CN110426434B - Construction and application of electrochemical sensor based on copper porphyrin-based covalent organic framework material - Google Patents
Construction and application of electrochemical sensor based on copper porphyrin-based covalent organic framework material Download PDFInfo
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Abstract
The invention provides a preparation method of an electrochemical sensor based on a copper porphyrin based covalent organic framework material, which comprises the steps of firstly modifying a bare electrode with a carboxylated carbon nanotube by using a drop coating part, then modifying the copper porphyrin based covalent organic framework material by using a cyclic voltammetry, and then depositing metal cobalt nano-particles CoNPs on the surface of a modified electrode by using a constant potential deposition method, wherein the prepared modified electrode is the electrochemical sensor based on the copper porphyrin based covalent organic framework material, namely MWCNTs-COOH/CuP-SQ COFs/CoNPs/GCE. The electrochemical sensor is used as a working electrode, a platinum electrode is used as a counter electrode, a saturated calomel electrode is used as a reference electrode, and the simultaneous detection of the guanine and the adenine is realized through a differential pulse voltammetry method. The electrochemical sensor constructed by the invention has the characteristics of high sensitivity, low detection limit, wide linear range, good stability, strong anti-interference capability and the like.
Description
Technical Field
The invention relates to a construction method of an electrochemical sensor based on a copper porphyrin-based covalent organic framework material, in particular to the simultaneous detection of guanine and adenine by the electrochemical sensor, and belongs to the field of electrochemical sensors and analysis and detection.
Background
Guanine (2-amino-6-keto purine) and adenine (6-aminopurine) are two important purine bases in deoxyribonucleic acid (DNA) and ribonucleic acid (RNA). Purine bases are important biomolecules and play an important role in the processes of genetic information storage, cell proliferation, protein biosynthesis and cardiovascular system regulation. Abnormal changes in purine base content in an organism may affect the immune system and cause various diseases including cancer, epileptic lupus erythematosus and anemia. Therefore, accurate detection of guanine and adenine in biological samples is of great significance for assessing disease progression and treatment status of several diseases and early warning of diseases. Currently, various analytical methods have been constructed for detecting the content of guanine and adenine, such as mass spectrometry, high performance liquid chromatography, flow injection chemiluminescence, capillary electrophoresis, and spectroscopic methods. Although these detection methods have high sensitivity and good selectivity, they are time-consuming, expensive, and cumbersome in sample pretreatment. Therefore, the development of a novel and efficient electrochemical sensor is of great significance for reliably, simply and sensitively detecting guanine and adenine simultaneously.
Covalent organic framework materials (COFs) are a new class of porous organic framework materials. The material has received attention from researchers due to its characteristics of good crystallinity, light weight, excellent thermal stability, regular pore structure, large specific surface area, designable structure, and the like. The excellent characteristics enable the material to have great application potential in gas adsorption and storage, heterogeneous catalysis, fluorescence sensing and the like. In 2005, the Yaghi group successfully synthesized COF-1 for the first time, which was obtained by self-condensation of 1, 4-p-diphenylboronic acid. Hitherto, many reactive monomers have been used by researchers to synthesize COFs, and they are roughly classified into triazine series, pyrene series, phthalocyanine series, porphyrin series, and the like, depending on their kinds. Porphyrin has a two-dimensional conjugated pi system and unique photoelectrochemical characteristics, so that the porphyrin has wide application in the fields of electronic devices and catalysis, and porphyrin is introduced into a COFs framework so that the porphyrin has excellent electrocatalytic activity and becomes a potential material applicable to electrochemical sensors.
Disclosure of Invention
The first purpose of the invention is to provide a construction method of an electrochemical sensor based on copper porphyrin-based covalent organic framework material;
the invention also aims to provide the application of the electrochemical sensor constructed as above in detecting guanine and adenine.
Construction of electrochemical sensor based on copper porphyrin-based covalent organic framework material
The invention relates to a construction method of an electrochemical sensor based on a copper porphyrin-based covalent organic framework material, which comprises the following specific steps:
(1) synthesis of copper porphyrin-based covalent organic framework material: mixing metal copper tetra-p-aminophenyl porphyrin and squaric acid (the mass ratio of the metal copper tetra-p-aminophenyl porphyrin to the squaric acid is 1: 2-1: 2.1), adding the mixture into a mixed solvent of n-butyl alcohol and o-dichlorobenzene (the volume ratio of the n-butyl alcohol to the o-dichlorobenzene is 1: 1-1: 1.5), and reacting for 156-168 hours at 90-110 ℃ in an oxygen-free nitrogen protection atmosphere after uniform ultrasonic dispersion; and after the reaction is finished, centrifugally washing, and drying in vacuum to obtain mauve powder, namely the copper porphyrin-based covalent organic framework material which is marked as CuP-SQ COFs.
(2) Preparing modified electrode MWCNTs-COOH/GCE: ultrasonically dispersing a carboxylated carbon nanotube (MWCNTs-COOH) in DMF (the concentration of the MWCNTs-COOH is 0.8 mg/mL-1.2 mg/mL), dripping the MWCNTs-COOH on the surface of a glassy carbon electrode which is polished completely, and drying to obtain a modified electrode MWCNTs-COOH/GCE;
preparation of carboxylated carbon nanotubes (MWCNTs-COOH): dispersing the multi-walled carbon nano-tube in concentrated nitric acid, stirring and heating at 70-85 ℃ for reflux for 35-40 h, cooling to room temperature, washing with distilled water to be neutral, and drying in vacuum to obtain a purified multi-walled carbon nano-tube; dispersing the purified multi-walled carbon nanotubes in a mixed solution of concentrated sulfuric acid and concentrated nitric acid (the concentration of the concentrated nitric acid is 69 wt%, the concentration of the concentrated sulfuric acid is 98 wt%, and the volume ratio of the concentrated nitric acid to the concentrated sulfuric acid is 1: 3.), stirring for 5-7 h at 45-60 ℃, filtering the mixture with a 0.22 mu m filter membrane after cooling, and repeatedly washing with distilled water to be neutral, wherein the product is the carboxylated carbon nanotube MWCNTs-COOH.
(3) Preparing modified electrode MWCNTs-COOH/CuP-SQ COFs/GCE: placing the modified electrode MWCNTs-COOH/GCE prepared in the step (2) in a DMF (dimethyl formamide) solution of CuP-SQ COFs, and uniformly electrodepositing the CuP-SQ COFs onto the surface of the modified electrode MWCNTs-COOH/GCE by using a cyclic voltammetry method to obtain the modified electrode MWCNTs-COOH/CuP-SQ COFs/GCE;
the concentration of the CuP-SQ COFs in the DMF solution is 1 mg/mL-1.5 mg/mL;
the technological conditions of cyclic voltammetry electrodeposition are as follows: the potential window is-0.8-1.6V, the scanning rate is 20-25 mV/s, and the number of scanning cycles is 3-7 cycles.
(4) Preparing modified electrode MWCNTs-COOH/CuP-SQ COFs/Co NPs/GCE: placing the modified electrode MWCNTs-COOH/CuP-SQ COFs/GCE prepared in the step (3) into a catalyst containing Co (NO)3)20.1M KNO3In the solution, depositing metal cobalt nanoparticles (CoNPs) on the surface of a modified electrode by using a constant potential deposition method to prepare the modified electrode MWCNTs-COOH/CuP-SQ COFs/CoNPs/GCE, namely the electrochemical sensor based on the copper porphyrin-based covalent organic framework material;
Co(NO3)20.1M KNO3In solution, Co (NO)3)2Is 2.0X 10-3M~3.5×10-3M；
The process conditions of the constant potential deposition method are as follows: the potential is-0.4V, and the deposition time is 50-400 s.
FIG. 1 shows a naked electrode GCE (a) and different modified electrodes MWCNTs-COOH/GCE (b), MWCNTs-COOH/CuP-SQ COFs/GCE (c), MWCNTs-COOH/CuP-SQ COFs/Co NPs/GCE (d) at 0.1 mM Fe (CN)6 3-/4-And Cyclic Voltammetry (CV) curves in 0.1M KCl solution. The CV diagram shows that the peak current intensity of the curves a-d is gradually increased, which shows that the modified materials MWCNTs-COOH, CuP-SQ COFs and Co NPs can effectively improve the conductivity of the glassy carbon electrode and is beneficial to the transfer of electrons on the surface of the electrode.
II, detecting guanine and adenine based on copper porphyrin based covalent organic framework material electrochemical sensor
The MWCNTs-COOH/CuP-SQ COFs/Co NPs/GCE prepared by the method is used as a working electrode, a glass slide electrode is used as a counter electrode, and a saturated calomel electrode is used as a reference electrode. In a phosphate buffer solution with pH =3.5, a Differential Pulse Voltammetry (DPV) is used for electrochemically detecting a solution to be detected of guanine and adenine, and a corresponding linear curve is obtained according to the relationship between the current intensity and the concentration of the sensor in an object to be detected.
FIG. 2 is a CV diagram of a naked electrode GCE (a) and different modified electrodes MWCNTs-COOH/GCE (b), MWCNTs-COOH/CuP-SQ COFs/GCE (c), MWCNTs-COOH/CuP-SQ COFs/Co NPs/GCE (d) in a mixed solution of guanine and adenine. As can be seen from FIG. 2, in the mixed solution of guanine and adenine, two pairs of obvious oxidation peaks appear and the peak current intensity gradually increases in different modified electrodes, which indicates that the constructed MWCNTs-COOH/CuP-SQ COFs/Co NPs/GCE modified electrode has better electrocatalytic activity on guanine and adenine, the potential difference between the two pairs of oxidation peaks is about 300 mV, and the simultaneous detection on guanine and adenine can be realized.
The concentration of guanine was varied (0.02, 0.05, 0.07, 0.5, 0.8, 2, 5, 8, 20, 40, 60, 80, 100, 130 μ M), the concentration of adenine was kept constant (20 μmol/L), detection was performed by DPV, a DPV curve of current intensity and guanine concentration was obtained (fig. 3), and a linear graph of peak current value and guanine concentration was obtained (fig. 4). As can be seen from FIG. 4, when the concentration of guanine is in the range of 0.02-40 [ mu ] mol/L, the linear relationship is as follows: ipa = -0.9967 c-0.7715 (r = 0.9962); when the concentration of guanine is in the range of 40-130 [ mu ] mol/L, the linear relation is Ipa = -0.2539 c-30.1341 (r = 0.9935); wherein, c-concentration of guanine, unit: mu mol/L; ipa-maximum peak current, unit: and mu A. The detection limit is: 0.0040 mu mol/L.
The concentration of adenine was varied (0.05, 0.08, 0.5, 0.8, 2, 5, 8, 15, 20, 25, 40, 60, 80, 100, 130 μ M), the concentration of guanine was kept constant (20 μmol/L), detection was performed by DPV, a DPV curve of current intensity and adenine concentration was obtained (fig. 5), and a linear graph of peak current value and adenine concentration was obtained (fig. 6). As can be seen from FIG. 6, when the concentration of adenine is in the range of 0.05 to 25 μmol/L, the linear relationship is Ipa = -0.6047 c-0.5828 (r = 0.9950); when the concentration of adenine is 25-130 [ mu ] mol/L, the linear relation is Ipa = -0.1898 c-11.0629 (r = 0.9953). Wherein, the concentration of c-adenine, unit: mu mol/L. Ipa-maximum peak current, unit: and mu A. The detection limit is: 0.0067 μmol/L.
And (3) repeatability test: under optimized experimental conditions, the prepared modified electrode is continuously and parallelly measured for 20 times by using DPV in the same solution to be measured. The relative standard deviation of the peak current intensity of guanine is about 4.73%, the relative standard deviation of the peak current intensity of adenine is about 4.13%, and the experimental result shows that the electrochemical sensor has better reproducibility.
And (3) testing the anti-interference capability: under optimized experimental conditions, 100 times of inorganic ion interferent (K)+、Na+、Ga2+、Zn2+、Mg2+、Cl-、NO3 -) And 50 times of organic small molecule interferent (uric acid, dopamine, ascorbic acid, glucose, sucrose and L-glutamic acid) is added into the substance to be detected to evaluate the selectivity and the anti-interference capability of the electrode on the detection of guanine and adenine. The result shows that the electrochemical sensor constructed by the invention has stronger anti-interference performance to the interferent (figure 7), and also shows better selectivity of the sensor.
Drawings
FIG. 1 shows a naked electrode GCE (a) and different modified electrodes MWCNTs-COOH/GCE (b), MWCNTs-COOH/CuP-SQ COFs/GCE (c), MWCNTs-COOH/CuP-SQ COFs/Co NPs/GCE (d) at 0.1 mM Fe (CN)6 3-/4-And cyclic voltammograms in 0.1M KCl solution.
FIG. 2 is a CV diagram of a naked electrode GCE (a) and different modified electrodes MWCNTs-COOH/GCE (b), MWCNTs-COOH/CuP-SQ COFs/GCE (c), MWCNTs-COOH/CuP-SQ COFs/Co NPs/GCE (d) in a mixed solution of guanine and adenine.
FIG. 3 is a DPV graph of guanine concentration variation when modified electrode MWCNTs-COOH/CuP-SQ COFs/Co NPs/GCE is used for simultaneously detecting guanine and adenine.
FIG. 4 is a linear relationship graph of peak current intensity and guanine concentration change when modified electrode MWCNTs-COOH/CuP-SQ COFs/Co NPs/GCE detects guanine and adenine simultaneously.
FIG. 5 is a DPV graph of the change of adenine concentration when simultaneously detecting guanine and adenine in modified electrode MWCNTs-COOH/CuP-SQ COFs/Co NPs/GCE.
FIG. 6 is a linear relation curve diagram of peak current intensity and adenine concentration change when simultaneously detecting guanine and adenine for modified electrode MWCNTs-COOH/CuP-SQ COFs/CoNPs/GCE.
FIG. 7 shows modified electrode MWCNTs-COOH/CuP-SQ COFs/Co NPs/GCE on uric acid, dopamine, ascorbic acid, glucose, sucrose, L-glutamic acid and various inorganic ions (K)+、Na+、Ga2+、Zn2+、Mg2+、Cl-、NO3 -) Schematic representation of interference rejection capability.
Detailed Description
The construction method and application of the electrochemical sensor based on copper porphyrin-based covalent organic framework material of the present invention are further illustrated by the following specific examples.
EXAMPLE 1 construction of electrochemical sensor
(1) Preparation of carboxylated multi-walled carbon nanotubes (MWCNTs-COOH): 0.5g of multi-walled carbon nanotubes is weighed and dispersed in 90mL of concentrated nitric acid, heated and refluxed at 80 ℃, and stirred for 40 h. And cooling to room temperature after the reaction is finished, washing to be neutral by using distilled water, and drying in vacuum at 50 ℃ to obtain the purified multi-walled carbon nano tube. Dispersing 300mg of purified multiwalled carbon nanotubes in a mixed solution of concentrated sulfuric acid (45 mL) and concentrated nitric acid (135 mL), stirring for 6h at 50 ℃, cooling, performing suction filtration on the mixture with a filter membrane of 0.22 mu m, and repeatedly washing the mixture with distilled water to be neutral, wherein the product is MWCNTs-COOH;
(2) synthesis of copper porphyrin-based covalent organic framework materials (CuP-SQ COFs): adding a mixture of 162 mg of metal copper tetra-p-aminophenylporphyrin and 51mg of squaric acid into 2mL of a mixed solvent of n-butanol and o-dichlorobenzene (volume ratio is 1: 1), ultrasonically dispersing the mixture uniformly, transferring the mixture into a 10 mL glass tube, performing three cycles of liquid nitrogen freezing-degassing-thawing, and sealing the tube opening by using a flame gun. After reaching room temperature, the reaction mixture was placed in an oven at 90 ℃ for 7 days. Opening the tube, collecting precipitates by high-speed centrifugation, washing the precipitates for a plurality of times by tetrahydrofuran and anhydrous acetone in sequence, and drying the precipitates for 24 hours in vacuum at 150 ℃ to obtain mauve powder, namely CuP-SQ COFs;
(3) preparing modified electrode MWCNTs-COOH/GCE: MWCNTs-COOH is dispersed in a DMF solvent, and the MWCNTs-COOH is dispersed uniformly by ultrasonic. Transferring a solution of 7 mu of LMWCNTs-COOH by using a micro-pipette gun, dripping the solution on the surface of the polished glassy carbon electrode, and drying to obtain a modified electrode MWCNTs-COOH/GCE;
(4) preparing modified electrode MWCNTs-COOH/CuP-SQ COFs/GCE: placing the modified electrode MWCNTs-COOH/GCE in a 1mg/mL solution of CuP-SQ COFs DMF, utilizing a cyclic voltammetry method, under a potential window of-0.8-1.6V, the scanning rate is 25mV/s, the number of scanning cycles is 4, and uniformly electrodepositing the CuP-SQ COFs on the surface of the modified electrode MWCNTs-COOH/GCE to obtain the modified electrode MWCNTs-COOH/CuP-SQ COFs/GCE;
(5) preparing modified electrode MWCNTs-COOH/CuP-SQ COFs/Co NPs/GCE: the prepared modified electrode MWCNTs-COOH/CuP-SQ COFs/GCE is placed in a medium containing 3.0 multiplied by 10-3M Co(NO3)20.1M KNO3In the solution, the Co NPs are electrodeposited for 300s under-0.2V by adopting a current-time curve method, and are deposited on the surface of a modified electrode to prepare the modified electrode MWCNTs-COOH/CuP-SQ COFs/Co NPs/GCE, namely the electrochemical sensor based on the copper porphyrin-based covalent organic framework material.
Example 2 detection of Low concentrations of guanine and adenine
(1) Preparation of sample solution: preparing guanine and adenine solutions of 15 micromole/L and 25mL in a phosphate buffer solution with pH =3.5 respectively;
(2) electrochemical detection: taking a modified electrode MWCNTs-COOH/CuP-SQ COFs/Co NPs/GCE as a working electrode, taking a platinum electrode as a counter electrode, taking a saturated calomel electrode as a reference electrode, carrying out electrochemical detection on a solution to be detected of guanine and adenine by using a Differential Pulse Voltammetry (DPV) method to obtain a maximum peak current Ipa value, and respectively calculating concentration values of guanine and adenine according to linear relations Ipa = -0.9967 c-0.7715 and Ipa = -0.6047 c-0.5828. The calculation result is 15.34 mu mol/L and 14.81 mu mol/L.
Example 3 detection of high concentrations of guanine and adenine
(1) Preparation of sample solution: preparing guanine and adenine solutions of 80 [ mu ] mol/L and 25mL in a phosphate buffer solution with pH =3.5 respectively;
(2) electrochemical detection: taking a modified electrode MWCNTs-COOH/CuP-SQ COFs/Co NPs/GCE as a working electrode, taking a platinum electrode as a counter electrode, taking a saturated calomel electrode as a reference electrode, carrying out electrochemical detection on a solution to be detected of guanine and adenine by using a Differential Pulse Voltammetry (DPV) method to obtain a maximum peak current Ipa value, and respectively calculating concentration values of guanine and adenine according to linear relations Ipa = -0.2539 c-30.1341 and Ipa = -0.1898 c-11.0629. The calculation result is 80.28 mu mol/L and 49.67 mu mol/L.
Claims (10)
1. The application of the electrochemical sensor based on the copper porphyrin group covalent organic framework material in the detection of guanine is characterized in that: the method comprises the following steps of taking a modified electrode MWCNTs-COOH/CuP-SQ COFs/Co NPs/GCE as a working electrode, taking a platinum electrode as a counter electrode and a saturated calomel electrode as a reference electrode, scanning in a potential range of 0.6-1.3V by using a differential pulse voltammetry method to obtain a maximum peak current Ipa value, and calculating according to the following linear relation to obtain the concentration of guanine:
when the concentration of guanine is in the range of 0.02-40 [ mu ] mol/L, the linear relation is as follows: ipa = -0.9967 c-0.7715, r = 0.9962; when the concentration of guanine is in the range of 40-130 [ mu ] mol/L, the linear relation is Ipa = -0.2539 c-30.1341, and r = 0.9935; wherein, c-the concentration of guanine, unit: mu mol/L; ipa-maximum peak current, in units: mu A;
the construction method of the electrochemical sensor based on the copper porphyrin based covalent organic framework material comprises the following specific steps:
(1) synthesis of copper porphyrin-based covalent organic framework material: mixing metal copper tetra-p-aminophenylporphyrin and squaric acid, adding the mixture into a mixed solvent of n-butyl alcohol and o-dichlorobenzene, performing ultrasonic dispersion uniformly, and reacting at 90-110 ℃ for 156-168 hours in an oxygen-free nitrogen protection atmosphere; after the reaction is finished, centrifugally washing and vacuum drying to obtain mauve powder, namely copper porphyrin-based covalent organic framework material marked as CuP-SQ COFs; the mass ratio of the metal copper tetra-p-aminophenylporphyrin to the squaric acid is 1:2 to 1: 2.1;
(2) preparing modified electrode MWCNTs-COOH/GCE: ultrasonically dispersing a carboxylated carbon nanotube (MWCNTs-COOH) in DMF (dimethyl formamide), dripping the DMF on the surface of a glassy carbon electrode which is polished cleanly, and drying to obtain a modified electrode MWCNTs-COOH/GCE;
(3) preparing modified electrode MWCNTs-COOH/CuP-SQ COFs/GCE: placing the modified electrode MWCNTs-COOH/GCE prepared in the step (2) in a DMF (dimethyl formamide) solution of CuP-SQ COFs, and uniformly electrodepositing the CuP-SQ COFs onto the surface of the modified electrode MWCNTs-COOH/GCE by using a cyclic voltammetry method to obtain the modified electrode MWCNTs-COOH/CuP-SQ COFs/GCE; the technological conditions of cyclic voltammetry electrodeposition are as follows: the potential window is-0.8-1.6V, the scanning speed is 20-25 mV/s, and the number of scanning turns is 3-7 turns;
(4) preparing modified electrode MWCNTs-COOH/CuP-SQ COFs/Co NPs/GCE: placing the modified electrode MWCNTs-COOH/CuP-SQ COFs/GCE prepared in the step (3) into a catalyst containing Co (NO)3)20.1M KNO3In the solution, depositing metallic cobalt nano-particles CoNPs on the surface of a modified electrode by using a constant potential deposition method to prepare the modified electrode MWCNTs-COOH/CuP-SQ COFs/CoNPs/GCE, namely the electrochemical sensor based on the copper porphyrin-based covalent organic framework material; the process conditions of the constant potential deposition method are as follows: the potential is-0.4V, and the deposition time is 50-400 s.
2. Use of an electrochemical sensor based on copper porphyrin based covalent organic framework material according to claim 1 for the detection of guanine, wherein: in the mixed solvent of n-butanol and o-dichlorobenzene in the step (1), the volume ratio of n-butanol to o-dichlorobenzene is 1: 1-1: 1.5.
3. Use of an electrochemical sensor based on copper porphyrin based covalent organic framework material according to claim 1 for the detection of guanine, wherein: in the step (2), the concentration of the carboxylated carbon nanotube MWCNTs-COOH in DMF is 0.8 mg/mL-1.2 mg/mL.
4. Use of an electrochemical sensor based on copper porphyrin based covalent organic framework material according to claim 1 for the detection of guanine, wherein: in the step (3), the concentration of the CuP-SQ COFs in the DMF solution is 1 mg/mL-1.5 mg/mL.
5. Use of an electrochemical sensor based on copper porphyrin based covalent organic framework material according to claim 1 for the detection of guanine, wherein: in step (4), Co (NO)3)20.1M KNO3In solution, Co (NO)3)2Is 2.0X 10-3M~3.5×10-3M。
6. The application of the electrochemical sensor based on the copper porphyrin group covalent organic framework material in the detection of adenine is characterized in that: the method is characterized in that: the method comprises the following steps of taking a modified electrode MWCNTs-COOH/CuP-SQ COFs/Co NPs/GCE as a working electrode, taking a platinum electrode as a counter electrode and a saturated calomel electrode as a reference electrode, scanning in a potential range of 0.6-1.3V by using a differential pulse voltammetry method to obtain a maximum peak current Ipa value, and calculating the concentration of adenine according to the following linear relation:
when the concentration of adenine is in the range of 0.05-25 [ mu ] mol/L, the linear relation is Ipa = -0.6047 c-0.5828, and r = 0.9950; when the concentration of adenine is 25-130 [ mu ] mol/L, the linear relation is Ipa = -0.1898 c-11.0629, and r = 0.9953; wherein, c-concentration of adenine, unit: mu mol/L; ipa-maximum peak current, in units: mu A;
the construction method of the electrochemical sensor based on the copper porphyrin based covalent organic framework material comprises the following specific steps:
(1) synthesis of copper porphyrin-based covalent organic framework material: mixing metal copper tetra-p-aminophenylporphyrin and squaric acid, adding the mixture into a mixed solvent of n-butyl alcohol and o-dichlorobenzene, performing ultrasonic dispersion uniformly, and reacting at 90-110 ℃ for 156-168 hours in an oxygen-free nitrogen protection atmosphere; after the reaction is finished, centrifugally washing and vacuum drying to obtain mauve powder, namely copper porphyrin-based covalent organic framework material marked as CuP-SQ COFs; the mass ratio of the metal copper tetra-p-aminophenylporphyrin to the squaric acid is 1:2 to 1: 2.1;
(2) preparing modified electrode MWCNTs-COOH/GCE: ultrasonically dispersing a carboxylated carbon nanotube (MWCNTs-COOH) in DMF (dimethyl formamide), dripping the DMF on the surface of a glassy carbon electrode which is polished cleanly, and drying to obtain a modified electrode MWCNTs-COOH/GCE;
(3) preparing modified electrode MWCNTs-COOH/CuP-SQ COFs/GCE: placing the modified electrode MWCNTs-COOH/GCE prepared in the step (2) in a DMF (dimethyl formamide) solution of CuP-SQ COFs, and uniformly electrodepositing the CuP-SQ COFs onto the surface of the modified electrode MWCNTs-COOH/GCE by using a cyclic voltammetry method to obtain the modified electrode MWCNTs-COOH/CuP-SQ COFs/GCE; the technological conditions of cyclic voltammetry electrodeposition are as follows: the potential window is-0.8-1.6V, the scanning speed is 20-25 mV/s, and the number of scanning turns is 3-7 turns;
(4) preparing modified electrode MWCNTs-COOH/CuP-SQ COFs/Co NPs/GCE: placing the modified electrode MWCNTs-COOH/CuP-SQ COFs/GCE prepared in the step (3) into a catalyst containing Co (NO)3)20.1M KNO3In the solution, depositing metallic cobalt nano-particles CoNPs on the surface of a modified electrode by using a constant potential deposition method to prepare the modified electrode MWCNTs-COOH/CuP-SQ COFs/CoNPs/GCE, namely the electrochemical sensor based on the copper porphyrin-based covalent organic framework material; the process conditions of the constant potential deposition method are as follows: the potential is-0.4V, and the deposition time is 50-400 s.
7. The use of the electrochemical sensor based on copper porphyrin based covalent organic framework material according to claim 6 for the detection of adenine, wherein: in the mixed solvent of n-butanol and o-dichlorobenzene in the step (1), the volume ratio of n-butanol to o-dichlorobenzene is 1: 1-1: 1.5.
8. The use of the electrochemical sensor based on copper porphyrin based covalent organic framework material according to claim 6 for the detection of adenine, wherein: in the step (2), the concentration of the carboxylated carbon nanotube MWCNTs-COOH in DMF is 0.8 mg/mL-1.2 mg/mL.
9. The use of the electrochemical sensor based on copper porphyrin based covalent organic framework material according to claim 6 for the detection of adenine, wherein: in the step (3), the concentration of the CuP-SQ COFs in the DMF solution is 1 mg/mL-1.5 mg/mL.
10. The use of the electrochemical sensor based on copper porphyrin based covalent organic framework material according to claim 6 for the detection of adenine, wherein: in step (4), Co (NO)3)20.1M KNO3In solution, Co (NO)3)2Is 2.0X 10-3M~3.5×10-3M。
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| CN113504274B (en) * | 2021-07-20 | 2023-11-21 | 郑州轻工业大学 | Covalent organic framework material, preparation method and application thereof, aptamer sensor and preparation method thereof |
| CN114324515B (en) * | 2021-12-01 | 2022-09-27 | 江南大学 | Electrochemical sensor for detecting glyphosate based on copper porphyrin metal organic framework modified carbon paper electrode |
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