CN115505104B - Quinoxalinyl conjugated microporous polymer, photoelectrochemical sensor, preparation method thereof and dopamine detection method - Google Patents
Quinoxalinyl conjugated microporous polymer, photoelectrochemical sensor, preparation method thereof 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 120
- 239000013317 conjugated microporous polymer Substances 0.000 title claims abstract description 96
- 229960003638 dopamine Drugs 0.000 title claims abstract description 60
- 125000001567 quinoxalinyl group Chemical group N1=C(C=NC2=CC=CC=C12)* 0.000 title claims abstract description 25
- 238000002360 preparation method Methods 0.000 title claims abstract description 23
- 238000001514 detection method Methods 0.000 title claims abstract description 16
- XSCHRSMBECNVNS-UHFFFAOYSA-N quinoxaline Chemical compound N1=CC=NC2=CC=CC=C21 XSCHRSMBECNVNS-UHFFFAOYSA-N 0.000 claims abstract description 26
- 238000000034 method Methods 0.000 claims abstract description 22
- 239000000178 monomer Substances 0.000 claims abstract description 22
- 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
- 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
- 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 7
- 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 7
- 239000006185 dispersion Substances 0.000 claims abstract description 7
- 239000007788 liquid Substances 0.000 claims abstract description 6
- 230000002194 synthesizing effect Effects 0.000 claims abstract description 6
- 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
- 239000012295 chemical reaction liquid Substances 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
- 239000012086 standard solution Substances 0.000 claims description 9
- 239000003792 electrolyte Substances 0.000 claims description 8
- 239000008055 phosphate buffer solution Substances 0.000 claims description 8
- 238000001291 vacuum drying Methods 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
- 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
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 claims description 4
- 238000000970 chrono-amperometry Methods 0.000 claims description 3
- 238000004519 manufacturing process Methods 0.000 claims 1
- 230000035945 sensitivity Effects 0.000 abstract description 2
- 230000000379 polymerizing effect Effects 0.000 abstract 1
- 230000004044 response Effects 0.000 description 4
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 3
- 238000010521 absorption reaction Methods 0.000 description 3
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- 238000010586 diagram Methods 0.000 description 2
- 230000005311 nuclear magnetism Effects 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- SYHVBRQKMHIAJQ-UHFFFAOYSA-N 3-(2-aminoethyl)benzene-1,2-diol Chemical compound NCCC1=CC=CC(O)=C1O SYHVBRQKMHIAJQ-UHFFFAOYSA-N 0.000 description 1
- 238000003547 Friedel-Crafts alkylation reaction Methods 0.000 description 1
- 241000124008 Mammalia Species 0.000 description 1
- 208000012902 Nervous system disease Diseases 0.000 description 1
- 208000025966 Neurological disease Diseases 0.000 description 1
- 208000018737 Parkinson disease Diseases 0.000 description 1
- 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
- 239000003054 catalyst Substances 0.000 description 1
- 150000003943 catecholamines Chemical class 0.000 description 1
- 210000003169 central nervous system Anatomy 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 230000019771 cognition Effects 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000010276 construction Methods 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
- 238000012423 maintenance Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 230000004060 metabolic process Effects 0.000 description 1
- 238000001000 micrograph Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000008450 motivation Effects 0.000 description 1
- 230000007659 motor function Effects 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 239000011368 organic material Substances 0.000 description 1
- 238000007146 photocatalysis Methods 0.000 description 1
- 230000001699 photocatalysis Effects 0.000 description 1
- 201000000980 schizophrenia Diseases 0.000 description 1
- 238000011896 sensitive detection Methods 0.000 description 1
- 238000002798 spectrophotometry method Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
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- 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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- 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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Abstract
The invention belongs to the technical field of electrochemical sensors, and provides a quinoxaline conjugated microporous polymer, a photoelectrochemical sensor, a preparation method thereof and a dopamine detection method. The preparation method of the quinoxalinyl conjugated microporous polymer comprises the steps of firstly synthesizing a monomer B1 by using a hexaketocyclohexane octahydrate, (1R, 2R) -1, 2-diphenylethylenediamine and glacial acetic acid, and then using o-dichlorobenzene, cyanuric chloride and CF 3 SO 3 H. And polymerizing the monomer B1 to obtain the quinoxalinyl conjugated microporous polymer. The photoelectrochemical sensor is prepared by modifying quinoxaline conjugated microporous polymer dispersion liquid on an ITO electrode. The dopamine is detected by firstly obtaining a linear relation between the photocurrent and the logarithm of the dopamine concentration, then testing a sample, and bringing the photocurrent value into a linear relation to obtain the dopamine concentration. The novel method for detecting dopamine has the advantages of high sensitivity, miniaturized device, simple operation, rapid detection, low cost and the like.
Description
Technical Field
The invention relates to the technical field of dopamine detection, in particular to a quinoxaline conjugated microporous polymer, a photoelectrochemical sensor, a preparation method thereof and a dopamine detection method.
Background
Dopamine (DA), also known as catecholethylamine, has the 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 in the hormonal system. Many behaviors of humans, including cognition, motor function, motivation, and the like are closely related to dopamine. Dopamine dysfunction may also cause neurological diseases such as parkinson's disease and schizophrenia. Therefore, effective and sensitive detection of dopamine concentration has become an important research content 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 pretreatment of the sample is complicated, and the cost and the maintenance cost are high. Therefore, development of a sensitive and rapid method for detecting dopamine has important research significance.
Conjugated microporous polymers (conjugated microporous polymer, CMP) have been extensively studied since their discovery as an important porous organic material with good chemical and thermal stability, large specific surface area, tunable structure and optical band gap, etc. CMP has good application prospect in the fields of gas storage, heterogeneous catalysis and photocatalysis. At present, a method for constructing a photoelectrochemical sensor to detect dopamine by utilizing CMP has not been reported yet.
Disclosure of Invention
The invention aims at: aiming at the problems, the invention provides a quinoxaline conjugated microporous polymer, a photoelectrochemical sensor, a preparation method thereof and a detection method of dopamine.
In order to achieve the above purpose, the technical scheme adopted by the invention is as follows:
a quinoxalinyl conjugated microporous polymer having the structural formula:
the invention also provides a preparation method of the quinoxalinyl conjugated microporous polymer, which comprises the following steps:
(1) Synthesizing a monomer: hexaketocyclohexane octahydrate, (1R, 2R) -1, 2-diphenylethylenediamine and glacial acetic acid were added to a round bottom flask at N 2 Under the protection, reacting for 10-14 h at 115-125 ℃, cooling the reaction product to room temperature, pouring the reaction product into a large beaker, adding ice cubes and distilled water to form an ice-water mixture; carrying out suction filtration on the ice-water mixture, washing the precipitate with ethanol, and drying to obtain a monomer B1;
(2) Synthetic CMP: o-dichlorobenzene, cyanuric chloride and CF 3 SO 3 H. Monomer B1 was added to a round bottom flask at N 2 Under the protection, reacting for 45-52 h at 135-145 ℃ to obtain a 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, each Soxhlet extraction is carried out for 20-28 hours by using methanol, THF and acetone, and the quinoxaline-based conjugated microporous polymer CMP is obtained after drying.
In the preparation method of the quinoxalinyl conjugated microporous polymer, preferably, in the step (1), the ratio of (1 r,2 r) -1, 2-diphenylethylenediamine to glacial acetic acid is 1:3: (50-70).
In the above preparation method of quinoxalinyl conjugated microporous polymer, preferably, in the step (2), cyanuric chloride, a monomer B1, o-dichlorobenzene, CF 3 SO 3 H is 4 in terms of mmol/mmol/mL/mL ratio: 3: (35 to45):(3~4)。
In the above preparation method of the 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 quinoxalinyl conjugated microporous polymer, which comprises the following steps: ultrasonically dispersing the quinoxalinyl conjugated microporous polymer in N, N-dimethylformamide to form a dispersion liquid; and (3) transferring the dispersion liquid 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 standby.
In the above method for preparing an electrochemical sensor, the quinoxaline-based conjugated microporous polymer is dispersed in N, N-dimethylformamide at a concentration of 1.5mg/mL.
The invention also provides a method for detecting dopamine, namely detecting dopamine by using the prepared photoelectrochemical sensor, which 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 so as to obtain a linear relation between photocurrent and the logarithm of the dopamine concentration;
(2) And (3) detection: and (3) detecting the concentration of dopamine in serum to be detected in a phosphate buffer solution by adopting a standard adding method, and determining the content of 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) was 0.2mol/L and the pH was 7.0.
In summary, due to the adoption of the technical scheme, the beneficial effects of the invention are as follows:
1. the invention prepares a novel quinoxaline Conjugated Microporous Polymer (CMP) through Friedel-crafts alkylation reaction, and applies the novel quinoxaline Conjugated Microporous Polymer (CMP) to construction of a photoelectrochemical sensor for detecting dopamine, belonging to the technical field of dopamine detection. The invention adopts a dripping method to drip and coat CMP onto 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 adopts a chronoamperometric detection method to detect dopamine. The result shows that the constructed photoelectrochemical sensor has good photoelectric response to dopamine, the logarithm of photocurrent and dopamine concentration shows 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 provides a new idea for detecting dopamine and widens the application field of conjugated microporous polymers.
2. The method for preparing the CMP has the advantages that the synthesis method is simple and easy to synthesize, the CMP is modified on the ITO electrode to serve as a working electrode, and compared with an electrode of unmodified CMP, 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 chart of CMP and monomer B;
FIG. 3 solid nuclear magnetism of CMP;
FIG. 4 is a photo-current diagram of different concentrations of dopamine solutions on a CMP modified electrode;
FIG. 5 is a plot of the logarithm of dopamine concentration versus photocurrent;
the photocurrent response of the different electrodes of fig. 6.
Detailed Description
The technical solutions of the present invention will be clearly and completely described in conjunction with the embodiments of the present invention, and it is apparent that the described embodiments are only some embodiments of the present invention, but not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without any inventive effort, are intended to be within the scope of the invention.
The invention provides a quinoxalinyl conjugated microporous polymer, which has the structural formula:
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 a monomer: into a round bottom flask, (2.00 mmol,0.62 g) of hexaketocyclohexane octahydrate, (6.00 mmol,1.27 g) (1R, 2R) -1, 2-diphenylethylenediamine and 120.00mL glacial acetic acid were added under N 2 Under protection, reacting for 10 hours at 115 ℃, cooling the reaction product to room temperature, pouring the reaction product into a large beaker, adding ice cubes and distilled water, and forming an ice-water mixture; carrying out suction filtration on the ice-water mixture, washing the precipitate with ethanol, and vacuum drying at 50 ℃ for 12 hours to obtain a monomer B1;
(2) Synthetic CMP: 12.00mL of o-dichlorobenzene, (1.20 mmol,0.22 g) cyanuric chloride, 1.08mLCF 3 SO 3 H. (0.89 mmol,0.61 g) monomer B1 was added to a round bottom flask at N 2 Under the protection, reacting for 52 hours at 135 ℃, 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, each Soxhlet extraction was performed with methanol, THF, acetone for 20 hours, and vacuum drying was performed at 50℃for 12 hours to obtain quinoxalinyl conjugated microporous polymer CMP.
The preparation route of the quinoxalinyl conjugated microporous polymer CMP is as follows:
EXAMPLE 2 preparation of CMP
The preparation method of the quinoxalinyl conjugated microporous polymer adopts the same synthetic route as in the example 1, and comprises the following steps:
(1) Synthesizing a monomer: (2.00 mmol,0.62 g) of hexaketocyclohexane octahydrate, (6.00 mmol,1.27 g) (1R, 2R) -1, 2-Di-hydratePhenylethylenediamine and 100.00mL glacial acetic acid were added to a round bottom flask at N 2 Under the protection, reacting for 12 hours at 120 ℃, cooling the reaction product to room temperature, pouring the reaction product into a large beaker, adding ice cubes and distilled water, and forming an ice-water mixture; carrying out suction filtration on the ice-water mixture, washing the precipitate with ethanol, and vacuum drying at 50 ℃ for 12 hours to obtain a monomer B1;
(2) Synthetic CMP: 10.50mL of o-dichlorobenzene, (1.20 mmol,0.22 g) cyanuric chloride, 0.90mLCF 3 SO 3 H. (0.90 mmol) monomer B1 was added to a round bottom flask at N 2 Under the protection, reacting for 50 hours at 140 ℃, 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, each Soxhlet extraction was performed with methanol, THF, acetone for 24 hours, and vacuum drying was performed at 50℃for 12 hours to obtain 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 in the example 1, and comprises the following steps:
(1) Synthesizing a monomer: into a round bottom flask, (2.00 mmol,0.62 g) of hexaketocyclohexane octahydrate, (6.00 mmol,1.27 g) (1R, 2R) -1, 2-diphenylethylenediamine and 140.00mL glacial acetic acid were added under N 2 Under protection, reacting for 10 hours at 125 ℃, cooling the reaction product to room temperature, pouring the reaction product into a large beaker, adding ice cubes and distilled water, and forming an ice-water mixture; carrying out suction filtration on the ice-water mixture, washing the precipitate with ethanol, and vacuum drying at 50 ℃ for 12 hours to obtain a monomer B1;
(2) Synthetic CMP: 13.50mL of o-dichlorobenzene, (1.20 mmol,0.22 g) cyanuric chloride, 1.20mLCF 3 SO 3 H. (0.89 mmol,0.61 g) monomer B1 was added to a round bottom flask at N 2 Under the protection, reacting for 45h at 145 ℃ to obtain a 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, each Soxhlet extraction was performed with methanol, THF, acetone for 28 hours, and vacuum drying was performed at 50℃for 12 hours to obtain quinoxalinyl conjugated microporous polymer CMP.
2. Characterization of CMP
Using TESCThe morphology of the CMP synthesized in examples 1-3 was characterized by a AN MIRA LMS scanning electron microscope, as shown in FIG. 1. It is clear from the sem image that CMP is of a block-like structure and has a smooth surface. Monomer B and CMP were structurally characterized by a specrum 65 fourier transform infrared spectrometer, as shown in fig. 2. At 1385-1622 cm -1 The absorption peak near the catalyst is the stretching vibration of benzene ring, 614cm -1 The absorption peak at this point is the out-of-plane bending vibration of the C-H bond of the benzene ring. At 3410cm -1 There was a pronounced-OH stretching vibration due to moisture absorption of the sample. It was found from FT-IR spectroscopy that the prepared CMP maintained the characteristic peak of the corresponding monomer at the same position. 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 a carbon atom on the benzene ring, and the peak at 174ppm was attributed to c=n.
3. Preparation of photoelectrochemical sensor
Example 4 preparation of photoelectrochemical sensor
The method for preparing the photoelectrochemical sensor by utilizing the quinoxalinyl conjugated microporous polymer comprises the following steps: 1.5mg of quinoxalinyl conjugated microporous polymer was ultrasonically dispersed in 1mLN, N-dimethylformamide to form a CMP dispersion of 1.5 mg/mL; transferring 15 mu L of dispersion liquid to the conductive surface of the ITO electrode, preparing the CMP modified electrode CMP/ITO, and airing at room temperature for standby.
4. Method for detecting dopamine
Comparative example 1 photoelectric response of ITO Bare electrode (Bare/ITO) to dopamine
The three-electrode system is formed by taking Bare/ITO and CMP/ITO which are not modified with any materials as working electrodes, taking a platinum electrode as an auxiliary electrode and taking an Ag/AgCl electrode as a reference electrode to detect 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 photoelectrochemical sensor prepared in example 4 was used to detect dopamine, comprising the following steps:
(1) Establishing a linear relation: preparing dopamine standard solutions with different concentrations, wherein the concentrations are respectively 0, 0.0125, 0.025, 0.05, 0.125, 0.2, 0.5, 2.5, 5, 12.5 and 35 mu mol/L; 4mL of 0.2mol/L phosphate buffer solution is used as electrolyte (pH 7.0), 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; and constructing a photoelectrochemical sensing platform by adopting a conventional electrochemical workstation, a photoelectrochemical reactor and a three-electrode system. And adding a dopamine standard solution into the electrolyte, and respectively detecting the dopamine standard solutions with different concentrations by adopting a chronoamperometry to obtain a photoelectric diagram (figure 5) of the dopamine solutions with different concentrations on the CMP modified electrode and a relation between the logarithm of the dopamine concentration and the photocurrent (figure 6), wherein the photocurrent increases with the increase of the dopamine concentration. As shown in the graph of fig. 6, the logarithm of the dopamine concentration and the photocurrent show a good linear relationship, the correlation coefficient is 0.9916, and the detection limit is 0.007 μmol/L by the formula lod=3s/K.
(2) And (3) detection: and (3) detecting the concentration of dopamine in serum to be detected in a phosphate buffer solution by adopting a standard adding method, and determining the content of dopamine in the serum according to the linear relation between the photocurrent obtained in the step (1) and the concentration.
5. Reproducibility, stability and selectivity
The reproducibility of the CMP/ITO sensor is continuously examined, 4 CMP/ITO sensors are modified under the same experimental condition, the dopamine with the same concentration is detected, and the obtained peak current value has the relative standard deviation of 0.66%, so that the sensor has good reproducibility. Meanwhile, 1 CMP/ITO electrode is prepared and kept at room temperature, and after 5 days, the peak current value is 96.69% of the first detection current, which indicates that the sensor has better stability.
The foregoing description is directed to the preferred embodiments of the present invention, but the embodiments are not intended to limit the scope of the invention, and all equivalent changes or modifications made under the technical spirit of the present invention should be construed to fall within the scope of the present invention.
Claims (10)
1. A quinoxaline-based conjugated microporous polymer, wherein the quinoxaline-based conjugated microporous polymer has a structural formula:
2. the method for preparing a quinoxalinyl conjugated microporous polymer according to claim 1, comprising the steps of:
(1) Synthesizing a monomer: hexaketocyclohexane octahydrate, (1R, 2R) -1, 2-diphenylethylenediamine and glacial acetic acid were added to a round bottom flask at N 2 Under the protection, reacting for 10-14 h at 115-125 ℃, cooling the reaction product to room temperature, pouring the reaction product into a large beaker, adding ice cubes and distilled water to form an ice-water mixture; carrying out suction filtration on the ice-water mixture, washing the precipitate with ethanol, and drying to obtain a monomer B1;
(2) Synthetic CMP: o-dichlorobenzene, cyanuric chloride and CF 3 SO 3 H. Monomer B1 was added to a round bottom flask at N 2 Under the protection, reacting for 45-52 h at 135-145 ℃ to obtain a 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, each Soxhlet extraction is carried out for 20-28 hours by using methanol, THF and acetone, and the quinoxaline-based conjugated microporous polymer CMP is obtained after drying.
3. The preparation method according to claim 2, characterized in that: in the step (1), the ratio of the (1R, 2R) -1, 2-diphenyl ethylenediamine to glacial acetic acid of the hexaketocyclohexane octahydrate is 1:3: (50-70).
4. The preparation 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 in terms of mmol/mmol/mL/mL ratio: 3: (35-45): (3-4).
5. The preparation method according to claim 2, characterized in that: the drying refers to vacuum drying at 50 ℃.
6. A photoelectrochemical sensor, characterized in that: is obtained by modifying the quinoxaline-based conjugated microporous polymer according to claim 1 on a conductive surface of an ITO electrode.
7. A method of making a photoelectrochemical sensor using a quinoxalinyl conjugated microporous polymer according to claim 1, comprising the steps of: ultrasonically dispersing the quinoxalinyl conjugated microporous polymer in N, N-dimethylformamide to form a dispersion liquid; and (3) transferring the dispersion liquid 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 standby.
8. The method according to claim 7, wherein: the concentration of the quinoxalinyl conjugated microporous polymer dispersed in N, N-dimethylformamide is 1.5mg/mL.
9. A method for detecting dopamine using the photoelectrochemical sensor prepared by the method of claim 7, comprising the steps of:
(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 so as to obtain a linear relation between photocurrent and the logarithm of the dopamine concentration;
(2) And (3) detection: and (3) detecting the concentration of dopamine in serum to be detected in a phosphate buffer solution by adopting a standard adding method, and determining the content of dopamine in the serum according to the linear relation between the photocurrent obtained in the step (1) and the concentration.
10. The method as claimed in 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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