CN112285175B - Preparation method and application of molecularly imprinted sensor of boric acid functionalized carbon quantum dot-polymer modified electrode - Google Patents

Preparation method and application of molecularly imprinted sensor of boric acid functionalized carbon quantum dot-polymer modified electrode Download PDF

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CN112285175B
CN112285175B CN202011077873.4A CN202011077873A CN112285175B CN 112285175 B CN112285175 B CN 112285175B CN 202011077873 A CN202011077873 A CN 202011077873A CN 112285175 B CN112285175 B CN 112285175B
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吴海燕
郑伟
闫煜
熊菊
高文俊
梁国斌
徐吉成
邱凤仙
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Jiangsu University of Technology
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Abstract

The invention relates to a preparation method and application of a molecularly imprinted sensor of a boric acid functionalized carbon quantum dot-polymer modified electrode, which comprises the following steps: heating 3-aminophenylboronic acid and sodium citrate in an alkaline solution to react to prepare a boric acid functionalized carbon quantum dot solution, adding a glucose solution, a PBS (phosphate buffer solution) and an electrode, adjusting the pH value to 8-11 at a chemical room temperature, and polymerizing to form a film by an electrochemical method to obtain the boric acid functionalized carbon quantum dot-polymer modified electrode; and finally, eluting the template molecule glucose to obtain the boric acid functionalized carbon quantum dot-polymer modified electrode molecularly imprinted sensor. The method is applied to the detection of glucose under physiological conditions or the detection of glucose in fermentation liquor products. The molecularly imprinted sensor of the boric acid functionalized carbon quantum dot-polymer modified electrode prepared by the method has good specificity recognition response on glucose, has high sensitivity and selectivity, and can realize quick and efficient detection on glucose.

Description

Preparation method and application of molecularly imprinted sensor of boric acid functionalized carbon quantum dot-polymer modified electrode
Technical Field
The invention relates to the technical field of electrochemical sensor preparation, in particular to a preparation method and application of a molecularly imprinted sensor of a boric acid functionalized carbon quantum dot-polymer modified electrode.
Background
Glucose is the energy source of the cell and is one of the most important biological species for diagnosing diabetes. Diabetes mellitus caused by long-term hyperglycemia and complications thereof is attracting high attention. In recent years, the prevalence of diabetes in china has gradually increased, as in countries around the world, and the influence of diabetes on the health of people in china has become more and more serious. In addition, glucose is a common reactant and an intermediate product in the microbial fermentation process, is one of the most important indexes needing to be controlled in the fermentation process, and is directly related to the yield and the quality of a product.
At present, a plurality of methods for detecting glucose exist, such as spectrophotometry, colorimetry, chromatography and the like, and the methods are labor-consuming and time-consuming and have low sensitivity. The electrochemical biosensor has the advantages of simple structure, simple and convenient operation, simple method, rapidness, real time, higher sensitivity and selectivity, and easy miniaturization. Wherein the enzyme-free electrochemical sensor results in poor selectivity of the sensor due to non-specific electrocatalytic effects of the active material on the analyte. The specific high selectivity of the sensor is combined with an electrochemical sensor by adopting a molecular imprinting technology, so that the molecular imprinting sensor with specific recognition response to glucose can be prepared. But the sensitivity and selectivity of a general electrochemical sensor are poor.
Boron affinity materials have been developed vigorously in recent ten years as a functional material for selectively separating and enriching cis-dihydroxy biomolecules. Boric acid derivatives have been widely used in the design and synthesis of cis-diol sensors. The fluorescent carbon dots, which are carbon nanomaterials newly explored in recent years, generally contain a large number of oxygen-containing groups on the surface, and the oxygen content of the surface can be differentiated by different synthesis methods and surface treatment methods. In addition, the fluorescent carbon dots have the characteristics of discontinuous emission and dispersion of fluorescence, high fluorescence stability, small particle size, low toxicity and the like. Chinese patent 201810044606.3 discloses preparation and application of a carbon dot-chitosan modified glassy carbon electrode-based molecular imprinting sensor, wherein a prepared solid carbon quantum dot and a chitosan acetic acid solution are mixed, then the glassy carbon electrode is subjected to surface treatment, then the carbon quantum dot-chitosan modified glassy carbon electrode is placed in a mixed solution of glucose serving as a template molecule, 3-aminophenylboronic acid serving as a functional monomer and a borax buffer solution, and polymerized into a film by an electrochemical method under an alkaline condition; in the patent, the carbon quantum dots modified by chitosan and 3-aminophenylboronic acid are compounded and polymerized to form a film, and the chitosan is used as a film forming agent. Although the molecular sensor prepared by the patent method has high selectivity and sensitivity to a certain extent, the sensitivity and the selectivity are still required to be further improved.
Disclosure of Invention
In order to further improve the technical problems of sensitivity and selectivity of the molecular imprinting sensor, a preparation method and application of the molecular imprinting sensor of the boric acid functionalized carbon quantum dot-polymer modified electrode are provided. The molecular imprinting sensor prepared by the method has higher selectivity and sensitivity.
In order to achieve the purpose, the invention is realized by the following technical scheme:
the preparation method of the molecularly imprinted sensor of the boric acid functionalized carbon quantum dot-polymer modified electrode comprises the following steps:
(1) Dissolving 3-aminophenylboronic acid and sodium citrate in water, adjusting the pH value to 9, introducing nitrogen to react for 1h, heating to 140-160 ℃, continuing to react for 6-8 h, cooling to room temperature after the reaction is finished, filtering and centrifuging to obtain a boronic acid functionalized carbon quantum dot stock solution, and adding water to dilute the stock solution to obtain a boronic acid functionalized carbon quantum dot solution;
(2) Stirring and mixing the boric acid functionalized carbon quantum dot solution, the glucose solution and the PBS buffer solution uniformly at room temperature to obtain a molecular imprinting precursor mixed solution; placing the electrode after polishing, grinding and cleaning in the molecular imprinting precursor mixed solution, adjusting the pH value to 8-11, and polymerizing to form a film by an electrochemical method to obtain a boric acid functionalized carbon quantum dot-polymer modified electrode;
(3) And eluting template molecule glucose of the boric acid functionalized carbon quantum dot-polymer modified electrode by adopting an organic acid washing stripping solution to obtain the boric acid functionalized carbon quantum dot-polymer modified electrode molecularly imprinted sensor.
Further, the mass ratio of the 3-aminophenylboronic acid to the sodium citrate in the step (1) is 1 (5-20), preferably 1:7; the concentration of the 3-aminophenylboronic acid in the water is 0.005 g-mL -1 。
Further, the volume ratio of the stock solution to the water added for diluting the stock solution in the step (1) is 1; the molar concentration of the glucose solution is 0.1M; the molar concentration of the PBS buffer solution is 0.05M; the volume ratio of the glucose solution to the boric acid functionalized carbon quantum dot solution to the PBS buffer solution is (0.1-1): 1.
Further, the heating temperature in the step (1) is preferably 160 ℃, and the reaction time is preferably 8h; the pH value in the step (2) is 9.
Further, the electrochemical method in the step (2) is carried out in a potential range of-0.2V to 0.6V at a value of 50 mV.s -1 The film was electrochemically polymerized into a film by scanning for 20 cycles at the scanning rate of (2).
Further, the organic acid eluent in the step (3) is 10% volume fraction acetic acid solution, and the acetic acid solution contains 1wt% of SDS. SDS contributes to the effective elution of glucose, and if SDS is not added, a large amount of glucose remaining on the subsequently prepared sensor adversely affects the electrochemical detection performance of the sensor for glucose.
Still further, the process of eluting the template molecule glucose is to place the obtained boric acid functionalized carbon quantum dot-polymer modified electrode in the eluent to carry out electrochemical elution for 50 to 300 circles, preferably 240 circles, by a cyclic voltammetry method.
On the other hand, the invention provides the application of the boric acid functionalized carbon quantum dot-polymer modified electrode molecular imprinting sensor prepared by the method in glucose detection under physiological conditions or glucose detection in fermentation liquor.
The synthesis principle of the invention is as follows: sodium citrate and 3-aminophenylboronic acid are taken as reaction raw materials, no additional modification reagent is needed to be added in the reaction preparation process, and the boric acid functionalized carbon quantum dot is prepared by a simple one-step method. The reaction raw materials of sodium citrate and benzene ring in 3-aminophenylboronic acid can be used as carbon sources for preparing carbon quantum dots. In addition, the boronic acid functional group in the 3-aminophenylboronic acid has a selective recognition effect on cis-diol molecules (such as polyols and saccharides).
The beneficial technical effects are as follows:
the preparation-functionalization is completed through a one-step method, and the boric acid functionalized carbon quantum dot is prepared by taking sodium citrate and 3-aminophenylboronic acid as precursors; adding template molecule glucose, synthesizing a molecular imprinting polymer film on the surface of the electrode by an electrochemical polymerization method, and eluting imprinted glucose molecules to obtain an electrochemical sensor with good specific recognition response to the glucose; the boric acid functionalized carbon quantum dot-polymer modified electrode molecularly imprinted sensor prepared by the method has high sensitivity and selectivity on glucose, and can realize rapid and efficient detection on glucose.
Drawings
Fig. 1 is a cyclic voltammogram of a molecularly imprinted sensor of a boronic acid functionalized carbon quantum dot-polymer modified electrode prepared in example 3 in a potassium ferricyanide solution, wherein an α -glassy carbon electrode, a β -unexlubilized molecularly imprinted sensor, a γ -eluted molecularly imprinted sensor, and a δ -molecularly imprinted sensor adsorbing 3mM glucose are provided.
Fig. 2 is a graph illustrating the interference resistance of the molecularly imprinted sensor of the boric acid functionalized carbon quantum dot-polymer modified electrode prepared in example 3.
FIG. 3 is the electrochemical response of the molecularly imprinted sensor with borate-functionalized carbon quantum dot-polymer modified electrode prepared in example 3 to glucose with different concentrations, wherein A is a graph of glucose profile measured by differential pulse voltammetry, and the concentrations of glucose are respectively 0.01mM, 0.1mM, 1mM, 2 mM, 3mM, 5mM, 7mM and 8mM from a → h; graph B is a linear relationship graph of glucose concentration and electrochemical signal.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the embodiments of the present invention and the accompanying drawings, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. The following description of at least one exemplary embodiment is merely illustrative in nature and is in no way intended to limit the invention, its application, or uses. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Unless specifically stated otherwise, the numerical values set forth in these examples do not limit the scope of the invention. Techniques, methods known to those of ordinary skill in the relevant art may not be discussed in detail, but are intended to be part of the specification where appropriate. In all examples shown and discussed herein, any particular value should be construed as exemplary only and not as limiting. Thus, other examples of the exemplary embodiments may have different values.
Example 1
Polishing, grinding and cleaning a glassy carbon electrode: polishing and grinding a glassy carbon electrode with the diameter of 3mm to a mirror surface by sequentially adopting three alumina powders with different particle sizes of 1.0 micron, 0.3 micron and 0.05 micron, and then repeatedly washing with secondary distilled water; the polished electrode was then placed in a bath containing 5mM K 3 [Fe(CN) 6 ]And 0.1M KCl in PBS (0.05M, pH 7.0.0), a standard pair of K appears on the polished electrode 3 [Fe(CN) 6 ]An oxidation reduction peak; repeatedly washing the polished glassy carbon electrode with secondary distilled water, sequentially ultrasonically cleaning with acetone and secondary distilled water, washing with secondary distilled water, and standing at room temperatureAnd (5) placing and drying for later use.
The preparation method of the molecularly imprinted sensor of the boric acid functionalized carbon quantum dot-polymer modified electrode comprises the following steps:
(1) Dissolving 0.2g of 3-aminophenylboronic acid and 1.0g of sodium citrate (the mass ratio of the two is 1:5) in 40mL of distilled water, adjusting the pH value to 9, introducing nitrogen to react for 1h, heating to 140 ℃, continuing to react for 6h, cooling to room temperature after the reaction is finished, filtering, and centrifuging to obtain a boric acid functionalized carbon quantum dot stock solution; taking the stock solution of 1mL, and adding 49mL of distilled water into the stock solution for dilution (50 times of volume) to obtain a boric acid functionalized carbon quantum dot solution;
(2) Adding 50mL of the boric acid functionalized carbon quantum dot solution obtained in the step (1), 0.1M glucose solution and 0.05M PBS buffer solution into a container according to a volume ratio of 1; the glassy carbon electrode which is polished and cleaned is placed in the molecular imprinting precursor mixed solution, the pH value is adjusted to be 8, and 50mV s is used in the potential range of-0.2V-0.6V -1 The scanning speed is 20 circles, and the boric acid functionalized carbon quantum dot-polymer modified electrode is obtained by electrochemical polymerization to form a film;
(3) The obtained boric acid functionalized carbon quantum dot-polymer modified electrode was placed in an acetic acid solution (10% volume fraction) containing 1wt% sds for electrochemical elution for 100 cycles, and the template molecular glucose was eluted to obtain a molecularly imprinted sensor of the boric acid functionalized carbon quantum dot-polymer modified electrode.
Example 2
The pretreatment steps of polishing, grinding and cleaning the glassy carbon electrode are the same as those in example 1.
The preparation method of the molecularly imprinted sensor of the boric acid functionalized carbon quantum dot-polymer modified electrode comprises the following steps:
(1) Dissolving 0.2g of 3-aminophenylboronic acid and 1.42g of sodium citrate (the mass ratio of the two is 1:7) in 40mL distilled water, adjusting the pH value to 9, introducing nitrogen to react for 1h, heating to 160 ℃, continuing to react for 6h, cooling to room temperature after the reaction is finished, filtering, and centrifuging to obtain a boric acid functionalized carbon quantum dot stock solution; taking 1mL of the stock solution, and adding 49mL of distilled water into the stock solution for dilution (with the volume being 50 times that of the stock solution) to obtain a boric acid functionalized carbon quantum dot solution;
(2) Adding 50mL of the boric acid functionalized carbon quantum dot solution, 0.1M of glucose solution and 0.05M of PBS buffer solution into a container according to a volume ratio of 1; the glassy carbon electrode which is polished and cleaned is placed in the mixed solution of the molecular imprinting precursor, the pH value is adjusted to be 8.5, and 50mV s is used in the potential range of-0.2V-0.6V -1 The scanning speed is 20 circles, and the boric acid functionalized carbon quantum dot-polymer modified electrode is obtained by electrochemical polymerization to form a film;
(3) And placing the obtained boric acid functionalized carbon quantum dot-polymer modified electrode in an acetic acid solution (10% volume fraction) containing 1wt% SDS, performing electrochemical elution for 150 circles by a cyclic voltammetry method, and eluting template molecular glucose to obtain the molecular imprinting sensor of the boric acid functionalized carbon quantum dot-polymer modified electrode.
Example 3
The pretreatment steps of polishing, grinding and cleaning the glassy carbon electrode are the same as those of the embodiment 1.
The preparation method of the molecularly imprinted sensor of the boric acid functionalized carbon quantum dot-polymer modified electrode comprises the following steps:
(1) Dissolving 0.2g of 3-aminophenylboronic acid and 1.42g of sodium citrate (the mass ratio of the two is 1:7) in 40mL distilled water, adjusting the pH value to 9, introducing nitrogen to react for 1h, heating to 160 ℃, continuing to react for 8h, cooling to room temperature after the reaction is finished, filtering, and centrifuging to obtain a boric acid functionalized carbon quantum dot stock solution; taking 1mL of the stock solution, and adding 49mL of distilled water into the stock solution for dilution (with the volume being 50 times that of the stock solution) to obtain a boric acid functionalized carbon quantum dot solution;
(2) Adding 50mL of the boric acid functionalized carbon quantum dot solution, 0.1M glucose solution and 0.05M PBS buffer solution into a container according to a volume ratio of 1.4; putting the glassy carbon electrode which is polished and cleaned into the molecular imprinting precursor mixed solution, and adjustingThe pH value is 9, and the voltage is 50mV s in the potential range of-0.2V to 0.6V -1 The scanning speed is 20 circles, and the boric acid functionalized carbon quantum dot-polymer modified electrode is obtained by electrochemical polymerization to form a film;
(3) And placing the obtained boric acid functionalized carbon quantum dot-polymer modified electrode in an acetic acid solution (10% volume fraction) containing 1wt% SDS, performing electrochemical elution for 240 circles by a cyclic voltammetry method, and eluting template molecular glucose to obtain the molecular imprinting sensor of the boric acid functionalized carbon quantum dot-polymer modified electrode.
Example 4
The pretreatment steps of polishing, grinding and cleaning the glassy carbon electrode are the same as those of the embodiment 1.
The preparation method of the molecularly imprinted sensor of the boric acid functionalized carbon quantum dot-polymer modified electrode comprises the following steps:
(1) Dissolving 0.2g of 3-aminophenylboronic acid and 3.0g of sodium citrate (the mass ratio of the two is 1; taking 1mL of the stock solution, and adding 49mL of distilled water into the stock solution for dilution (with the volume being 50 times that of the stock solution) to obtain a boric acid functionalized carbon quantum dot solution;
(2) Adding 5 mL of the boric acid functionalized carbon quantum dot solution, 0.1M of glucose solution and 0.05M of PBS buffer solution into a container according to a volume ratio of 1; the glassy carbon electrode which is polished and cleaned is placed in the molecular imprinting precursor mixed solution, the pH value is adjusted to 9.5, and 50mV s is used in the potential range of-0.2V-0.6V -1 The scanning speed is 20 circles, and the boric acid functionalized carbon quantum dot-polymer modified electrode is obtained by electrochemical polymerization to form a film;
(3) And placing the obtained boric acid functionalized carbon quantum dot-polymer modified electrode in an acetic acid solution (10% volume fraction) containing 1wt% SDS, performing electrochemical elution for 240 circles by a cyclic voltammetry method, and eluting template molecular glucose to obtain the molecular imprinting sensor of the boric acid functionalized carbon quantum dot-polymer modified electrode.
Example 5
The pretreatment steps of polishing, grinding and cleaning the glassy carbon electrode are the same as those of the embodiment 1.
The preparation method of the molecularly imprinted sensor of the boric acid functionalized carbon quantum dot-polymer modified electrode comprises the following steps:
(1) Dissolving 0.2g of 3-aminophenylboronic acid and 4.0g of sodium citrate (the mass ratio of the two is 1; taking 1mL of the stock solution, and adding 49mL of distilled water into the stock solution for dilution (50 times of volume) to obtain a boric acid functionalized carbon quantum dot solution;
(2) Adding the boric acid functionalized carbon quantum dot solution, 0.1M glucose solution and 0.05M PBS buffer solution into a container according to a volume ratio of 1; the glassy carbon electrode which is polished and cleaned is placed in the molecular imprinting precursor mixed solution, the pH value is adjusted to 10, and 50mV s is used in the potential range of-0.2V-0.6V -1 The scanning speed is 20 circles, and the boric acid functionalized carbon quantum dot-polymer modified electrode is obtained by electrochemical polymerization to form a film;
(3) The obtained boric acid functionalized carbon quantum dot-polymer modified electrode was placed in an acetic acid solution (10% volume fraction) containing 1wt% sds for 300 cycles by cyclic voltammetry, and glucose as a template molecule was eluted to obtain a molecularly imprinted sensor of the boric acid functionalized carbon quantum dot-polymer modified electrode.
Application example 1
Detection of glucose
At 5mM K 3 [Fe(CN) 6 ]And 0.1M KCl mixed solution, the molecular imprinting sensor of the boric acid functionalized carbon quantum dot-polymer modified glassy carbon electrode prepared in the embodiment 3 is used as a working electrode, an Ag/AgCl/electrode is used as a reference electrode, and a platinum wire is used as an auxiliary electrode; detection tool using electrochemical workstationThe results of the electrochemical signals from the electrodes are shown in FIGS. 1 to 3.
Fig. 1 is a cyclic voltammogram of a molecular imprinting sensor of a boric acid functionalized carbon quantum dot-polymer modified electrode in a potassium ferricyanide solution, and a test system is as follows: containing 0.1M KCl and 5mM K 3 [Fe(CN) 6 ]PBS solution (0.05M, pH 7.0.0), scan rate: 50mV s -1 . In FIG. 1, the alpha-bare glassy carbon electrode, the beta-unexluded molecularly imprinted sensor, the gamma-eluted molecularly imprinted sensor after glucose elution, and the delta-eluted molecularly imprinted sensor adsorb 3mM glucose. As can be seen from FIG. 1, the molecularly imprinted sensor with the beta curve not eluting the glucose as the template molecule is not conductive; and the response anode peak current 46.54 muA generated by the molecular imprinting sensor after the glucose is eluted by the gamma curve when being excited by the applied scanning voltage is higher than the response anode peak current 42.77 muA generated by the alpha curve bare glassy carbon electrode, which shows that the electrochemical performance of the glassy carbon electrode modified by the boric acid functionalized carbon quantum dot-polymer is remarkably improved compared with that of the bare glassy carbon electrode before modification.
Chinese patent 201810044606.3 also discloses a molecularly imprinted sensor for detecting glucose, and the preparation process of the molecularly imprinted sensor is as follows: the carbon quantum dots are firstly compounded with chitosan, then the carbon quantum dots are used for modifying a glassy carbon electrode, and the glassy carbon electrode modified by the carbon dots and the chitosan is subjected to electrochemical polymerization to form a membrane by taking glucose as a template molecule and 3-aminophenylboronic acid as a functional monomer under alkaline conditions, so that the molecularly imprinted membrane is formed. As can be seen from the attached figure 1 of the specification, after the template molecule glucose is eluted, the current of the prepared molecularly imprinted electrochemical sensor is 35.67 muA, which is lower than the current of a bare glassy carbon electrode by 38.32 muA.
Compared with the method of the Chinese patent 201810044606.3, the method is simple and convenient, and the prepared molecular imprinting sensor has better electrochemical performance.
Fig. 2 is a graph showing the anti-interference capability of a molecularly imprinted sensor of a boric acid functionalized carbon quantum dot-polymer modified electrode to different solutions, and the test system is as follows: containing 0.1M KCl and 5mM K 3 [Fe(CN) 6 ]PBS solution (0.05M, pH 7.0.0), scan rate: 50mV s -1 . The abscissa represents different solutions to be measuredThe solution comprises a Glucose-Glucose solution, an AA-ascorbic acid solution, a DA-dopamine solution and a D-fructose solution, and the concentration of all samples to be detected is 3mM; MIP is the molecular engram sensor polymer prepared by the method of the invention, NIP is blank control, namely no template molecule is added during polymerization. As can be seen from FIG. 2, the molecularly imprinted sensor of the boronic acid functionalized carbon quantum dot-polymer modified electrode prepared by the invention has better specific recognition response to glucose.
FIG. 3 shows the electrochemical response of the molecularly imprinted electrochemical sensor with the boric acid functionalized carbon quantum dot-polymer modified electrode to glucose with different concentrations, and the test system: containing 0.1M KCl and 5mM K 3 [Fe(CN) 6 ]PBS solution (0.05m, ph 7.0), scan rate: 50mV s -1 . As can be seen from fig. 3, when glucose was detected by differential pulse voltammetry, the current value was significantly decreased with the increase in glucose concentration in the range of 0.01mM to 8mM, and the linear relationship was good, with the detection limit of glucose being 3.52 μ M (S/N = 3). Can be applied to the detection of glucose under physiological conditions or the detection of glucose in fermentation liquor products.
The tests show that the molecularly imprinted sensor of the boric acid functionalized carbon quantum dot-polymer modified electrode prepared by the method has good specificity recognition response on glucose, has high sensitivity and selectivity on the detection of the glucose, and can realize the rapid and efficient detection of the glucose.
The above description is only for the preferred embodiment of the present invention, but the scope of the present invention is not limited thereto, and any person skilled in the art should be considered to be within the technical scope of the present invention, and the technical solutions and the inventive concepts thereof according to the present invention should be equivalent or changed within the scope of the present invention.

Claims (8)

1. The preparation method of the molecularly imprinted sensor of the boric acid functionalized carbon quantum dot-polymer modified electrode is characterized by comprising the following steps of:
(1) Dissolving 3-aminophenylboronic acid and sodium citrate in water, adjusting the pH value to 9, introducing nitrogen to react for 1h, heating to 140-160 ℃, continuing to react for 6-8 h, cooling to room temperature after the reaction is finished, filtering and centrifuging to obtain a boronic acid functionalized carbon quantum dot stock solution, and adding water to dilute the stock solution to obtain a boronic acid functionalized carbon quantum dot solution;
(2) Stirring and mixing the boric acid functionalized carbon quantum dot solution, the glucose solution and the PBS buffer solution uniformly at room temperature to obtain a molecular imprinting precursor mixed solution; placing the electrode after polishing, grinding and cleaning in the molecular imprinting precursor mixed solution, adjusting the pH value to 8-11, and polymerizing to form a film by an electrochemical method to obtain a boric acid functionalized carbon quantum dot-polymer modified electrode;
(3) And eluting template molecule glucose of the boric acid functionalized carbon quantum dot-polymer modified electrode by adopting an organic acid washing stripping solution to obtain the boric acid functionalized carbon quantum dot-polymer modified electrode molecularly imprinted sensor.
2. The method for preparing the molecularly imprinted sensor of the boric acid functionalized carbon quantum dot-polymer modified electrode according to claim 1, wherein the mass ratio of the 3-aminophenylboronic acid to the sodium citrate in the step (1) is 1 (5-20); the concentration of the 3-aminophenylboronic acid in the water is 0.005 g-mL -1 。
3. The method for preparing the molecularly imprinted sensor of the boronic acid functionalized carbon quantum dot-polymer modified electrode according to claim 1, wherein the volume ratio of the stock solution to the water added for diluting the stock solution in the step (1) is 1; the molar concentration of the glucose solution is 0.1M; the molar concentration of the PBS buffer solution is 0.05M; the volume ratio of the glucose solution to the boric acid functionalized carbon quantum dot solution to the PBS buffer solution is (0.1-1): 1.
4. The method for preparing the molecularly imprinted sensor of the boronic acid functionalized carbon quantum dot-polymer modified electrode according to claim 1, wherein the heating temperature in the step (1) is 160 ℃, and the reaction time is 8 hours; the pH value in the step (2) is 9.
5. The method for preparing a molecularly imprinted sensor of a boronic acid functionalized carbon quantum dot-polymer modified electrode according to claim 1, wherein the electrochemical method in the step (2) is performed at a potential range of-0.2V to 0.6V and at a voltage of 50 mV-s -1 The film was polymerized by scanning for 20 cycles at the scanning rate of (2).
6. The method for preparing a molecularly imprinted sensor of a boronic acid functionalized carbon quantum dot-polymer modified electrode according to claim 1, wherein the organic acid eluent in the step (3) is an acetic acid solution with a volume fraction of 10%, and the acetic acid solution contains 1wt% of SDS.
7. The method for preparing a molecularly imprinted sensor of the boronic acid functionalized carbon quantum dot-polymer modified electrode according to claim 6, wherein the step of eluting template molecular glucose is to place the obtained boronic acid functionalized carbon quantum dot-polymer modified electrode in the eluent to perform electrochemical elution for 50-300 circles.
8. The molecularly imprinted sensor of the boronic acid functionalized carbon quantum dot-polymer modified electrode prepared by the preparation method according to any one of claims 1 to 7 is applied to glucose detection under physiological conditions or glucose detection in fermentation liquor products.
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