity in the step (1).
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