CN111272600B - Quartz crystal microbalance sensor and modification method and application of gold electrode thereof - Google Patents
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Abstract
The invention belongs to the technical field of biosensor detection, and particularly relates to a quartz crystal microbalance sensor and a modification method and application of a gold electrode of the quartz crystal microbalance sensor. The invention aims to solve the problems of complex sample pretreatment steps, expensive instruments and equipment, need of professional technicians for operation and the like in the traditional tetracycline detection method and the technical problems of low detection sensitivity, poor stability and the like of a quartz crystal microbalance.
Description
Technical Field
The invention belongs to the technical field of biosensor detection, and particularly relates to a quartz crystal microbalance sensor and a modification method and application of a gold electrode of the quartz crystal microbalance sensor.
Background
With the development of the traditional animal husbandry to the modernization and the intensification scale, antibiotic medicines become indispensable factors for promoting the development of the modern animal husbandry. Tetracyclines (TET) are widely used in animal husbandry due to their low price and broad antimicrobial spectrum, and are added as growth promoters in animal feeds. However, because the bioavailability of tetracycline in animals is low, tetracycline which is discharged at will enters human bodies through the action of food chain transmission in the environment, and poses great threat to human health.
At present, the traditional detection methods for tetracycline antibiotics mainly comprise an enzyme-linked immunosorbent assay, a thin-layer chromatography, a capillary electrophoresis method, a microbiological method, a high-performance liquid chromatography and the like, but have the defects of poor specificity, long time consumption, complex operation, professional technical operators, expensive instruments and equipment and the like. Therefore, the rapid tetracycline detection technology which is simple, convenient, rapid, sensitive and reliable to research has important practical significance.
A Quartz Crystal Microbalance (QCM) is a highly sensitive detecting instrument which converts the surface quality change of a quartz crystal oscillator electrode into the frequency change of an output electric signal of a quartz crystal oscillation circuit by using the piezoelectric property of a quartz crystal resonator and detects the surface quality change. Aptamers, also known as aptamers (Apt), are short functional oligonucleotide fragments, typically RNA or single-stranded DNA. The aptamer has the advantages of high specificity and high selectivity combination with various target substances. The Metal-organic framework Material (MOF) is a framework structure formed by combining organic ligands with different connection numbers and Metal ion nodes, and has the advantages of high porosity, low density, large specific surface area, regular pore channels, adjustable pore diameter, structural diversity and the like. The nanogold (AuNPs) has good biocompatibility and large specific surface area, and can be covalently combined with an aptamer with sulfydryl through an Au-S bond, so that the sensitivity and stability of the sensor are improved.
Disclosure of Invention
The invention aims to solve the problems of complex sample pretreatment steps, expensive instruments and equipment, need of professional technicians for operation and the like in the traditional tetracycline detection method and the technical problems of low detection sensitivity, poor stability and the like of a quartz crystal microbalance, and provides a simple, convenient, quick, sensitive and reliable method for detecting tetracycline in food by using the quartz crystal microbalance aptamer sensor. The invention relies on the step-by-step modification of copper 1,3, 5-benzenetricarboxylate (HKUST-1), nanogold (AuNPs) and tetracycline aptamer (Apt) on the surface of a quartz gold electrode to construct a novel quartz crystal microbalance sensor for sensitively and specifically detecting tetracycline. Firstly, coating and modifying HKUST-1 on a quartz crystal microbalance gold electrode in a dropping mode, then modifying AuNPs on the surface of the electrode by adopting a method of electrodepositing chloroauric acid, then fixing a sulfhydryl-modified tetracycline aptamer on the surface of the quartz crystal microbalance gold electrode through an Au-S bond, and sealing an unbound site by using MCH to prepare the tetracycline aptamer modified gold electrode (MCH/Apt/AuNPs/HKUST-1/AuE) treated by 6-mercaptohexanol. During detection, tetracycline is captured and identified by an aptamer modified on the surface of MCH/Apt/AuNPs/HKUST-1/AuE, so that the constructed quartz crystal microbalance sensor can generate corresponding frequency signal change, a standard curve is established, and quantitative detection of the target tetracycline is achieved. In order to solve the technical problems, the technical scheme adopted by the invention is as follows:
a quartz crystal microbalance sensor comprises a working electrode of the quartz crystal microbalance sensor, wherein metal organic framework materials of copper 1,3, 5-benzenetricarboxylate, nanogold and tetracycline aptamers are sequentially modified on the working electrode, and the working electrode is a gold electrode.
A method for modifying a gold electrode of a quartz crystal microbalance sensor comprises the following steps:
step 1, weighing 1,3, 5-copper benzenetricarboxylate, dispersing in ultrapure water, and performing ultrasonic treatment by using an ultrasonic cleaning instrument to obtain a uniform MOF dispersion liquid;
step 2, modifying the uniform MOF dispersion liquid obtained in the step 1 on the surface of a gold electrode in a dripping mode, and drying the uniform MOF dispersion liquid under an infrared lamp to form an MOF film so as to obtain the 1,3, 5-copper pyromellitic tricarboxylate modified gold electrode;
step 3, placing the gold electrode modified by the copper 1,3, 5-benzenetricarboxylate obtained in the step 2 in AuHCl4In the solution, modifying nano gold on the surface of the gold electrode modified by the copper 1,3, 5-benzenetricarboxylate by adopting an electrodeposition method to obtain a gold electrode modified by the nano gold and modified by the copper 1,3, 5-benzenetricarboxylate;
step 4, dripping tetracycline aptamer on the surface of the gold electrode modified by the nano-gold and modified by the 1,3, 5-copper pyromellitic tricarboxylate obtained in the step 3 for incubation, and cleaning to obtain a tetracycline aptamer modified gold electrode;
and 5, dripping a 6-mercaptohexanol solution on the tetracycline aptamer modified gold electrode obtained in the step 4, and cleaning to obtain the tetracycline aptamer modified gold electrode treated by 6-mercaptohexanol.
Further, the concentration of the MOF dispersion liquid obtained in the step 1 is 0.5-2.0 mg/mL.
Further, the amount of the uniform MOF dispersion in step 2 is 20 μ L, and the drying time for drying under an infrared lamp to form the MOF film in step 2 is 30min to 1 h.
Further, AuHCl in step 3 is4The concentration of the solution was 1%.
Further, the electrodeposition method in the step 3 is cyclic voltammetry, the scanning voltage range of the cyclic voltammetry is-0.3V-0V, the scanning rate is 20mV/s-100mV/s, and the number of scanning circles is 3-10 circles.
Furthermore, the concentration of the tetracycline aptamer in the step 4 is 0.6 μ M, the incubation time of the tetracycline aptamer in the step 4 is 60min-120min, and the concentration of the 6-mercaptohexanol solution in the step 5 is 1.0mol/L, and the dosage is 20 μ L.
Further, the tetracycline aptamer sequence is: 5' -SH- (CH)2)6-CGT ACG GAA TTC GCT AGC CCC CCG GCA GGC CAC GGC TTG GGT TGG TCC CAC TGC GCG TGG ATC CGA GCT CCA CGT G-3'。
The application of the quartz crystal microbalance sensor is applied to detecting the trace tetracycline.
The quartz crystal microbalance sensor is applied to detecting trace tetracycline, and the specific detection method comprises the following steps:
step 1, placing a tetracycline aptamer modified gold electrode treated by 6-mercaptohexanol as a working electrode in a detection chamber of a quartz crystal microbalance detection system; simultaneously, recording frequency corresponding data sensed by a quartz crystal microbalance crystal oscillator in the detection chamber and acquired by a frequency meter through a computer of a signal acquisition system;
step 2, dripping 100 mu L of phosphate buffer solution with the concentration of 0.1M and the pH value of 7.0 on the tetracycline aptamer modified gold electrode treated by the 6-mercaptohexanol in the step 1, dripping 50 mu L of tetracycline solutions with different concentrations on the tetracycline aptamer modified gold electrode treated by the 6-mercaptohexanol when the frequency is stable, simultaneously recording corresponding frequency change data, and establishing a linear relation between a logarithmic value of the tetracycline concentration and a frequency change value of a quartz crystal microbalance sensor;
and 3, when detecting the tetracycline content in the sample, placing the tetracycline aptamer modified gold electrode treated by 6-mercaptohexanol as a working electrode into a detection chamber of a quartz crystal microbalance detection system, dropwise adding 100 mu L of phosphate buffer solution with the concentration of 0.1M and the pH value of 7.0, when the frequency is stable, dropwise adding 50 mu L of the treated sample solution onto the tetracycline aptamer modified gold electrode treated by 6-mercaptohexanol, recording the corresponding frequency change of the quartz crystal microbalance sensor, and substituting the frequency change value into the linear relation equation in the step 2 to calculate the tetracycline content in the sample.
Compared with the prior art, the invention has the beneficial effects that:
1. the invention relies on modifying HKUST-1, AuNPs and Apt layer by layer on the surface of a gold electrode of a quartz crystal microbalance, so as to construct a novel quartz crystal microbalance sensor for sensitively and specifically detecting tetracycline. The specific surface area of a detection interface of the quartz crystal microbalance can be improved by modifying the metal organic framework material HKUST-1, the load capacity of the aptamer and the detection sensitivity of the sensor can be improved, and the aptamer is covalently bonded on the detection interface through a gold-sulfur bond between the nanogold and a sulfydryl on the aptamer, so that the stability of the sensor is improved.
2. The invention mainly solves the defects of complicated sample pretreatment process, expensive instrument, complex operation and the like in the prior tetracycline detection method based on the chromatographic technology, provides a simple, convenient, sensitive and reliable analysis and detection means for detecting tetracycline in a complex sample in the practical application process, and applies the quartz crystal microbalance sensor to the detection of tetracycline for the first time.
Drawings
FIG. 1 is a cyclic voltammetry characterization diagram during preparation of an aptamer sensor for a quartz crystal microbalance (a.AuE, b.HKUST-1/AuE, c.AuNPs/HKUST-1/AuE, d.Apt/AuNPs/HKUST-1/AuE, e.MCH/Apt/AuNPs/HKUST-1/AuE, f.TET/MCH/Apt/AuNPs/HKUST-1/AuE);
FIG. 2 is a standard curve of a quartz crystal microbalance aptamer sensor for detecting tetracycline with different concentrations, wherein the abscissa of the graph is a logarithmic value of the concentration of a target object, and the ordinate of the graph is a frequency change value before and after incubation during detection of the target object.
Detailed Description
The technical solutions in the embodiments of the present invention are clearly and completely described below with reference to the drawings in the embodiments of the present invention, 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. 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.
1) QCM gold electrode pretreatment
Firstly, physical cleaning is carried out before electrode modification, 2mmol/L Al is taken2O3And (3) slightly wiping the surface of the gold electrode with the powder aqueous dispersion, repeatedly washing the gold electrode with deionized water and absolute ethyl alcohol, then placing the gold electrode in the absolute ethyl alcohol for ultrasonic cleaning for 5min, repeatedly washing the gold electrode with the deionized water, blow-drying the gold electrode with nitrogen, and completely drying the gold electrode for later use. And (3) preparing a mixed solution of 98% sulfuric acid and 30% hydrogen peroxide in a volume ratio of 3:1, dropwise adding the mixed solution on a gold electrode, repeatedly washing the gold electrode with deionized water after 3min, and drying the gold electrode under a nitrogen atmosphere.
2) Treatment of aptamers
Aptamers readily attach to the walls of the test tubes and therefore need to be centrifuged (5000rpm) for 1 minute before use, 150. mu.L buffer (0.1M PBS, pH 7.0) per OD primer is added to make a 10. mu.M stock, which is stored at-20 ℃ until use.
Example 1
A quartz crystal microbalance sensor comprises a working electrode of the quartz crystal microbalance sensor, wherein metal organic framework materials of 1,3, 5-copper benzenetricarboxylic acid (HKUST-1), nanogold (AuNPs) and tetracycline aptamer (Apt) are sequentially modified on the working electrode, and the working electrode is a gold electrode (AuE).
Example 2
A method for modifying a gold electrode of a quartz crystal microbalance sensor comprises the following steps:
step 1, weighing 1,3, 5-copper benzenetricarboxylate (HKUST-1), dispersing in ultrapure water, and ultrasonically treating by using an ultrasonic cleaner to obtain an uniform MOF dispersion liquid with the concentration of 0.5 mg/mL;
step 2, taking 20 mu L of the uniform MOF dispersion liquid obtained in the step 1, modifying the surface of the gold electrode in a dripping mode, and drying for 30min under an infrared lamp to form an MOF film so as to obtain a 1,3, 5-copper benzenetricarboxylate (HKUST-1/AuE) modified gold electrode;
step 3, placing the 1,3, 5-copper pyromellitic tricarboxylate modified gold electrode (HKUST-1/AuE) obtained in the step 2 in 1% AuHCl4Modifying nano gold (AuNPs) on the surface of a gold electrode (HKUST-1/AuE) modified by copper 1,3, 5-benzenetricarboxylate by adopting a cyclic voltammetry method in a solution to obtain a gold electrode (AuNPs) modified by nano gold (AuNPs) and modified by copper 1,3, 5-benzenetricarboxylate (AuNPs/HKUST-1/AuE); the scanning voltage range of the cyclic voltammetry is-0.3V-0V, the scanning rate is 20mV/s, and the number of scanning cycles is 3 cycles;
step 4, dripping tetracycline aptamer (Apt) with the concentration of 0.6 mu M on the surface of the gold electrode (AuNPs/HKUST-1/AuE) modified by nano-gold and modified by 1,3, 5-copper pyromellitic tricarboxylate and obtained in the step 3, incubating for 60min, and cleaning to obtain the tetracycline aptamer modified gold electrode (Apt/AuNPs/HKUST-1/AuE);
and 5, dripping 20 mu L of 6-mercaptohexanol solution with the concentration of 1.0mol/L on the tetracycline aptamer modified gold electrode obtained in the step 4, and cleaning to obtain the tetracycline aptamer modified gold electrode (MCH/Apt/AuNPs/HKUST-1/AuE) treated by 6-mercaptohexanol.
The tetracycline aptamer sequence is: 5' -SH- (CH)2)6-CGT ACG GAA TTC GCT AGC CCC CCG GCA GGC CAC GGC TTG GGT TGG TCC CAC TGC GCG TGG ATC CGA GCT CCA CGT G-3'。
Example 3
A method for modifying a gold electrode of a quartz crystal microbalance sensor comprises the following steps:
step 1, weighing 1,3, 5-copper benzenetricarboxylate (HKUST-1) and dispersing in ultrapure water, and ultrasonically treating the ultrapure water by using an ultrasonic cleaner to obtain an MOF dispersion liquid with a uniform concentration of 2 mg/mL;
step 2, taking 20 mu L of the uniform MOF dispersion liquid obtained in the step 1, modifying the surface of the gold electrode in a dripping mode, and drying for 1h under an infrared lamp to form an MOF film so as to obtain a 1,3, 5-copper benzenetricarboxylate (HKUST-1/AuE) modified gold electrode;
step 3, placing the 1,3, 5-copper pyromellitic tricarboxylate modified gold electrode (HKUST-1/AuE) obtained in the step 2 in 1% AuHCl4Modifying nano gold (AuNPs) on the surface of a gold electrode (HKUST-1/AuE) modified by copper 1,3, 5-benzenetricarboxylate by adopting a cyclic voltammetry method in a solution to obtain a gold electrode (AuNPs) modified by nano gold (AuNPs) and modified by copper 1,3, 5-benzenetricarboxylate (AuNPs/HKUST-1/AuE); the scanning voltage range of the cyclic voltammetry is-0.3V-0V, the scanning rate is 100mV/s, and the number of scanning cycles is 10 cycles;
step 4, dripping tetracycline aptamer (Apt) with the concentration of 0.6 mu M on the surface of the gold electrode (AuNPs/HKUST-1/AuE) modified by nano-gold and modified by 1,3, 5-copper pyromellitic tricarboxylate and obtained in the step 3, incubating for 120min, and cleaning to obtain the tetracycline aptamer modified gold electrode (Apt/AuNPs/HKUST-1/AuE);
and 5, dripping 20 mu L of 6-mercaptohexanol solution with the concentration of 1.0mol/L on the tetracycline aptamer modified gold electrode obtained in the step 4, and cleaning to obtain the tetracycline aptamer modified gold electrode (MCH/Apt/AuNPs/HKUST-1/AuE) treated by 6-mercaptohexanol.
The tetracycline aptamer sequence is: 5' -SH- (CH)2)6-CGT ACG GAA TTC GCT AGC CCC CCG GCA GGC CAC GGC TTG GGT TGG TCC CAC TGC GCG TGG ATC CGA GCT CCA CGT G-3'。
Example 4
A method for modifying a gold electrode of a quartz crystal microbalance sensor comprises the following steps:
step 1, weighing 1,3, 5-copper benzenetricarboxylate (HKUST-1), dispersing in ultrapure water, and ultrasonically treating by using an ultrasonic cleaner to obtain an uniform MOF dispersion liquid with the concentration of 1 mg/mL;
step 2, taking 20 mu L of the uniform MOF dispersion liquid obtained in the step 1, modifying the surface of the gold electrode in a dripping mode, and drying for 45min under an infrared lamp to form an MOF film so as to obtain a 1,3, 5-copper benzenetricarboxylate (HKUST-1/AuE) modified gold electrode;
step 3, placing the 1,3, 5-copper pyromellitic tricarboxylate modified gold electrode (HKUST-1/AuE) obtained in the step 2 in 1% AuHCl4In the solution, modifying (AuNPs) on the surface of a gold electrode (HKUST-1/AuE) modified by 1,3, 5-copper benzenetricarboxylic acid by adopting a cyclic voltammetry method to obtain a gold electrode (AuNPs) modified by nano gold (AuNPs) and a gold electrode (AuNPs/HKUST-1/AuE) modified by 1,3, 5-copper benzenetricarboxylic acid; the scanning voltage range of the cyclic voltammetry is-0.3V-0V, the scanning rate is 60mV/s, and the number of scanning cycles is 6;
step 4, dripping tetracycline aptamer (Apt) with the concentration of 0.6 mu M on the surface of the gold electrode (AuNPs/HKUST-1/AuE) modified by the nano-gold modified copper 1,3, 5-benzenetricarboxylic acid obtained in the step 3, incubating for 90min, and cleaning to obtain the tetracycline aptamer modified gold electrode (Apt/AuNPs/HKUST-1/AuE);
and 5, dripping 20 mu L of 6-mercaptohexanol solution with the concentration of 1.0mol/L on the tetracycline aptamer modified gold electrode obtained in the step 4, and cleaning to obtain the tetracycline aptamer modified gold electrode (MCH/Apt/AuNPs/HKUST-1/AuE) treated by 6-mercaptohexanol.
The tetracycline aptamer sequence is: 5' -SH- (CH)2)6-CGT ACG GAA TTC GCT AGC CCC CCG GCA GGC CAC GGC TTG GGT TGG TCC CAC TGC GCG TGG ATC CGA GCT CCA CGT G-3'。
Example 5
The application of the quartz crystal microbalance sensor is applied to detecting the trace tetracycline.
The quartz crystal microbalance sensor is applied to detecting trace tetracycline, and the specific detection method comprises the following steps:
step 1, placing a tetracycline aptamer modified gold electrode treated by 6-mercaptohexanol as a working electrode in a detection chamber of a quartz crystal microbalance detection system; simultaneously, recording frequency corresponding data sensed by a quartz crystal microbalance crystal oscillator in the detection chamber and acquired by a frequency meter through a computer of a signal acquisition system;
step 2, dripping 100 mu L of phosphate buffer solution with the concentration of 0.1M and the pH value of 7.0 on the tetracycline aptamer modified gold electrode treated by the 6-mercaptohexanol in the step 1, dripping 50 mu L of tetracycline solutions with different concentrations on the tetracycline aptamer modified gold electrode treated by the 6-mercaptohexanol when the frequency is stable, simultaneously recording corresponding frequency change data, and establishing a linear relation between a logarithmic value of the tetracycline concentration and a frequency change value of a quartz crystal microbalance sensor;
and 3, when detecting the tetracycline content in the sample, placing the tetracycline aptamer modified gold electrode treated by 6-mercaptohexanol as a working electrode into a detection chamber of a quartz crystal microbalance detection system, dropwise adding 100 mu L of phosphate buffer solution with the concentration of 0.1M and the pH value of 7.0, when the frequency is stable, dropwise adding 50 mu L of the treated sample solution onto the tetracycline aptamer modified gold electrode treated by 6-mercaptohexanol, recording the corresponding frequency change of the quartz crystal microbalance sensor, and substituting the frequency change value into the linear relation equation in the step 2 to calculate the tetracycline content in the sample.
FIG. 1 is a diagram of cyclic voltammetry characterization of the construction process of an aptamer sensor on a quartz crystal microbalance, with CV curves of different modified electrodes (a AuE, b HKUST-1/AuE, c AuNPs/HKUST-1/AuE, d Apt/AuNPs/HKUST-1/AuE, e MCH/Apt/AuNPs/HKUST-1/AuE, f TET/MCH/Apt/AuNPs/HKUST-1/AuE) in a solution containing 1mM K3Fe (CN)6 and 0.2M KNO 3. Curve a is the cyclic voltammetry response of the bare electrode (AuE) and a typical pair of redox peaks for the potassium ferricyanide probe can be observed. Curve b is the cyclic voltammetry response graph of HKUST-1/AuE after modifying HKUST-1 with bare AuE, and it can be observed that HKUST-1/AuE is obviously smaller than the response current of bare electrode AuE, because after HKUST-1 film is formed on the surface of the electrode, the potassium ferricyanide probe is difficult to reach the surface of the electrode through the modifying layer, and the transfer of electrons on the surface of the electrode is hindered, so the current is reduced. And the curve c shows that after the surface of the HKUST-1/AuE electrode is modified with AuNPs, the current signal is obviously increased, because the nano gold particles improve the conductivity of the electrode. Curve d is the CV curve of the aptamer modified on the AuNPs/HKUST-1/AuE electrode, and after the aptamer is modified, the current is reduced because the thiol-modified aptamer is connected to the electrode surface through a gold-sulfur bond, the transfer of electrons on the electrode surface is blocked, and the current is further reduced after the blocking with the MCH blocking agent, and the result is shown as curve e. After the aptamer on the surface of the electrode recognizes the target tetracycline (curve f), the aptamer conformation changes, a large steric hindrance is formed, the electronic transfer inhibition effect on potassium ferricyanide is increased, and the cyclic voltammetry current response is continuously reduced. The cyclic voltammetry results show that the quartz crystal microbalance aptamer sensor is successfully constructed and can be used for the determination of tetracycline.
As shown in figure 2, the frequency variation value of the constructed sensor is continuously reduced along with the increase of the concentration of the tetracycline, and the linear detection range of the tetracycline is 1.0 multiplied by 10-10～1.0×10-5g/mL。
While there have been shown and described what are at present considered the fundamental principles and essential features of the invention and its advantages, it will be apparent to those skilled in the art that the invention is not limited to the details of the foregoing exemplary embodiments, but is capable of other specific forms without departing from the spirit or essential characteristics thereof. The present embodiments are therefore to be considered in all respects as illustrative and not restrictive, the scope of the invention being indicated by the appended claims rather than by the foregoing description, and all changes which come within the meaning and range of equivalency of the claims are therefore intended to be embraced therein. Any reference sign in a claim should not be construed as limiting the claim concerned.
Furthermore, it should be understood that although the present description refers to embodiments, not every embodiment may contain only a single embodiment, and such description is for clarity only, and those skilled in the art should integrate the description, and the embodiments may be combined as appropriate to form other embodiments understood by those skilled in the art.
Claims (7)
1. A method for modifying a gold electrode of a quartz crystal microbalance sensor is characterized by comprising the following steps: the method comprises the following steps:
step 1, weighing 1,3, 5-copper benzenetricarboxylate, dispersing in ultrapure water, and performing ultrasonic treatment by using an ultrasonic cleaning instrument to obtain a uniform MOF dispersion liquid;
step 2, modifying the uniform MOF dispersion liquid obtained in the step 1 on the surface of a gold electrode in a dripping mode, and drying the uniform MOF dispersion liquid under an infrared lamp to form an MOF film so as to obtain the 1,3, 5-copper pyromellitic tricarboxylate modified gold electrode;
step 3, placing the gold electrode modified by the copper 1,3, 5-benzenetricarboxylate obtained in the step 2 in AuHCl4In the solution, modifying nano gold on the surface of the gold electrode modified by the copper 1,3, 5-benzenetricarboxylate by adopting an electrodeposition method to obtain a gold electrode modified by the nano gold and modified by the copper 1,3, 5-benzenetricarboxylate;
step 4, dripping tetracycline aptamer on the surface of the gold electrode modified by the nano-gold and modified by the 1,3, 5-copper pyromellitic tricarboxylate obtained in the step 3 for incubation, and cleaning to obtain a tetracycline aptamer modified gold electrode;
and 5, dripping a 6-mercaptohexanol solution on the tetracycline aptamer modified gold electrode obtained in the step 4, and cleaning to obtain the tetracycline aptamer modified gold electrode treated by 6-mercaptohexanol.
2. The method for modifying the gold electrode of the quartz crystal microbalance sensor according to claim 1, wherein the method comprises the following steps: the concentration of the MOF dispersion liquid obtained in the step 1 is 0.5-2 mg/mL.
3. The method for modifying the gold electrode of the quartz crystal microbalance sensor according to claim 1, wherein the method comprises the following steps: the usage amount of the uniform MOF dispersion liquid in the step 2 is 20 mu L, and the drying time of drying under an infrared lamp to form the MOF film in the step 2 is 30min-1 h.
4. The method for modifying the gold electrode of the quartz crystal microbalance sensor according to claim 1, wherein the method comprises the following steps: AuHCl in the step 34The concentration of the solution was 1%.
5. The method for modifying the gold electrode of the quartz crystal microbalance sensor according to claim 1, wherein the method comprises the following steps: the electrodeposition method in the step 3 is cyclic voltammetry, the scanning voltage range of the cyclic voltammetry is-0.3V-0V, the scanning rate is 20mV/s-100mV/s, and the number of scanning cycles is 3-10 cycles.
6. The method for modifying the gold electrode of the quartz crystal microbalance sensor according to claim 1, wherein the method comprises the following steps: the concentration of the tetracycline aptamer in the step 4 is 0.6 mu M, the incubation time of the tetracycline aptamer in the step 4 is 60min-120min, and the concentration of the 6-mercaptohexanol solution in the step 5 is 1.0mol L-1The dosage is 20 μ L.
7. The method for modifying the gold electrode of the quartz crystal microbalance sensor according to claim 1, wherein the method comprises the following steps: the tetracycline aptamer sequence is: 5' -SH- (CH)2)6-CGT ACG GAA TTC GCT AGC CCC CCG GCA GGC CAC GGC TTG GGT TGG TCC CAC TGC GCG TGG ATC CGA GCT CCA CGT G-3'。
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