CN111423563B - For detecting Fe3+Fused heterocyclic conjugated polymer and preparation method and application thereof - Google Patents
For detecting Fe3+Fused heterocyclic conjugated polymer and preparation method and application thereof Download PDFInfo
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- CN111423563B CN111423563B CN202010446544.6A CN202010446544A CN111423563B CN 111423563 B CN111423563 B CN 111423563B CN 202010446544 A CN202010446544 A CN 202010446544A CN 111423563 B CN111423563 B CN 111423563B
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- fused heterocyclic
- conjugated polymer
- heterocyclic conjugated
- polymer
- monomer
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- 229920000547 conjugated polymer Polymers 0.000 title claims abstract description 38
- 125000000623 heterocyclic group Chemical group 0.000 title claims abstract description 38
- 238000002360 preparation method Methods 0.000 title abstract description 11
- 229920000642 polymer Polymers 0.000 claims abstract description 31
- 238000000034 method Methods 0.000 claims abstract description 13
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims abstract description 9
- 238000006243 chemical reaction Methods 0.000 claims abstract description 8
- -1 carbomethoxy Chemical group 0.000 claims abstract description 3
- 125000003754 ethoxycarbonyl group Chemical group C(=O)(OCC)* 0.000 claims abstract description 3
- 125000005059 halophenyl group Chemical class 0.000 claims abstract description 3
- 239000000178 monomer Substances 0.000 claims description 14
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 7
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 7
- 239000003513 alkali Substances 0.000 claims description 5
- 229910021595 Copper(I) iodide Inorganic materials 0.000 claims description 4
- 125000003172 aldehyde group Chemical group 0.000 claims description 4
- 150000001345 alkine derivatives Chemical class 0.000 claims description 4
- 150000001879 copper Chemical class 0.000 claims description 4
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 4
- LSXDOTMGLUJQCM-UHFFFAOYSA-M copper(i) iodide Chemical compound I[Cu] LSXDOTMGLUJQCM-UHFFFAOYSA-M 0.000 claims description 3
- 229910021589 Copper(I) bromide Inorganic materials 0.000 claims description 2
- 229910021591 Copper(I) chloride Inorganic materials 0.000 claims description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 2
- 125000003545 alkoxy group Chemical group 0.000 claims description 2
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- OXBLHERUFWYNTN-UHFFFAOYSA-M copper(I) chloride Chemical compound [Cu]Cl OXBLHERUFWYNTN-UHFFFAOYSA-M 0.000 claims description 2
- NKNDPYCGAZPOFS-UHFFFAOYSA-M copper(i) bromide Chemical compound Br[Cu] NKNDPYCGAZPOFS-UHFFFAOYSA-M 0.000 claims description 2
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- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 abstract description 16
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- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 abstract description 8
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- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 27
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 12
- 230000008859 change Effects 0.000 description 9
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- OTMRXENQDSQACG-UHFFFAOYSA-N thiophene-2,5-dicarbaldehyde Chemical compound O=CC1=CC=C(C=O)S1 OTMRXENQDSQACG-UHFFFAOYSA-N 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- FCEHBMOGCRZNNI-UHFFFAOYSA-N 1-benzothiophene Chemical compound C1=CC=C2SC=CC2=C1 FCEHBMOGCRZNNI-UHFFFAOYSA-N 0.000 description 2
- NFPDFDTYANKKIU-UHFFFAOYSA-N 1-ethynyl-4-hexylbenzene Chemical compound CCCCCCC1=CC=C(C#C)C=C1 NFPDFDTYANKKIU-UHFFFAOYSA-N 0.000 description 2
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
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- FNQJDLTXOVEEFB-UHFFFAOYSA-N 1,2,3-benzothiadiazole Chemical compound C1=CC=C2SN=NC2=C1 FNQJDLTXOVEEFB-UHFFFAOYSA-N 0.000 description 1
- DHXBYSVTYFPDMW-UHFFFAOYSA-N 1-benzyl-9h-carbazole Chemical compound C=1C=CC(C2=CC=CC=C2N2)=C2C=1CC1=CC=CC=C1 DHXBYSVTYFPDMW-UHFFFAOYSA-N 0.000 description 1
- UMZCLZPXPCNKML-UHFFFAOYSA-N 2h-imidazo[4,5-d][1,3]thiazole Chemical group C1=NC2=NCSC2=N1 UMZCLZPXPCNKML-UHFFFAOYSA-N 0.000 description 1
- XFOFHELUDYDYMX-UHFFFAOYSA-N 3-imino-4h-chromen-2-one Chemical compound C1=CC=C2OC(=O)C(=N)CC2=C1 XFOFHELUDYDYMX-UHFFFAOYSA-N 0.000 description 1
- VCMLCMCXCRBSQO-UHFFFAOYSA-N 3h-benzo[f]chromene Chemical compound C1=CC=CC2=C(C=CCO3)C3=CC=C21 VCMLCMCXCRBSQO-UHFFFAOYSA-N 0.000 description 1
- 239000005964 Acibenzolar-S-methyl Substances 0.000 description 1
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- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 1
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- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 238000000559 atomic spectroscopy Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- RFRXIWQYSOIBDI-UHFFFAOYSA-N benzarone Chemical compound CCC=1OC2=CC=CC=C2C=1C(=O)C1=CC=C(O)C=C1 RFRXIWQYSOIBDI-UHFFFAOYSA-N 0.000 description 1
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- UFBBWLWUIISIPW-UHFFFAOYSA-N imidazo[2,1-b][1,3]thiazole Chemical class C1=CSC2=NC=CN21 UFBBWLWUIISIPW-UHFFFAOYSA-N 0.000 description 1
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- QPCKXALBLLVOLL-UHFFFAOYSA-N penta-1,4-diynylbenzene Chemical group C#CCC#CC1=CC=CC=C1 QPCKXALBLLVOLL-UHFFFAOYSA-N 0.000 description 1
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Abstract
The invention discloses a method for detecting Fe3+The fused heterocyclic conjugated polymer, the preparation method and the application thereof, and the preparation method and the application of the polymerThe structural unit is
R1Represents
Or
R2Represents phenyl, C1～C8Alkyl-substituted phenyl, halophenyl, C1～C3Alkoxy substituted phenyl, carbomethoxy or carbethoxy. The polymer is synthesized by utilizing A3-grafting reaction, and has the advantages of multi-component reaction, such as good atom utilization rate, product diversity and the like. Fe3+Ion pair synthesized main chain imidazo [2,1-b]The fluorescence of tetrahydrofuran solution of the fused heterocyclic conjugated polymer with a thiazole structure has obvious quenching effect and can be used for Fe in an organic phase3+Detection of ions, and of Fe3+High ion selectivity and low detection limit.
Description
Technical Field
The invention belongs to the technical field of high molecular polymers, and particularly relates to a novel fused heterocyclic conjugated polymer, specifically to a conjugated polymer with a main chain containing imidazo [2,1-b ]]Thiazole fused heterocycle conjugated polymer, preparation method of polymer and Fe detection method3+The use of (1).
Background
The fused heterocyclic conjugated polymer is a novel advanced functional polymer material, and attracts the wide attention of scientists due to the excellent photoelectric activity of the fused heterocyclic conjugated polymer. In the past decades, a series of fused heterocyclic polymers have been developed and studied, such as polymers containing benzodipyrrole, benzofuran, benzothiophene, benzothiadiazole, benzylcarbazole and naphthopyran, poly- (iminocoumarin) and the like. The unique conjugated condensed heterocyclic structure in the polymers endows the polymers with excellent electron transmission performance, so that the polymers can be widely applied to the fields of polymer light-emitting diodes, organic photovoltaic cells, organic field effect transistors, optical sensors and the like.
Of the many fused heterocyclic structures, imidazo [2,1-b ] thiazoles have attracted our attention for their wide range of applications. Imidazole [2,1-b ] thiazole is a nitrogen-containing condensed heterocyclic compound, exists in a plurality of natural products and drug molecules, and has remarkable physiological and pharmacological activities, such as anticancer, antibacterial, antianxiety and the like. In addition, the compounds are also widely applied to the technical fields of dyes, multifunctional materials, fluorescent probes and the like. However, to date, the successful preparation of polymers containing imidazothiazole groups has not been reported.
In recent years, due to the important role of transition metal ions in living bodies and their influence on the environment, their detection techniques have been the focus of attention. Among them, iron (Fe) is a trace metal element essential to the human body, and is involved in various biological processes of cells and tissues, and plays an important role particularly in processes of hemoglobin synthesis, redox reaction, energy metabolism, and the like. Iron deficiency most commonly causes iron deficiency anemia, resulting in impaired heme synthesis, which in turn results in decreased hemoglobin content in red blood cells and decreased oxygen carrying capacity of red blood cells. After the iron is excessive, it may cause the deposition of iron in various organs of the whole body, such as liver, heart, brain, etc., thereby causing the dysfunction of various systems. There are also a number of studies that indicate that parkinson and alzheimer's disease are closely related to iron. Secondly, the Fe content is an important index for detecting the drinking water. According to the regulations of the world health organization, the Fe content in domestic application water is less than 5.4 mu mol/L, so how to rapidly, simply, sensitively and selectively detect Fe3+Is one of the important subjects of human research. At present, there are many methods for detecting metal ions, such as electrochemical analysis, atomic spectrometry, ion mass spectrometry, and the like. However, these conventional detection methods have the limitations of poor stability, complex operation, expensive instruments and equipment, etc., and the sample preparation process is also quite complicated.
Disclosure of Invention
The invention aims to provide a method for detecting Fe3+Fused heterocyclic conjugated polymer with simple operation, short response time, higher stability and selectivity and preparation of polymerA method and an application.
In view of the above object, the structural units of the fused heterocyclic conjugated polymer used in the present invention are as follows:
in the formula R1Represents
Any one of them, R2Represented by phenyl, C1～C8Alkyl-substituted phenyl, halophenyl, C1～C3The alkoxy is substituted for any one of phenyl, carbomethoxy and carbethoxy.
The preparation method of the fused heterocyclic conjugated polymer comprises the following steps: adding a bisazine monomer shown as a formula I, a monomer shown as a formula II and containing two aldehyde groups, an alkyne monomer shown as a formula III, copper salt and alkali into dimethyl sulfoxide, carrying out polymerization reaction under the protection of inert gas and stirring at 70-90 ℃, and extracting, drying and dialyzing after the reaction is finished to obtain a fused heterocyclic conjugated polymer;
in the formula III, R3Represents hydrogen or carboxyl.
In the preparation method, the copper salt is any one of cuprous chloride, cuprous iodide and cuprous bromide; the alkali is any one of anhydrous potassium carbonate and anhydrous sodium carbonate.
In the preparation method, the molar ratio of the bisazine monomer to the monomer containing two aldehyde groups to the alkyne monomer is preferably 1: 1.0-3.0: 2.0-5.0, and the molar ratio of the bisazine monomer to the cuprous iodide and the anhydrous potassium carbonate is preferably 1: 0.02-0.5: 2.0-5.0.
The invention relates to a fused heterocyclic ringDetection of Fe by yoke Polymer3+The specific detection method comprises the following steps: dissolving the conjugated polymer in tetrahydrofuran or water to obtain 1.0 × 10-6A mol/L polymer solution; then adding Fe of different concentrations thereto3+Standard sample, detecting the fluorescence intensity of the system, and drawing Fe with different concentrations3+Maximum fluorescence intensity of the corresponding system with Fe3+A standard curve of concentration change; then testing and adding Fe to be tested3+The fluorescence intensity of the system in the sample solution can be determined according to the fluorescence intensity and the standard curve equation3+The content of (a).
The invention has the following beneficial effects:
1. the invention utilizes A3-Coupling reaction to synthesize a fused heterocyclic conjugated polymer, and the method is similar to the traditional method: compared with Suzuki cross-coupling reaction, Still reaction, Kumada reaction, Sonogashira reaction and the like, the synthesis method disclosed by the invention has the advantages of commercialized raw materials, simplicity in operation and no need of multi-step reaction and intermediate purification.
2、Fe3+The ion has obvious quenching effect on the fluorescence of tetrahydrofuran solution of the fused heterocyclic conjugated polymer synthesized by the invention, and can be used for Fe in an organic phase3+The detection of ions is simple to operate, has short response time and can be used for detecting Fe3+High ion selectivity and low detection limit.
Drawings
FIG. 1 shows the fluorescence intensity of polymer P1 as a function of Fe3+Fluorescence spectrum of concentration change.
FIG. 2 is the relative fluorescence intensity of Polymer P1 as a function of Fe3+Linear dependence of concentration change.
FIG. 3 shows the fluorescence intensity of Polymer P2 as a function of Fe3+Fluorescence spectrum of concentration change.
FIG. 4 is a graph of the relative fluorescence intensity of Polymer P2 as a function of Fe3+Linear dependence of concentration change.
FIG. 5 shows the fluorescence intensity of Polymer P3 as a function of Fe3+Fluorescence spectrum of concentration change.
FIG. 6 is the relative fluorescence intensity of Polymer P3 as a function of Fe3+Concentration ofA graph of the linear relationship of the changes.
FIG. 7 shows the fluorescence intensity of polymer P5 as a function of Fe3+Fluorescence spectrum of concentration change.
FIG. 8 is the relative fluorescence intensity of Polymer P5 as a function of Fe3+Linear dependence of concentration change.
FIG. 9 is a graph comparing the relative fluorescence intensity of the polymer P1 in different cationic systems.
FIG. 10 is a graph comparing the relative fluorescence intensity of the polymer P2 in different cationic systems.
FIG. 11 is a graph comparing the relative fluorescence intensity of the polymer P3 in different cationic systems.
FIG. 12 is a graph comparing the relative fluorescence intensity of polymer P5 in different cationic systems.
Detailed Description
The invention will be further described in detail with reference to the following figures and examples, but the scope of the invention is not limited to these examples.
Example 1
0.2g (6.71X 10)-4mol)2,2 '-diamino-6, 6' -bibenzobisthiazole, 0.099g (7.381X 10)- 4mol)1, 4-terephthalaldehyde, 0.0256g (1.34X 10)-4mol)CuI、0.206g(1.41×10-3mol) anhydrous K2CO3Adding into a dry three-neck flask, vacuumizing and filling argon, and circulating for three times. 0.263g (1.41X 10)-3mol) 1-ethynyl-4-hexylbenzene was dissolved in 6.7mL of anhydrous DMSO, and the resulting solution was added to the above three-necked flask by syringe, heated to 80 ℃ and stirred for 72 hours. After completion of the reaction, the reaction mixture was cooled to room temperature, 100mL of methylene chloride was added to the reaction mixture, and then the mixture was washed with 50mL of saturated saline and 50mL of saturated aqueous ammonium chloride solution for 3 times, and the organic layer was dried over anhydrous magnesium sulfate overnight and distilled under reduced pressure to obtain a crude product. The crude product obtained is dissolved in tetrahydrofuran and dialyzed for 2 days, finally at 54.3% strengthThe yield of the obtained fused heterocyclic conjugated polymer P1 is yellow brown powder, and the structural characterization result is as follows:
1H NMR(400MHz,CDCl3)δ(ppm)8.10-7.25(22H,ArH),4.29(s,4H,CH2), 2.69-2.65(m,8H,CH2),1.58-1.55(m,8H,CH2),1.32-1.24(m,8H,CH2),0.96-0.87(t,6H, CH3)；FT-IR(KBr)3031,2923,2852,2729,1604,1465,1207,1122,1014,817。
the polymer had Mn of 5.7X 10 as determined by gel permeation chromatography4，Mw＝9.1×104，Mw/Mn＝1.59。
Example 2
In this example, 1, 4-terephthalaldehyde in example 1 was replaced with equimolar 2, 5-thiophenedicarboxaldehyde, and the other steps were the same as in example 1, to finally obtain a tan solid fused heterocyclic conjugated polymer P2 in 58.9% yield, which was characterized by the following structure:
1H NMR(400MHz,CDCl3)δ(ppm)8.03-7.06(18H,ArH),4.62(s,4H,CH2), 2.63-2.55(m,8H,CH2),1.55-1.51(m,8H,CH2),1.23-1.19(m,8H,CH2),0.81-0.77(t,6H, CH3)；FT-IR(KBr)2930,2862,2725,1701,1606,1465,1261,1099,1018,833。
the polymer had Mn of 6.8X 10 as determined by gel permeation chromatography4，Mw＝12.4×104，Mw/Mn＝1.81。
Example 3
In this example, 1-ethynyl-4-hexylbenzene in example 1 was replaced with equimolar ethyl propiolate, and after the reaction was completed, the reaction solution was poured into 100mL of cold water, allowed to stand for 30min, and filtered to obtain a crude product, and the other steps were the same as in example 1, to finally obtain a yellow solid fused heterocyclic conjugated polymer P3 in a yield of 45.5%, and the structural characterization results were as follows:
1H NMR(400MHz,CDCl3)δ(ppm)8.13-7.29(14H,ArH),4.32(s,4H,CH2), 4.13-4.09(m,4H,CH2),1.22-1.18(t,6H,CH3)；FT-IR(KBr)2985,2902,2827,2735,1720, 1607,1271,1219,1166,1039,985,825。
the polymer had Mn of 1.9X 10 as determined by gel permeation chromatography4，Mw＝3.7×104，Mw/Mn＝1.88。
Example 4
In this example, 1, 4-terephthalaldehyde in example 3 was replaced by equimolar 2, 5-thiophenedicarboxaldehyde, and the other steps were the same as in example 3, to finally obtain a yellow solid fused heterocyclic conjugated polymer P4 in 47.3% yield, which was structurally characterized as follows:
1H NMR(400MHz,CDCl3)δ(ppm)8.41-7.30(10H,ArH),4.32(s,4H,CH2), 4.23-4.18(m,4H,CH2),1.22-1.88(t,6H,CH3)；FT-IR(KBr)2979,2933,2862,1722,1637, 1537,1444,1373,1205,1026,810。
the polymer had Mn of 1.8X 10 as determined by gel permeation chromatography4，Mw＝3.3×104，Mw/Mn＝1.78。
Example 5
In this example, the ethyl propiolate in example 3 was replaced by equimolar phenylpropargyl acetylene acid, and the other steps were the same as in example 3, to obtain a yellow solid fused heterocyclic conjugated polymer P5 with a yield of 44.9%, and the structural characterization results were as follows:
1H NMR(400MHz,CDCl3)δ(ppm)7.91-7.22(24H,ArH),4.02(s,4H,CH2)；FT-IR (KBr)3080,2920,1701,1625,1446,1299,1186,1107,1107,817。
the polymer has Mn of 0.8 × 10 by gel permeation chromatography test4，Mw＝1.7×104，Mw/Mn＝2.01。
Example 6
In this example, 1, 4-terephthalaldehyde in example 5 was replaced by equimolar 2, 5-thiophenedicarboxaldehyde, and the other steps were the same as in example 5, to finally obtain a yellow solid fused heterocyclic conjugated polymer P6 in 47.7% yield, which was structurally characterized as follows:
1H NMR(400MHz,CDCl3)δ(ppm)8.02-7.18(20H,ArH),4.12(s,4H,CH2)；FT-IR (KBr)2962,2921,2852,1718,1604,1244,1174,1107,1020,833。
the polymer had Mn of 1.1X 10 as determined by gel permeation chromatography4，Mw＝2.1×104，Mw/Mn＝1.89。
Example 7
Fused-heterocycle conjugated polymer P1 prepared in example 1 for detecting Fe3+The specific method comprises the following steps:
the fused heterocyclic conjugated polymer P1 was dissolved in tetrahydrofuran to prepare 1.0X 10-6A tetrahydrofuran solution of mol/L P1; 3mL of 10-6Adding a tetrahydrofuran solution of mol/L P1 into a cuvette, and adding Fe into the cuvette3+Standard samples, respectively adding Fe to the obtained mixed solution3+The concentration of (1) is 0, 3.33, 6.67, 10, 13.3, 16.67 and 20 mu mol/L, and a fluorescence spectrometer is adopted to measure Fe with different concentrations3+Fluorescence spectra of the corresponding systems (see FIG. 1) and plotted for different concentrations of Fe at 440nm3+Relative fluorescence intensity of the corresponding system with Fe3+Standard curve of concentration change.
As can be seen from FIG. 1, the fluorescence intensity of P1 is affected by Fe3+The effect of the concentration changes clearly, accompanied by Fe3+Increase in concentration, fluorescence intensity of the SystemGradually decreases. As can be seen from FIG. 2, Fe3+When the concentration of (b) is 0-20 [ mu ] mol/L, the relative fluorescence intensity is dependent on Fe3+The concentration increases linearly, the linear equation is:
y＝0.3604x1+1
wherein y is the relative fluorescence intensity, x1Is Fe3+Concentration, coefficient of correlation R2Is 0.9861. From this, the relative fluorescence intensity and Fe were observed3+The linear relationship of the concentrations is good. Calculating the lowest detection limit by using the formula of the lowest detection limit, P1 for Fe3+Has high detection sensitivity and detection limit of 9.483 multiplied by 10-6mol/L。
Example 8
Detection of Fe in fused heterocyclic conjugated Polymer (P2) prepared in example 23+The specific method is the same as in example 7. As can be seen from FIG. 3, the fluorescence intensity of P2 is affected by Fe3+The effect of the concentration changes clearly, with Fe3+The fluorescence intensity of the system gradually decreases with increasing concentration. As can be seen from FIG. 4, Fe3+When the concentration of (b) is 0-20 [ mu ] mol/L, the relative fluorescence intensity is dependent on Fe3+The concentration increases linearly, the linear equation is:
y＝0.3259x2+1
wherein y is the relative fluorescence intensity, x2Is Fe3+Concentration, coefficient of correlation R2Is 0.9914. From this, the relative fluorescence intensity and Fe were observed3+The linear relationship of the concentrations is good. Calculating the lowest detection limit by using the formula of the lowest detection limit, P2 for Fe3+Has high detection sensitivity and detection limit of 5.860 multiplied by 10-6mol/L。
Example 9
Fused-heterocycle conjugated polymer P3 prepared in example 3 for detecting Fe3+The specific method used in (1) is the same as in example 7. As can be seen from FIG. 5, the fluorescence intensity of P3 is affected by Fe3+The effect of the concentration changes clearly, accompanied by Fe3+The fluorescence intensity of the system gradually decreases with increasing concentration. As can be seen from FIG. 6, Fe3+When the concentration of (b) is 0-20 [ mu ] mol/L, the relative fluorescence intensity is dependent on Fe3+The concentration increases linearly, the linear equation is:
y＝0.3499x3+1
wherein y is the relative fluorescence intensity, x3Is Fe3+Concentration, coefficient of correlation R2Is 0.9633. From this, the relative fluorescence intensity and Fe were observed3+The linear relationship of the concentrations is good. Calculating the lowest detection limit by using a formula of the lowest detection limit, namely P3 for Fe3+Has high detection sensitivity and detection limit of 8.377 multiplied by 10-6mol/L。
Example 10
Detection of Fe in fused heterocyclic conjugated polymer P5 prepared in example 53+The specific method is the same as in example 7. As can be seen from FIG. 7, the fluorescence intensity of P1 is affected by Fe3+The effect of the concentration changes clearly, accompanied by Fe3+The fluorescence intensity of the system gradually decreases with increasing concentration. As can be seen from FIG. 8, Fe3+When the concentration of (b) is 0-20 [ mu ] mol/L, the relative fluorescence intensity is dependent on Fe3+The concentration increases linearly, the linear equation is:
y＝0.2119x4+1
wherein y is the relative fluorescence intensity, x4Is Fe3+Concentration, coefficient of correlation R2Is 0.9676. From this, the relative fluorescence intensity and Fe were observed3+The linear relationship of the concentrations is good. Calculating the lowest detection limit by using the formula of the lowest detection limit, P5 for Fe3+Has high detection sensitivity and detection limit of 1.18 multiplied by 10-6mol/L。
To prove the fused heterocyclic conjugated polymer of the present invention is p-Fe3+The inventors employed the fused heterocyclic conjugated polymers of examples 1, 2, 3, and 5, respectively, for Ag+、Ba2+、Ca2+、Cd2+、Cu2+、Mg2+、Mn2+、 Ni2+、Pd2+、Zn2+、Hg2+、Al3+And Fe3+These 13 heavy metal cations (wherein the polymer concentration is 1.0X 10)-6mol/L, prepared by taking tetrahydrofuran as a solvent, and the concentration of metal ions in a detection system is 1.0 multiplied by 10-4mol/L) were tested, and the results are shown in FIGS. 9 to 12. As can be seen, when Fe is added3+When the fluorescence quenching effect of the detection system is strongest,and other ions almost have no fluorescence quenching effect, which shows that the fused heterocyclic conjugated polymer can detect Fe with high selectivity3+。
Claims (7)
1. For detecting Fe3+The fused heterocyclic conjugated polymer of (2) is characterized in that the structural unit of the polymer is as follows:
in the formula R1Represents
Any one of, R2Represented by phenyl, C1～C8Alkyl-substituted phenyl, halophenyl, C1～C3The alkoxy is substituted for any one of phenyl, carbomethoxy and carbethoxy.
2. The process for producing a fused heterocyclic conjugated polymer according to claim 1, wherein: adding a bisazine monomer shown in a formula I, a monomer shown in a formula II and containing two aldehyde groups, an alkyne monomer shown in a formula III, copper salt and alkali into dimethyl sulfoxide, carrying out a polymerization reaction under the conditions of inert gas protection and stirring at 70-90 ℃, and after the reaction is finished, extracting, drying and dialyzing to obtain a fused heterocyclic conjugated polymer;
in the formula III, R3Represents hydrogen or a carboxyl group.
3. The method for producing a fused heterocyclic conjugated polymer according to claim 2, wherein: the cupric salt is any one of cuprous chloride, cuprous iodide and cuprous bromide.
4. The method for producing a fused heterocyclic conjugated polymer according to claim 2, wherein: the alkali is any one of anhydrous potassium carbonate and anhydrous sodium carbonate.
5. The method for producing a fused heterocyclic conjugated polymer according to any one of claims 2 to 4, wherein: the molar ratio of the bisazine monomer to the monomer containing two aldehyde groups to the alkyne monomer is 1: 1.0-3.0: 2.0-5.0.
6. The method for producing a fused heterocyclic conjugated polymer according to any one of claims 2 to 4, wherein: the molar ratio of the bisazine monomer to the copper salt to the alkali is 1: 0.02-0.5: 2.0-5.0.
7. The fused heterocyclic conjugated polymer of claim 1 for detecting Fe3+The use of (1).
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