CN115505104A - Quinoxaline-based conjugated microporous polymer, photoelectrochemical sensor, preparation method of quinoxaline-based conjugated microporous polymer and dopamine detection method - Google Patents
Quinoxaline-based conjugated microporous polymer, photoelectrochemical sensor, preparation method of quinoxaline-based conjugated microporous polymer and dopamine detection method Download PDFInfo
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- VYFYYTLLBUKUHU-UHFFFAOYSA-N dopamine Chemical compound NCCC1=CC=C(O)C(O)=C1 VYFYYTLLBUKUHU-UHFFFAOYSA-N 0.000 title claims abstract description 118
- 239000013317 conjugated microporous polymer Substances 0.000 title claims abstract description 97
- 229960003638 dopamine Drugs 0.000 title claims abstract description 59
- XSCHRSMBECNVNS-UHFFFAOYSA-N quinoxaline Chemical compound N1=CC=NC2=CC=CC=C21 XSCHRSMBECNVNS-UHFFFAOYSA-N 0.000 title claims abstract description 46
- 238000001514 detection method Methods 0.000 title claims abstract description 17
- 238000002360 preparation method Methods 0.000 title abstract description 17
- 238000000034 method Methods 0.000 claims abstract description 27
- 239000000178 monomer Substances 0.000 claims abstract description 22
- 125000001567 quinoxalinyl group Chemical group N1=C(C=NC2=CC=CC=C12)* 0.000 claims abstract description 18
- RFFLAFLAYFXFSW-UHFFFAOYSA-N 1,2-dichlorobenzene Chemical compound ClC1=CC=CC=C1Cl RFFLAFLAYFXFSW-UHFFFAOYSA-N 0.000 claims abstract description 16
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims abstract description 16
- 230000002194 synthesizing effect Effects 0.000 claims abstract description 11
- MQIMWEBORAIJPP-UHFFFAOYSA-N cyclohexane-1,2,3,4,5,6-hexone;octahydrate Chemical compound O.O.O.O.O.O.O.O.O=C1C(=O)C(=O)C(=O)C(=O)C1=O MQIMWEBORAIJPP-UHFFFAOYSA-N 0.000 claims abstract description 9
- PONXTPCRRASWKW-ZIAGYGMSSA-N (1r,2r)-1,2-diphenylethane-1,2-diamine Chemical compound C1([C@@H](N)[C@H](N)C=2C=CC=CC=2)=CC=CC=C1 PONXTPCRRASWKW-ZIAGYGMSSA-N 0.000 claims abstract description 8
- 229960000583 acetic acid Drugs 0.000 claims abstract description 8
- MGNCLNQXLYJVJD-UHFFFAOYSA-N cyanuric chloride Chemical compound ClC1=NC(Cl)=NC(Cl)=N1 MGNCLNQXLYJVJD-UHFFFAOYSA-N 0.000 claims abstract description 8
- 239000012362 glacial acetic acid Substances 0.000 claims abstract description 8
- 239000007788 liquid Substances 0.000 claims abstract description 6
- 239000006185 dispersion Substances 0.000 claims abstract description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 20
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 15
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 13
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 10
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 10
- 239000007795 chemical reaction product Substances 0.000 claims description 10
- 238000001816 cooling Methods 0.000 claims description 10
- 239000012153 distilled water Substances 0.000 claims description 10
- 239000005457 ice water Substances 0.000 claims description 10
- 239000000203 mixture Substances 0.000 claims description 10
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 10
- 238000000967 suction filtration Methods 0.000 claims description 10
- 238000005406 washing Methods 0.000 claims description 10
- 239000012295 chemical reaction liquid Substances 0.000 claims description 9
- 239000003792 electrolyte Substances 0.000 claims description 8
- 239000008055 phosphate buffer solution Substances 0.000 claims description 8
- 239000012086 standard solution Substances 0.000 claims description 8
- 239000007787 solid Substances 0.000 claims description 7
- 238000001035 drying Methods 0.000 claims description 6
- 210000002966 serum Anatomy 0.000 claims description 6
- 238000001291 vacuum drying Methods 0.000 claims description 6
- 238000000944 Soxhlet extraction Methods 0.000 claims description 5
- 229910052697 platinum Inorganic materials 0.000 claims description 5
- 239000002244 precipitate Substances 0.000 claims description 5
- 229910021607 Silver chloride Inorganic materials 0.000 claims description 4
- 238000000970 chrono-amperometry Methods 0.000 claims description 4
- 238000004519 manufacturing process Methods 0.000 claims description 4
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 claims description 4
- 230000035945 sensitivity Effects 0.000 abstract description 2
- 230000000379 polymerizing effect Effects 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 7
- 230000004044 response Effects 0.000 description 4
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 3
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 150000003943 catecholamines Chemical class 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000001157 Fourier transform infrared spectrum Methods 0.000 description 1
- 238000003547 Friedel-Crafts alkylation reaction Methods 0.000 description 1
- 241000124008 Mammalia Species 0.000 description 1
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- 230000006399 behavior Effects 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229940075397 calomel Drugs 0.000 description 1
- 238000005251 capillar electrophoresis Methods 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 210000003169 central nervous system Anatomy 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 230000019771 cognition Effects 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- ZOMNIUBKTOKEHS-UHFFFAOYSA-L dimercury dichloride Chemical compound Cl[Hg][Hg]Cl ZOMNIUBKTOKEHS-UHFFFAOYSA-L 0.000 description 1
- 230000004064 dysfunction Effects 0.000 description 1
- 230000002526 effect on cardiovascular system Effects 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 238000007210 heterogeneous catalysis Methods 0.000 description 1
- 238000004128 high performance liquid chromatography Methods 0.000 description 1
- 230000003054 hormonal effect Effects 0.000 description 1
- AMGQUBHHOARCQH-UHFFFAOYSA-N indium;oxotin Chemical compound [In].[Sn]=O AMGQUBHHOARCQH-UHFFFAOYSA-N 0.000 description 1
- 230000005415 magnetization Effects 0.000 description 1
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- 230000005311 nuclear magnetism Effects 0.000 description 1
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- 239000011368 organic material Substances 0.000 description 1
- 238000007146 photocatalysis Methods 0.000 description 1
- 230000001699 photocatalysis Effects 0.000 description 1
- 230000000717 retained effect Effects 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
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- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G61/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
- C08G61/12—Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule
- C08G61/122—Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule derived from five- or six-membered heterocyclic compounds, other than imides
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
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- G01N27/28—Electrolytic cell components
- G01N27/30—Electrodes, e.g. test electrodes; Half-cells
- G01N27/305—Electrodes, e.g. test electrodes; Half-cells optically transparent or photoresponsive electrodes
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- G01N27/00—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means
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- C08G2261/10—Definition of the polymer structure
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Abstract
The invention belongs to the technical field of electrochemical sensors, and provides a quinoxaline-based conjugated microporous polymer, a photoelectrochemical sensor, a preparation method of the quinoxaline-based conjugated microporous polymer and a dopamine detection method. The preparation method of the quinoxalinyl conjugated microporous polymer comprises the steps of synthesizing a monomer B1 by utilizing a hexaketocyclohexane octahydrate, (1R, 2R) -1, 2-diphenyl ethylenediamine and glacial acetic acid, and then utilizing o-dichlorobenzene, cyanuric chloride and CF 3 SO 3 H. Polymerizing the monomer B1 to obtain the quinoxalinyl conjugated microporous polymer. The photoelectrochemical sensor is prepared by modifying quinoxaline based conjugated microporous polymer dispersion liquid on an ITO electrode. The dopamine detection is that firstly, the linear relation between the photocurrent and the logarithm of the concentration of the dopamine is obtained, then, a sample is tested, and the photocurrent value is brought into the linear relation to obtain the dopamineAnd (4) concentration. The novel method for detecting dopamine has the advantages of high sensitivity, miniaturization of the device, simplicity in operation, rapidness in detection, low cost and the like.
Description
Technical Field
The invention relates to the technical field of dopamine detection, in particular to a quinoxaline-based conjugated microporous polymer, a photoelectrochemical sensor, a preparation method of the quinoxaline-based conjugated microporous polymer and a dopamine detection method.
Background
Dopamine (DA), also known as catecholamine, with molecular formula C 8 H 11 NO 2 The structural formula is as follows:
dopamine, a natural catecholamine, is widely distributed in the central nervous system of mammals and plays an important role in cardiovascular, human metabolism, and hormonal systems. Many human behaviors, including cognition, motor function, motivation, and the like, are closely related to dopamine. Dopamine dysfunction can also cause neurological disorders such as parkinson's disease and schizophrenia. Therefore, the efficient and sensitive detection of dopamine concentrations has become an important research item in the medical or health care field. Currently, many techniques for detecting dopamine have been developed, such as high performance liquid chromatography, fluorescence spectrophotometry, and capillary electrophoresis. Although the detection methods can accurately detect the content of the dopamine, the sample pretreatment is complicated, and the cost and the maintenance cost are high. Therefore, the development of a method for sensitively and rapidly detecting dopamine is of great research significance.
Conjugated Microporous Polymers (CMP) have been widely studied since their discovery, and as an important porous organic material, they have the advantages of good chemical and thermal stability, large specific surface area, adjustable structure and optical band gap, and the like. CMP has good application prospect in the fields of gas storage, heterogeneous catalysis and photocatalysis. At present, no report is found on a method for detecting dopamine by constructing a photoelectrochemical sensor by utilizing CMP.
Disclosure of Invention
The invention aims to: aiming at the existing problems, the invention provides a quinoxaline based conjugated microporous polymer, a photoelectrochemical sensor, a preparation method thereof and a dopamine detection method.
In order to achieve the purpose, the technical scheme adopted by the invention is as follows:
a quinoxalinyl conjugated microporous polymer, the structural formula of which is:
the invention also provides a preparation method of the quinoxaline-based conjugated microporous polymer, which comprises the following steps:
(1) Synthesizing monomers: hexaketocyclohexane octahydrate, (1R, 2R) -1, 2-diphenylethylenediamine and glacial acetic acid were added to a round bottom flask in N 2 Reacting at 115-125 ℃ for 10-14 h under protection, cooling the reaction product to room temperature, pouring the reaction product into a large beaker, and adding ice cubes and distilled water to form an ice-water mixture; carrying out suction filtration treatment on the ice-water mixture, washing the precipitate with ethanol, and drying to obtain a monomer B1;
(2) Synthesizing CMP: o-dichlorobenzene, cyanuric chloride and CF 3 SO 3 H. Monomer B1 was added to a round bottom flask at N 2 Under protection, reacting for 45-52 h at 135-145 ℃, cooling the obtained reaction liquid to room temperature, carrying out suction filtration on the obtained reaction liquid, and washing the obtained solid with distilled water and ethanol respectively; then, methanol, THF, acetone are used for Soxhlet extraction for 20-28h respectively, and drying is carried out to obtain the quinoxalinyl conjugated microporous polymer CMP.
In the above-mentioned method for producing a quinoxalinyl-conjugated microporous polymer, preferably, in the step (1), the hexaketocyclohexane octahydrate, (1R, 2R) -1, 2-diphenylethylenediamine and glacial acetic acid are mixed at a ratio of mmol/mmol/mL of 1:3: (50 to 70).
In the above method for preparing a quinoxalinyl conjugated microporous polymer, preferably, in the step (2), cyanuric chloride, monomer B1, o-dichlorobenzene, CF 3 SO 3 H is 4 in mmol/mmol/mL/mL ratio: 3: (35-45): (3-4).
In the above method for preparing a quinoxalinyl conjugated microporous polymer, preferably, the drying means vacuum drying at 50 ℃.
The invention also provides a photoelectrochemical sensor which is obtained by modifying the quinoxaline-based conjugated microporous polymer on the conductive surface of the ITO electrode.
The invention also provides a method for preparing a photoelectrochemical sensor by utilizing the quinoxaline-based conjugated microporous polymer, which comprises the following steps: ultrasonically dispersing the quinoxaline-based conjugated microporous polymer in N, N-dimethylformamide to form a dispersion liquid; and transferring the dispersed liquid drops to be coated on the conductive surface of the ITO electrode to prepare the CMP modified electrode CMP/ITO, and airing at room temperature for later use.
In the above method for preparing an electrochemical sensor, the concentration of the quinoxalinyl conjugated microporous polymer dispersed in N, N-dimethylformamide is 1.5mg/mL.
The invention also provides a dopamine detection method, namely the method for detecting dopamine by using the photoelectrochemical sensor prepared by the method comprises the following steps:
(1) Establishing a linear relation: preparing dopamine standard solutions with different concentrations; a phosphate buffer solution is used as electrolyte, a CMP modified electrode CMP/ITO is used as a working electrode, a platinum electrode is used as an auxiliary electrode, and an Ag/AgCl electrode is used as a reference electrode to form a three-electrode system; adding a dopamine standard solution into the electrolyte, and respectively detecting the dopamine standard solutions with different concentrations by adopting a chronoamperometry method, thereby obtaining a linear relation between photocurrent and logarithm of the dopamine concentration;
(2) And (3) detection: and (3) detecting the concentration of the dopamine in the serum to be detected in a phosphate buffer solution by adopting a standard addition method, and determining the content of the dopamine in the serum according to the linear relation between the photocurrent obtained in the step (1) and the concentration.
The concentration of the phosphate buffer solution used in the above steps (1) and (2) is 0.2mol/L, and the pH value is 7.0.
In summary, due to the adoption of the technical scheme, the invention has the beneficial effects that:
1. the invention discloses a novel quinoxaline-based Conjugated Microporous Polymer (CMP) prepared through a Friedel-crafts alkylation reaction, and the novel quinoxaline-based conjugated microporous polymer is applied to constructing a photoelectrochemical sensor to detect dopamine, belonging to the technical field of dopamine detection. The method adopts a dripping coating method to drip and coat the CMP on an Indium Tin Oxide (ITO) electrode to prepare a CMP modified electrode, constructs a three-electrode system with a platinum electrode and a calomel electrode, and detects the dopamine by adopting a chronoamperometry. The result shows that the constructed photoelectrochemical sensor has good photoelectric response to dopamine, the photocurrent and the logarithm of the dopamine concentration present a good linear relation, the linear range is 0.0125-35 mu mol/L, and the detection limit is 0.007 mu mol/L. In addition, the method has good repeatability and stability. The determination method of the invention provides a new idea for detecting dopamine and widens the application field of the conjugated microporous polymer.
2. The method for preparing the CMP is simple in synthesis method and easy to synthesize, and compared with an electrode without modifying the CMP, the electrode modified by the CMP on the ITO electrode is used as a working electrode, so that the photocurrent is obviously enhanced, and the sensitivity is higher.
Drawings
FIG. 1 is a scanning electron microscope image of CMP;
FIG. 2 FT-IR plot of CMP and monomer B;
FIG. 3 solid nuclear magnetization for CMP;
FIG. 4 is a photo-amperometric graph of dopamine solutions of different concentrations on a CMP modified electrode;
FIG. 5 a standard curve between the logarithm of the dopamine concentration and the photocurrent;
fig. 6 photocurrent responses of different electrodes.
Detailed Description
The technical solutions of the present invention will be described clearly and completely with reference to the following embodiments of the present invention, and it should be understood that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be obtained by a person skilled in the art based on the embodiments of the present invention without inventive step, are within the scope of the present invention.
The invention provides a quinoxaline based conjugated microporous polymer, which has a structural formula as follows:
1. preparation example of CMP
EXAMPLE 1 preparation of CMP
The preparation method of the quinoxalinyl conjugated microporous polymer comprises the following steps:
(1) Synthesizing monomers: hexaketocyclohexane octahydrate (2.00mmol, 0.62g), (6.00mmol, 1.27g) (1R, 2R) -1, 2-diphenylethylenediamine and 120.00mL of glacial acetic acid were added to a round bottom flask in N 2 Reacting at 115 ℃ for 10 hours under protection, cooling the reaction product to room temperature, pouring the reaction product into a large beaker, and adding ice cubes and distilled water to form an ice-water mixture; carrying out suction filtration treatment on the ice-water mixture, washing the precipitate with ethanol, and carrying out vacuum drying at 50 ℃ for 12h to obtain a monomer B1;
(2) Synthesizing CMP: 12.00mL of o-dichlorobenzene, (1.20mmol, 0.22g) of cyanuric chloride, and 1.08mL of CF 3 SO 3 H. (0.89mmol, 0.61g) monomer B1 was added to a round bottom flask in N 2 Reacting at 135 ℃ for 52 hours under protection, cooling the obtained reaction liquid to room temperature, carrying out suction filtration on the obtained reaction liquid, and washing the obtained solid with distilled water and ethanol respectively; subsequently, methanol, THF, acetone were used each for Soxhlet extraction for 20h, vacuum dried at 50 ℃ for 12h to obtain the quinoxalinyl conjugated microporous polymer CMP.
The preparation route of the quinoxaline conjugated microporous polymer CMP is as follows:
EXAMPLE 2 preparation of CMP
The preparation method of the quinoxaline-based conjugated microporous polymer adopts the same synthetic route as the example 1, and comprises the following steps:
(1) Synthesizing monomers: hexaketocyclohexane octahydrate (2.00mmol, 0.62g), (6.00mmol, 1.27g) (1R, 2R) -1, 2-diphenylethylenediamine and 100.00mL of glacial acetic acid were added to a round bottom flask in N 2 Reacting at 120 ℃ for 12 hours under protection, cooling the reaction product to room temperature, pouring the reaction product into a large beaker, and adding ice cubes and distilled water to form an ice-water mixture; carrying out suction filtration treatment on the ice-water mixture, washing the precipitate with ethanol, and carrying out vacuum drying at 50 ℃ for 12h to obtain a monomer B1;
(2) Synthesizing CMP: 10.50mL of o-dichlorobenzene, (1.20mmol, 0.22g) of cyanuric chloride, and 0.90mL of CF 3 SO 3 H. (0.90 mmol) of monomer B1 was added to a round-bottom flask in N 2 Reacting at 140 ℃ for 50 hours under protection to obtain reaction liquid, cooling the reaction liquid to room temperature, carrying out suction filtration on the obtained reaction liquid, and washing the obtained solid with distilled water and ethanol respectively; subsequently, methanol, THF, acetone are used for Soxhlet extraction for 24h respectively, and vacuum drying is carried out for 12h at 50 ℃ to obtain the quinoxalinyl conjugated microporous polymer CMP.
EXAMPLE 3 preparation of CMP
The preparation method of the quinoxalinyl conjugated microporous polymer adopts the same synthetic route as the example 1 and comprises the following steps:
(1) Synthesizing monomers: hexaketocyclohexane octahydrate (2.00mmol, 0.62g), hexaketocyclohexane octahydrate, (6.00mmol, 1.27g) (1R, 2R) -1, 2-diphenylethylenediamine and 140.00mL of glacial acetic acid were added to a round bottom flask in N 2 Reacting at 125 ℃ for 10 hours under protection, cooling the reaction product to room temperature, pouring the reaction product into a large beaker, and adding ice cubes and distilled water to form an ice-water mixture; carrying out suction filtration treatment on the ice water mixture, washing the precipitate with ethanol, and carrying out vacuum drying at 50 ℃ for 12h to obtain a monomer B1;
(2) Synthesizing CMP: 13.50mL of o-dichlorobenzene, (1.20mmol, 0.22g) of cyanuric chloride, and 1.20mL of CF 3 SO 3 H. (0.89mmol, 0.61g) monomer B1 was charged to a round bottom flask in N 2 Reacting at 145 ℃ for 45 hours under the protection of the reaction solution, cooling the reaction solution to room temperature, and reactingCarrying out suction filtration on the solution, and washing the obtained solid with distilled water and ethanol respectively; subsequently, methanol, THF, acetone were used each for Soxhlet extraction for 28h, vacuum dried at 50 ℃ for 12h to obtain the quinoxalinyl conjugated microporous polymer CMP.
2. Characterization of CMP
The topography of the CMP synthesized in examples 1-3 was characterized using a scanning electron microscope, model TESCAN MIRA LMS, as shown in FIG. 1. It is clear from the scanning electron micrograph that CMP is a bulk structure and has a smooth surface. Monomer B and CMP were structurally characterized by a spectrum 65 fourier transform infrared spectrometer, as shown in figure 2. In the range of 1385-1622 cm -1 The nearby absorption peak is the stretching vibration of the benzene ring, 614cm -1 The absorption peak at (A) is the out-of-plane bending vibration of the C-H bond of the benzene ring. At 3410cm -1 There was a significant-OH stretching vibration due to the sample absorbing moisture. It can be found from the FT-IR spectrum that the prepared CMP retained the characteristic peaks of the corresponding monomers at the same positions. In addition, the structure of CMP was also characterized by solid nuclear magnetism, and as shown in fig. 3, the peak at 129.76ppm was carbon atom on the benzene ring, and the peak at 174ppm was assigned as C = N.
3. Preparation of photoelectrochemical sensor
EXAMPLE 4 preparation of photoelectric chemical sensor
The method for preparing the photoelectrochemical sensor by utilizing the quinoxaline-based conjugated microporous polymer comprises the following steps: ultrasonically dispersing 1.5mg of quinoxalinyl conjugated microporous polymer in 1mLN, N-dimethylformamide to form 1.5mg/mL of CMP dispersion; and transferring 15 mu L of dispersion liquid drop to be coated on the conductive surface of the ITO electrode to prepare a CMP modified electrode CMP/ITO, and airing at room temperature for later use.
4. Method for detecting dopamine
Comparative example 1 photoelectric response of Bare ITO electrode (Bare/ITO) to dopamine
Bare/ITO and CMP/ITO which do not modify any materials are respectively used as working electrodes, a platinum electrode is used as an auxiliary electrode, an Ag/AgCl electrode is used as a reference electrode to form a three-electrode system for detecting dopamine, and the photoelectric corresponding situation is shown in figure 4. In the electrolyte without dopamine, the CMP/ITO has good photoelectric response, and the photocurrent of the CMP modified electrode is obviously increased when 25 mu mol/L of dopamine exists in the electrolyte.
Example 5 method for detecting dopamine
The method for detecting dopamine by using the photoelectrochemical sensor prepared in the embodiment 4 comprises the following steps:
(1) Establishing a linear relation: preparing standard dopamine solutions with different concentrations, wherein the concentrations are 0, 0.0125, 0.025, 0.05, 0.125, 0.2, 0.5, 2.5, 5, 12.5 and 35 mu mol/L respectively; forming a three-electrode system by using a phosphate buffer solution (4 mL, 0.2mol/L) as an electrolyte (pH 7.0), a CMP modified electrode (CMP/ITO) as a working electrode, a platinum electrode as an auxiliary electrode and an Ag/AgCl electrode as a reference electrode; a conventional electrochemical workstation, a photoelectrochemical reactor and a three-electrode system are adopted to construct a photoelectrochemical sensing platform. Adding a dopamine standard solution into the electrolyte, and respectively detecting the dopamine standard solutions with different concentrations by adopting a chronoamperometry method to obtain a photoelectrogram (figure 5) of the dopamine solutions with different concentrations on the CMP modified electrode and a relation (figure 6) between the logarithm of the dopamine concentration and the photocurrent, wherein the photocurrent increases along with the increase of the dopamine concentration. The curves shown in fig. 6 show that the logarithm of the dopamine concentration and the photocurrent showed a good linear relationship, with a correlation coefficient of 0.9916, and a detection limit of 0.007 μmol/L was obtained by the formula LOD = 3S/K.
(2) And (3) detection: and (2) detecting the concentration of the dopamine in the serum to be detected in a phosphate buffer solution by adopting a standard addition method, and determining the content of the dopamine in the serum according to the linear relation between the photocurrent obtained in the step (1) and the concentration.
5. Reproducibility, stability, selectivity
The reproducibility of the CMP/ITO sensor is continuously considered, 4 CMP/ITO sensors are modified under the same experimental conditions, dopamine with the same concentration is detected, and the relative standard deviation of the obtained peak current value is 0.66%, which indicates that the sensor has good reproducibility. Meanwhile, 1 prepared CMP/ITO electrode is stored at room temperature, and the peak current value is 96.69% of the first detection current after 5 days of measurement under the same condition, which indicates that the sensor has good stability.
The above description is intended to describe in detail the preferred embodiments of the present invention, but the embodiments are not intended to limit the scope of the claims of the present invention, and all equivalent changes and modifications made within the technical spirit of the present invention should fall within the scope of the claims of the present invention.
Claims (10)
1. A quinoxaline-based conjugated microporous polymer, characterized in that the quinoxaline-based conjugated microporous polymer has the structural formula:
2. the method for preparing a quinoxalinyl conjugated microporous polymer according to claim 1, characterized in that it comprises the following steps:
(1) Synthesizing monomers: hexaketocyclohexane octahydrate, (1R, 2R) -1, 2-diphenylethylenediamine and glacial acetic acid were added to a round bottom flask in N 2 Reacting at 115-125 ℃ for 10-14 h under protection, cooling the reaction product to room temperature, pouring the reaction product into a large beaker, and adding ice cubes and distilled water to form an ice-water mixture; carrying out suction filtration treatment on the ice-water mixture, washing the precipitate with ethanol, and drying to obtain a monomer B1;
(2) Synthesizing CMP: o-dichlorobenzene, cyanuric chloride and CF 3 SO 3 H. Monomer B1 was added to a round bottom flask at N 2 Under protection, reacting for 45-52 h at 135-145 ℃, cooling the obtained reaction liquid to room temperature, carrying out suction filtration on the obtained reaction liquid, and washing the obtained solid with distilled water and ethanol respectively; then, the quinoxalinyl conjugated microporous polymer CMP is obtained by Soxhlet extraction for 20-28h respectively by using methanol, THF and acetone and drying.
3. The production method according to claim 2, characterized in that: in step (1), the hexaketocyclohexane octahydrate, (1R, 2R) -1, 2-diphenylethylenediamine and glacial acetic acid are 1:3: (50 to 70).
4. The production method according to claim 2, characterized in that: in the step (2), cyanuric chloride, a monomer B1, o-dichlorobenzene and CF 3 SO 3 H is 4:3: (35-45): (3-4).
5. The production method according to claim 2, characterized in that: the drying refers to vacuum drying at 50 ℃.
6. A photoelectrochemical sensor, comprising: is obtained by modifying the quinoxaline conjugated microporous polymer described in claim 1 on the conductive surface of an ITO electrode.
7. A method for preparing a photoelectrochemical sensor using the quinoxalinyl conjugated microporous polymer according to claim 1, characterized in that it comprises the following steps: ultrasonically dispersing the quinoxaline-based conjugated microporous polymer in N, N-dimethylformamide to form a dispersion liquid; and transferring the dispersed liquid drops to be coated on the conductive surface of the ITO electrode to prepare the CMP modified electrode CMP/ITO, and airing at room temperature for later use.
8. The method of claim 7, wherein: the concentration of the quinoxalinyl conjugated microporous polymer dispersed in N, N-dimethylformamide is 1.5mg/mL.
9. The method for detecting dopamine by using the photoelectrochemical sensor prepared by the method according to claim 7, which is characterized by comprising the following steps:
(1) Establishing a linear relation: preparing dopamine standard solutions with different concentrations; a phosphate buffer solution is used as an electrolyte, a CMP modified electrode CMP/ITO is used as a working electrode, a platinum electrode is used as an auxiliary electrode, and an Ag/AgCl electrode is used as a reference electrode to form a three-electrode system; adding a dopamine standard solution into the electrolyte, and respectively detecting the dopamine standard solutions with different concentrations by adopting a chronoamperometry method, thereby obtaining a linear relation between photocurrent and logarithm of the dopamine concentration;
(2) And (3) detection: and (3) detecting the concentration of the dopamine in the serum to be detected in a phosphate buffer solution by adopting a standard addition method, and determining the content of the dopamine in the serum according to the linear relation between the photocurrent obtained in the step (1) and the concentration.
10. The method of claim 7, wherein: the concentration of the phosphate buffer solution used in the steps (1) and (2) is 0.2mol/L, and the pH value is 7.0.
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