CN113155923B - Carbon nanotube modified cyclodextrin electrode material applied to electrochemical detection and preparation method thereof - Google Patents

Carbon nanotube modified cyclodextrin electrode material applied to electrochemical detection and preparation method thereof Download PDF

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CN113155923B
CN113155923B CN202110289099.1A CN202110289099A CN113155923B CN 113155923 B CN113155923 B CN 113155923B CN 202110289099 A CN202110289099 A CN 202110289099A CN 113155923 B CN113155923 B CN 113155923B
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刘春晔
李晓梅
李云鹏
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Yinuoxin Electric Shenzhen Co ltd
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Abstract

The invention relates to the technical field of electrochemical analysis and detection, and discloses a carbon nano tube modified cyclodextrin electrode material applied to electrochemical detection, wherein an epoxy functionalized carbon nano tube reacts with sodium azide to obtain an azide functionalized carbon nano tube, 4-maleimide butyric acid reacts with beta-cyclodextrin to obtain maleimide cyclodextrin, the maleimide cyclodextrin further reacts with the azide functionalized carbon nano tube to obtain the carbon nano tube modified cyclodextrin electrode material applied to electrochemical detection, the carbon nano tube is covalently grafted with the cyclodextrin to enable the carbon nano tube to be stripped into small bundles or single bundles, the effective catalytic area of the carbon nano tube is increased, the oxidation peak potential is reduced, a three-dimensional network structure is formed at the same time, the interface charge transfer impedance is reduced, the oxidation peak current of an electrode is increased, and the cyclodextrin and bisphenol A can form a host-guest inclusion compound to enable the bisphenol A to be enriched on the surface of the electrode, so that the electrode has excellent performance of analyzing and detecting the bisphenol A.

Description

Carbon nanotube modified cyclodextrin electrode material applied to electrochemical detection and preparation method thereof
Technical Field
The invention relates to the technical field of electrochemical analysis and detection, in particular to a carbon nano tube modified cyclodextrin electrode material applied to electrochemical detection and a preparation method thereof.
Background
Bisphenol A is an important chemical raw material, can be used for producing polycarbonate and epoxy resin, is also an environmental hormone at the same time, can reduce hormone content in human body, thus produce the negative influence to human body, if run short in the bisphenol A environment of high concentration for a long time, even can cause heart disease, diabetes, etc., also there is probability that making a certain liver enzyme content too high even increase and suffer from cancer, polycarbonate plastics and epoxy resin products produced by using bisphenol A as raw materials have also been applied to people's daily life extensively, therefore, it is very important to detect the test method of bisphenol A fast and accurately, even trace, compare with large-scale instrument analytical methods such as liquid chromatogram, gas chromatography, etc., electrochemical detection has advantages such as faster response speed, lower cost, etc., have broad application prospects in bisphenol A detection, but its solid electrode is apt to be polluted, thus cause selectivity and sensitivity to reduce, greatly restrict its application range.
The carbon nano tube has the advantages of unique structure, excellent electrocatalytic performance and the like, is widely applied to the fields of electrochemistry, adsorption and the like, can accelerate electron transfer of an electroactive substance on the surface of an electrode, catalyzes electrochemical reaction of the electroactive substance on the surface of the electrode, enables the electrode modified by the carbon nano tube to have excellent analysis and detection performance, but has strong van der Waals force among the carbon nano tube and cyclodextrin to be easily agglomerated, greatly influences the analysis and detection performance of the modified electrode, has unique hydrophobic internal cavity structure and hydrophilic conical structure, and can form a complex by inclusion of molecules with the sizes matched with the internal cavity structure, so that the cyclodextrin can be widely applied to the fields of molecular recognition, adsorption, biosensing and the like.
Technical problem to be solved
Aiming at the defects of the prior art, the invention provides a carbon nano tube modified cyclodextrin electrode material applied to electrochemical detection and a preparation method thereof, and solves the problems that the carbon nano tube material is easy to agglomerate and has poor detection performance.
(II) technical scheme
In order to achieve the purpose, the invention provides the following technical scheme: a preparation method of a carbon nanotube modified cyclodextrin electrode material applied to electrochemical detection comprises the following steps:
(1) Adding a deionized water solvent, 3-glycidyl ether oxypropyl trimethoxysilane and a carbon nano tube into a reaction bottle, ultrasonically dispersing uniformly, adding acetic acid, ultrasonically dispersing uniformly, reacting for 5-10h at 70-90 ℃, cooling to room temperature, performing centrifugal separation, washing with deionized water, and drying to obtain an epoxy functionalized carbon nano tube;
(2) Adding an N, N-dimethylformamide solvent and an epoxy functionalized carbon nano tube into a reaction bottle, uniformly dispersing by ultrasonic, adding sodium azide and a catalyst aluminum chloride, uniformly dispersing by ultrasonic, reacting, centrifugally separating, washing with deionized water, and drying to obtain an azide functionalized carbon nano tube;
(3) Adding N, N-dimethylformamide solvent, 4-maleimide butyric acid and beta-cyclodextrin into a reaction bottle, uniformly dispersing at a temperature of between 5 ℃ below zero and 0 ℃, adding a condensing agent dicyclohexylcarbodiimide and a catalyst 4-dimethylaminopyridine, uniformly dispersing, carrying out condensation reaction, precipitating a product by using anhydrous ether, carrying out centrifugal separation, and carrying out vacuum drying to obtain maleimide cyclodextrin;
(4) Adding an N, N-dimethylformamide solvent and an azide functionalized carbon nano tube into a reaction bottle, uniformly dispersing by ultrasonic, adding an N, N-dimethylformamide solution of maleimide cyclodextrin, uniformly dispersing by ultrasonic, carrying out cycloaddition reaction, cooling to room temperature, carrying out centrifugal separation, washing with deionized water, and drying to obtain the carbon nano tube modified cyclodextrin electrode material applied to electrochemical detection.
Preferably, in the step (1), the mass ratio of the 3-glycidoxypropyltrimethoxysilane to the carbon nanotube to the acetic acid is 4-6.
Preferably, the mass ratio of the epoxy functionalized carbon nanotube, the sodium azide and the aluminum chloride in the step (2) is 100.
Preferably, the reaction condition in the step (2) is that the reaction is carried out for 18-30h at 20-40 ℃.
Preferably, in the step (3), the mass ratio of the 4-maleimide butyric acid to the beta-cyclodextrin to the dicyclohexylcarbodiimide to the 4-dimethylaminopyridine is 30-60.
Preferably, the condensation reaction in step (3) is carried out at-5 ℃ to 0 ℃ for 6-10h.
Preferably, in the step (4), the mass ratio of the azide functionalized carbon nanotubes to the maleimide cyclodextrin is 3-5.
Preferably, the cycloaddition reaction in the step (4) is carried out at 50-70 ℃ for 18-36h.
(III) advantageous technical effects
Compared with the prior art, the invention has the following beneficial technical effects:
the carbon nanotube modified cyclodextrin electrode material applied to electrochemical detection is characterized in that in an acidic environment, 3-glycidyl ether oxypropyl trimethoxy silane is used for modifying a carbon nanotube to obtain an epoxy functionalized carbon nanotube, rich epoxy groups are introduced, under the catalytic action of Lewis acid and aluminum chloride, the epoxy groups are subjected to ring opening by azido groups, so that rich azido groups are introduced onto the carbon nanotube to obtain an azido functionalized carbon nanotube, under the action of a condensing agent dicyclohexylcarbodiimide and a catalyst 4-dimethylaminopyridine, a carboxyl group on 4-maleimide butyric acid and a hydroxyl group on beta-cyclodextrin undergo dehydration condensation reaction to obtain aminated maleimide cyclodextrin, maleimide rings are introduced, and further undergo 1,3-dipolar cycloaddition with the azido groups on the carbon nanotube to generate triazole five-membered rings, so that the carbon nanotube and the cyclodextrin are subjected to covalent grafting to obtain the carbon nanotube modified cyclodextrin electrode material applied to electrochemical detection.
According to the carbon nanotube modified cyclodextrin electrode material applied to electrochemical detection, the carbon nanotube and cyclodextrin are subjected to covalent grafting, so that the carbon nanotube is stripped into small bundles or single pieces, the dispersibility of the carbon nanotube in an organic solution is improved, the agglomeration phenomenon is reduced, the effective catalytic area of the carbon nanotube is increased, more bisphenol A can be oxidized, the oxidation peak potential is reduced, the analysis detection efficiency of the electrode is improved, a three-dimensional network structure is formed, the interface charge transfer impedance is reduced, the transfer rate of electrons on the surface of the electrode is accelerated, the oxidation peak current of the electrode is increased, the cyclodextrin and the bisphenol A can form a host-guest inclusion compound, the bisphenol A is enriched on the surface of the electrode, the oxidation peak potential of the electrode is further reduced, and the electrode has excellent performance of analyzing and detecting the bisphenol A.
Drawings
FIG. 1 is a schematic diagram of the generation of azide-functionalized carbon nanotubes;
FIG. 2 is a schematic diagram of the formation of maleimido cyclodextrin;
FIG. 3 is a schematic diagram of the generation of a carbon nanotube-modified cyclodextrin electrode material for electrochemical detection.
Detailed Description
To achieve the above object, the present invention provides the following embodiments and examples: a preparation method of a carbon nanotube modified cyclodextrin electrode material applied to electrochemical detection comprises the following steps:
(1) Adding a deionized water solvent, 3-glycidoxypropyltrimethoxysilane and a carbon nano tube into a reaction bottle, ultrasonically dispersing uniformly, adding acetic acid, wherein the mass ratio of the 3-glycidoxypropyltrimethoxysilane to the carbon nano tube to the acetic acid is 4-6 and 10-18, ultrasonically dispersing uniformly, reacting at 70-90 ℃ for 5-10h, cooling to room temperature, performing centrifugal separation, washing with deionized water, and drying to obtain an epoxy functionalized carbon nano tube;
(2) Adding an N, N-dimethylformamide solvent and an epoxy functionalized carbon nanotube into a reaction bottle, uniformly dispersing by ultrasonic, adding sodium azide and a catalyst aluminum chloride, wherein the mass ratio of the epoxy functionalized carbon nanotube to the sodium azide to the aluminum chloride is (100-30);
(3) Adding an N, N-dimethylformamide solvent, 4-maleimide butyric acid and beta-cyclodextrin into a reaction bottle, uniformly dispersing at a temperature of between-5 ℃ and 0 ℃, adding a condensation agent dicyclohexylcarbodiimide and a catalyst 4-dimethylaminopyridine, wherein the mass ratio of the 4-maleimide butyric acid to the beta-cyclodextrin to the dicyclohexylcarbodiimide to the 4-dimethylaminopyridine is (30-60);
(4) Adding an N, N-dimethylformamide solvent and an azide functionalized carbon nanotube into a reaction bottle, uniformly dispersing by ultrasonic, adding an N, N-dimethylformamide solution of maleimide cyclodextrin, wherein the mass ratio of the azide functionalized carbon nanotube to the maleimide functionalized cyclodextrin is 3-5, uniformly dispersing by ultrasonic, carrying out cycloaddition reaction at 50-70 ℃ for 18-36h, cooling to room temperature, carrying out centrifugal separation, washing with deionized water, and drying to obtain the carbon nanotube modified cyclodextrin electrode material applied to electrochemical detection.
Example 1
(1) Adding a deionized water solvent, 3-glycidoxypropyltrimethoxysilane and a carbon nano tube into a reaction bottle, ultrasonically dispersing uniformly, adding acetic acid, wherein the mass ratio of the 3-glycidoxypropyltrimethoxysilane to the carbon nano tube to the acetic acid is 4 to 10, ultrasonically dispersing uniformly, reacting at 70 ℃ for 5 hours, cooling to room temperature, performing centrifugal separation, washing with deionized water, and drying to obtain an epoxy functionalized carbon nano tube;
(2) Adding an N, N-dimethylformamide solvent and an epoxy functionalized carbon nano tube into a reaction bottle, uniformly dispersing by ultrasonic, adding sodium azide and a catalyst aluminum chloride, wherein the mass ratio of the epoxy functionalized carbon nano tube to the sodium azide to the aluminum chloride is 100.2, uniformly dispersing by ultrasonic, reacting for 18h at 20 ℃, performing centrifugal separation, washing with deionized water, and drying to obtain the azide functionalized carbon nano tube;
(3) Adding an N, N-dimethylformamide solvent, 4-maleimide butyric acid and beta-cyclodextrin into a reaction bottle, uniformly dispersing at-5 ℃, adding a condensing agent dicyclohexylcarbodiimide and a catalyst 4-dimethylaminopyridine, wherein the mass ratio of the 4-maleimide butyric acid to the beta-cyclodextrin to the dicyclohexylcarbodiimide to the 4-dimethylaminopyridine is (30);
(4) Adding an N, N-dimethylformamide solvent and an azide functionalized carbon nanotube into a reaction bottle, uniformly dispersing by ultrasonic, adding an N, N-dimethylformamide solution of maleimide cyclodextrin, wherein the mass ratio of the azide functionalized carbon nanotube to the maleimide functionalized cyclodextrin is 3.
Example 2
(1) Adding a deionized water solvent, 3-glycidoxypropyltrimethoxysilane and a carbon nanotube into a reaction bottle, uniformly dispersing by ultrasonic, adding acetic acid, wherein the mass ratio of the 3-glycidoxypropyltrimethoxysilane to the carbon nanotube to the acetic acid is 4.5;
(2) Adding an N, N-dimethylformamide solvent and an epoxy functionalized carbon nanotube into a reaction bottle, performing ultrasonic dispersion uniformly, adding sodium azide and a catalyst aluminum chloride, wherein the mass ratio of the epoxy functionalized carbon nanotube to the sodium azide to the aluminum chloride is 100.5, performing ultrasonic dispersion uniformly, reacting for 21h at 25 ℃, performing centrifugal separation, washing with deionized water, and drying to obtain the azide functionalized carbon nanotube;
(3) Adding an N, N-dimethylformamide solvent, 4-maleimide butyric acid and beta-cyclodextrin into a reaction bottle, uniformly dispersing at the temperature of-4 ℃, adding a condensing agent dicyclohexylcarbodiimide and a catalyst 4-dimethylaminopyridine, wherein the mass ratio of the 4-maleimide butyric acid to the beta-cyclodextrin to the dicyclohexylcarbodiimide to the 4-dimethylaminopyridine is (37.5);
(4) Adding an N, N-dimethylformamide solvent and an azide functionalized carbon nano tube into a reaction bottle, uniformly dispersing by ultrasonic, adding an N, N-dimethylformamide solution of maleimide cyclodextrin, wherein the mass ratio of the azide functionalized carbon nano tube to the maleimide functionalized cyclodextrin is 3.5, uniformly dispersing by ultrasonic, carrying out cycloaddition reaction at 55 ℃ for 22.5h, cooling to room temperature, carrying out centrifugal separation, washing with deionized water, and drying to obtain the carbon nano tube modified cyclodextrin electrode material applied to electrochemical detection.
Example 3
(1) Adding a deionized water solvent, 3-glycidoxypropyltrimethoxysilane and a carbon nano tube into a reaction bottle, ultrasonically dispersing uniformly, adding acetic acid, wherein the mass ratio of the 3-glycidoxypropyltrimethoxysilane to the carbon nano tube to the acetic acid is 5 to 14, ultrasonically dispersing uniformly, reacting for 7.5h at 80 ℃, cooling to room temperature, performing centrifugal separation, washing with deionized water, and drying to obtain an epoxy functionalized carbon nano tube;
(2) Adding an N, N-dimethylformamide solvent and an epoxy functionalized carbon nanotube into a reaction bottle, uniformly dispersing by ultrasonic, adding sodium azide and a catalyst aluminum chloride, wherein the mass ratio of the epoxy functionalized carbon nanotube to the sodium azide to the aluminum chloride is 100.25, uniformly dispersing by ultrasonic, reacting for 24 hours at 30 ℃, performing centrifugal separation, washing with deionized water, and drying to obtain the azide functionalized carbon nanotube;
(3) Adding an N, N-dimethylformamide solvent, 4-maleimide butyric acid and beta-cyclodextrin into a reaction bottle, uniformly dispersing at-3 ℃, adding a condensing agent dicyclohexylcarbodiimide and a catalyst 4-dimethylaminopyridine, wherein the mass ratio of the 4-maleimide butyric acid to the beta-cyclodextrin to the dicyclohexylcarbodiimide to the 4-dimethylaminopyridine is 45;
(4) Adding an N, N-dimethylformamide solvent and an azide functionalized carbon nanotube into a reaction bottle, uniformly dispersing by ultrasonic, adding an N, N-dimethylformamide solution of maleimide cyclodextrin, wherein the mass ratio of the azide functionalized carbon nanotube to the maleimide functionalized carbon nanotube is 4.
Example 4
(1) Adding a deionized water solvent, 3-glycidoxypropyltrimethoxysilane and a carbon nano tube into a reaction bottle, ultrasonically dispersing uniformly, adding acetic acid, wherein the mass ratio of the 3-glycidoxypropyltrimethoxysilane to the carbon nano tube to the acetic acid is 5.5 to 16, ultrasonically dispersing uniformly, reacting at 85 ℃ for 8.75h, cooling to room temperature, performing centrifugal separation, washing with deionized water, and drying to obtain an epoxy functionalized carbon nano tube;
(2) Adding an N, N-dimethylformamide solvent and an epoxy functionalized carbon nanotube into a reaction bottle, uniformly dispersing by using ultrasonic waves, adding sodium azide and a catalyst aluminum chloride, wherein the mass ratio of the epoxy functionalized carbon nanotube to the sodium azide to the aluminum chloride is (100.5), uniformly dispersing by using ultrasonic waves, reacting for 27 hours at 35 ℃, performing centrifugal separation, washing with deionized water, and drying to obtain the azide functionalized carbon nanotube;
(3) Adding an N, N-dimethylformamide solvent, 4-maleimide butyric acid and beta-cyclodextrin into a reaction bottle, uniformly dispersing at-2 ℃, adding a condensing agent dicyclohexylcarbodiimide and a catalyst 4-dimethylaminopyridine, wherein the mass ratio of the 4-maleimide butyric acid to the beta-cyclodextrin to the dicyclohexylcarbodiimide to the 4-dimethylaminopyridine is (52.5);
(4) Adding an N, N-dimethylformamide solvent and an azide functionalized carbon nano tube into a reaction bottle, uniformly dispersing by ultrasonic, adding an N, N-dimethylformamide solution of maleimide cyclodextrin, wherein the mass ratio of the azide functionalized carbon nano tube to the maleimide functionalized cyclodextrin is 4.5, uniformly dispersing by ultrasonic, carrying out cycloaddition reaction at 65 ℃ for 31.5h, cooling to room temperature, carrying out centrifugal separation, washing with deionized water, and drying to obtain the carbon nano tube modified cyclodextrin electrode material applied to electrochemical detection.
Example 5
(1) Adding a deionized water solvent, 3-glycidoxypropyltrimethoxysilane and a carbon nano tube into a reaction bottle, ultrasonically dispersing uniformly, adding acetic acid, wherein the mass ratio of the 3-glycidoxypropyltrimethoxysilane to the carbon nano tube to the acetic acid is 6 to 18, ultrasonically dispersing uniformly, reacting for 10 hours at 90 ℃, cooling to room temperature, performing centrifugal separation, washing with deionized water, and drying to obtain an epoxy functionalized carbon nano tube;
(2) Adding an N, N-dimethylformamide solvent and an epoxy functionalized carbon nano tube into a reaction bottle, uniformly dispersing by ultrasonic, adding sodium azide and a catalyst aluminum chloride, wherein the mass ratio of the epoxy functionalized carbon nano tube to the sodium azide to the aluminum chloride is 100.3, uniformly dispersing by ultrasonic, reacting for 30h at 40 ℃, performing centrifugal separation, washing with deionized water, and drying to obtain the azide functionalized carbon nano tube;
(3) Adding an N, N-dimethylformamide solvent, 4-maleimide butyric acid and beta-cyclodextrin into a reaction bottle, uniformly dispersing at 0 ℃, adding a condensing agent dicyclohexylcarbodiimide and a catalyst 4-dimethylaminopyridine, wherein the mass ratio of the 4-maleimide butyric acid to the beta-cyclodextrin to the dicyclohexylcarbodiimide to the 4-dimethylaminopyridine is 60;
(4) Adding an N, N-dimethylformamide solvent and an azide functionalized carbon nanotube into a reaction bottle, uniformly dispersing by ultrasonic, adding an N, N-dimethylformamide solution of maleimide cyclodextrin, wherein the mass ratio of the azide functionalized carbon nanotube to the maleimide functionalized carbon nanotube is 5.
Comparative example 1
(1) Adding a deionized water solvent, 3-glycidoxypropyltrimethoxysilane and a carbon nanotube into a reaction bottle, uniformly dispersing by ultrasonic, adding acetic acid, wherein the mass ratio of the 3-glycidoxypropyltrimethoxysilane to the carbon nanotube to the acetic acid is 3.2 to 10, uniformly dispersing by ultrasonic, reacting for 7.5h at 80 ℃, cooling to room temperature, performing centrifugal separation, washing with deionized water, and drying to obtain an epoxy functionalized carbon nanotube;
(2) Adding an N, N-dimethylformamide solvent and an epoxy functionalized carbon nano tube into a reaction bottle, uniformly dispersing by ultrasonic, adding sodium azide and a catalyst aluminum chloride, wherein the mass ratio of the epoxy functionalized carbon nano tube to the sodium azide to the aluminum chloride is 100.16, uniformly dispersing by ultrasonic, reacting for 24 hours at 30 ℃, performing centrifugal separation, washing with deionized water, and drying to obtain the azide functionalized carbon nano tube;
(3) Adding an N, N-dimethylformamide solvent, 4-maleimide butyric acid and beta-cyclodextrin into a reaction bottle, uniformly dispersing at-2 ℃, adding a condensing agent dicyclohexylcarbodiimide and a catalyst 4-dimethylaminopyridine, wherein the mass ratio of the 4-maleimide butyric acid to the beta-cyclodextrin to the dicyclohexylcarbodiimide to the 4-dimethylaminopyridine is (24);
(4) Adding an N, N-dimethylformamide solvent and an azide functionalized carbon nano tube into a reaction bottle, uniformly dispersing by ultrasonic, adding an N, N-dimethylformamide solution of maleimide cyclodextrin, wherein the mass ratio of the azide functionalized carbon nano tube to the maleimide cyclodextrin is 4, uniformly dispersing by ultrasonic, carrying out cycloaddition reaction for 27h at 60 ℃, cooling to room temperature, carrying out centrifugal separation, washing with deionized water, and drying to obtain the carbon nano tube modified cyclodextrin electrode material applied to electrochemical detection.
Deionized water, the carbon nanotube modified cyclodextrin electrode material for electrochemical detection obtained in the examples and comparative examples are added into a reaction bottle, ultrasonic dispersion is uniform, the mass concentration is controlled to be 1.0mg/mL, a micropipette is used for transferring 10uL of mixed solution to a bare glass electrode, the mixture is dried only in a nitrogen atmosphere after a solvent is volatilized, the mixture is used as a working electrode, a saturated calomel electrode is used as a reference electrode, a platinum sheet is used as a counter electrode, 0.1mol/L KCl solution containing 10umol/L bisphenol A phenol is used as electrolyte, and a CS350H type electrochemical workstation is used for testing the oxidation peak potential and the oxidation peak current of the electrode material.
Figure BDA0002981705120000101

Claims (4)

1. The carbon nanotube modified cyclodextrin electrode material applied to electrochemical detection is characterized in that: the preparation method of the carbon nanotube modified cyclodextrin electrode material applied to electrochemical detection comprises the following steps:
(1) Adding 3-glycidoxypropyltrimethoxysilane and a carbon nano tube into a deionized water solvent, uniformly dispersing by ultrasonic, adding acetic acid, wherein the mass ratio of the 3-glycidoxypropyltrimethoxysilane to the carbon nano tube to the acetic acid is 4-6 and 10-18, uniformly dispersing by ultrasonic, reacting at 70-90 ℃ for 5-10h, cooling, centrifugally separating, washing and drying to obtain the epoxy functionalized carbon nano tube;
(2) Adding an epoxy functionalized carbon nanotube into an N, N-dimethylformamide solvent, uniformly dispersing by ultrasonic, adding sodium azide and a catalyst aluminum chloride, uniformly dispersing by ultrasonic, reacting, centrifugally separating, washing and drying to obtain an azide functionalized carbon nanotube;
(3) Adding 4-maleimidobutyric acid and beta-cyclodextrin into an N, N-dimethylformamide solvent, uniformly dispersing at the temperature of between 5 ℃ below zero and 0 ℃, adding a condensing agent dicyclohexylcarbodiimide and a catalyst 4-dimethylaminopyridine, wherein the mass ratio of the 4-maleimidobutyric acid to the beta-cyclodextrin to the dicyclohexylcarbodiimide to the 4-dimethylaminopyridine is (30-60);
(4) Adding an azide functionalized carbon nanotube into an N, N-dimethylformamide solvent, uniformly dispersing by ultrasonic, adding an N, N-dimethylformamide solution of maleimide cyclodextrin, wherein the mass ratio of the azide functionalized carbon nanotube to the maleimide cyclodextrin is 3-5, uniformly dispersing by ultrasonic, carrying out cycloaddition reaction, cooling, carrying out centrifugal separation, washing and drying to obtain the carbon nanotube modified cyclodextrin electrode material applied to electrochemical detection.
2. The carbon nanotube modified cyclodextrin electrode material applied to electrochemical detection as claimed in claim 1, wherein: the mass ratio of the epoxy functionalized carbon nanotube, the sodium azide and the aluminum chloride in the step (2) is (100).
3. The carbon nanotube modified cyclodextrin electrode material applied to electrochemical detection as claimed in claim 1, wherein: the reaction condition in the step (2) is that the reaction is carried out for 18 to 30 hours at the temperature of between 20 and 40 ℃.
4. The carbon nanotube modified cyclodextrin electrode material applied to electrochemical detection as claimed in claim 1, wherein: the cycloaddition reaction in the step (4) is carried out for 18-36h at 50-70 ℃.
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