CN114019003B - Electrochemical sensor for UA detection through molecular wire regulation and control nano interface, and preparation and application thereof - Google Patents
Electrochemical sensor for UA detection through molecular wire regulation and control nano interface, and preparation and application thereof Download PDFInfo
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Classifications
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- G—PHYSICS
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- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N27/00—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means
- G01N27/26—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating electrochemical variables; by using electrolysis or electrophoresis
- G01N27/28—Electrolytic cell components
- G01N27/30—Electrodes, e.g. test electrodes; Half-cells
- G01N27/327—Biochemical electrodes, e.g. electrical or mechanical details for in vitro measurements
- G01N27/3275—Sensing specific biomolecules, e.g. nucleic acid strands, based on an electrode surface reaction
- G01N27/3277—Sensing specific biomolecules, e.g. nucleic acid strands, based on an electrode surface reaction being a redox reaction, e.g. detection by cyclic voltammetry
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N27/00—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means
- G01N27/26—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating electrochemical variables; by using electrolysis or electrophoresis
- G01N27/28—Electrolytic cell components
- G01N27/30—Electrodes, e.g. test electrodes; Half-cells
- G01N27/327—Biochemical electrodes, e.g. electrical or mechanical details for in vitro measurements
- G01N27/3275—Sensing specific biomolecules, e.g. nucleic acid strands, based on an electrode surface reaction
- G01N27/3278—Sensing specific biomolecules, e.g. nucleic acid strands, based on an electrode surface reaction involving nanosized elements, e.g. nanogaps or nanoparticles
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N27/00—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means
- G01N27/26—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating electrochemical variables; by using electrolysis or electrophoresis
- G01N27/416—Systems
- G01N27/49—Systems involving the determination of the current at a single specific value, or small range of values, of applied voltage for producing selective measurement of one or more particular ionic species
Abstract
The invention discloses a method for electrochemically detecting cerebral uric acid by regulating and controlling a nano interface through a molecular wire. The invention also discloses a molecular wire and a preparation method thereof, and the molecular wire of different types is obtained by reaction in an organic solvent. The molecular wire is modified on the surface of a gold electrode through the interaction of gold and sulfur, and then Ni is modified 3 HHTP 2 An electrochemical sensor is obtained. The method is simple to operate, and the prepared electrochemical sensor is used for detecting uric acid in the brain of a mouse, has high selectivity, high sensitivity and low detection limit, and has important significance for exploring the behavior of uric acid in organisms and the relationship between uric acid and learning and memory capacity.
Description
Technical Field
The invention belongs to the technical field of sensing detection of carbon fiber microelectrodes, and particularly relates to an electrochemical sensor for UA detection by using a molecular wire regulated nano interface, and preparation and application thereof.
Background
Most neurological diseases are closely related to the lack or imbalance of neurochemical substances, and in-situ detection of neurochemical substances in the brain is an important method for understanding brain science and solving brain diseases. However, the brain environment is very complex, there are many substances with many redox activities, and there is an overlap between signals, which greatly affects the detection of neurochemical substances in the brain. Therefore, there is a need to develop an efficient electrochemical sensor that maintains the intrinsic signal of the chemical species while improving selectivity and enabling reversible detection, which is critical for the long-term dynamic detection of neurochemical species.
Wherein uric acid is used as a natural antioxidant in human body, can remove peroxide, hydroxyl, oxygen free radicals and the like, effectively lightens oxidative damage of the free radicals to the human body and damages to blood brain barrier, has strong protective effect on neurons, and has preventive and therapeutic effects on a plurality of nervous system diseases. In the existing electrochemical technology, the problems of low stability, poor selectivity, high detection limit, unidirectional detection and the like of the nano material generally exist, and the challenges make the technology for detecting uric acid in a living body difficult to obtain substantial breakthrough.
Disclosure of Invention
In order to overcome the defects in the prior art, the invention provides a novel method for detecting uric acid. The method has the advantages of high selectivity, high sensitivity and low detection limit, and is very beneficial to dynamic detection.
The invention provides a two-dimensional conductive MOF material Ni 3 HHTP 2 The structure of the compound is shown as a formula (a):
the invention also provides a two-dimensional conductive MOF material Ni 3 HHTP 2 In aqueous solution, 2,3,6,7,10, 11-hexahydroxybenzo and nickel (II) tetrahydrate react to obtain the two-dimensional conductive MOF material Ni 3 HHTP 2 。
Wherein the aqueous solution refers to deionized water.
The invention also discloses three molecular wires, the structures of which are respectively shown in formulas (b), (c) and (d):
the invention also discloses a preparation method of the molecular wire shown in the formula (c), which comprises the following specific steps: 4-iodobenzaldehyde, pdCl 2 (PPh 3 ) 2 And CuI was suspended in 15mL dry THF and 5mL TEA at room temperature; then3-ethynyl thiophene was added and stirred at 50 ℃; the reaction is continuously stirred for 16 hours after the 4-iodobenzaldehyde is consumed, and a yellow solid, namely a molecular line shown in a formula (c), is obtained;
wherein the 4-iodobenzaldehyde and PdCl 2 (PPh 3 ) 2 The molar ratio of CuI to 3-ethynyl thiophene is 5:20:10:6.
The invention also discloses a preparation method of the molecular wire shown in the formula (d), which comprises the following specific steps:
step (1): 4-iodobenzaldehyde, pdCl 2 (PPh 3 ) 2 And CuI was added to 5mL TEA suspension in 15mL dry THF at room temperature, then 1-ethynyl-4-iodobenzene was added, and the mixture was stirred at 50 ℃ until 4-iodobenzaldehyde was consumed, then stirred for reaction for 16h to give an intermediate product;
the 4-iodobenzaldehyde and PdCl 2 (PPh 3 ) 2 The molar ratio of CuI to 1-ethynyl-4-iodobenzene is 5:20:10:6;
step (2): the intermediate was dissolved in 8mL dry THF at room temperature and was purified in N 2 The reaction was followed by 2.8mL TEA and PdCl 2 (PPh 3 ) 2 And CuI dissolution; then adding 3-ethynyl thiophene, and stirring the mixture at 50 ℃ for 16 hours to obtain a yellow solid, wherein the molecular line is shown in a formula (d);
said intermediate product, pdCl 2 (PPh 3 ) 2 The molar ratio of CuI to 3-ethynyl thiophene is 2.80:11:5.6:3.06.
In one embodiment, the preparation method of the molecular wire shown in the formula (c) comprises the following specific steps: 4-iodobenzaldehyde (5 mmol), pdCl 2 (PPh 3 ) 2 (20 mmol) and CuI (10 mmol) were suspended in 15mL dry THF and 5mL TEA at room temperature. Then, 3-ethynyl thiophene (6 mmol) was added and stirred at 50 ℃. The reaction was stirred for 16h after consumption of 4-iodobenzaldehyde. Finally, the crude product was purified by column chromatography (silica gel, petroleum ether/ethyl acetate=9/1) to give a yellow solid.
In one embodiment, the preparation method of the molecular wire shown in the formula (d) comprises the following specific steps: first, 4-iodobenzaldehyde (5 mmol) and PdCl 2 (PPh 3 ) 2 (20 mmol) and CuI (10 mmol) were added to a suspension of TEA (5 mL) in dry THF (15 mL) at room temperature. Next, 1-ethynyl-4-iodobenzene (6 mmol) was added and the mixture was stirred at 50℃until 4-iodobenzaldehyde was consumed, followed by stirring for 16h. Finally, the crude product was purified by column chromatography (silica gel, petroleum ether/ethyl acetate=10/1) to give the product.
Then, the product (2.80 mmol) was dissolved in 8mL dry THF at room temperature and under N 2 TEA (2.8 mL), pdCl were used as follows 2 (PPh 3 ) 2 (11 mmol) and CuI (5.6 mmol) were dissolved. After that, 3-ethynyl thiophene (3.06 mmol) was added and the mixture was stirred at 50 ℃ for 16h. The residue was purified by column chromatography (silica gel, diethyl ether/ethyl acetate=10/1) to give a yellow solid.
The reaction routes of the formulas (c) and (d) of the present invention are shown below:
the invention also provides a preparation method of the electrochemical sensor, which comprises the following specific steps:
(1) Preparing a carbon fiber microelectrode: the carbon fiber is fixed on the copper wire through silver conductive adhesive and is dried in a drying oven at 60 ℃ for 1 hour; then, the above product was inserted into a capillary tube and dried at 60℃for 8 hours to obtain a carbon fiber microelectrode.
(2) Electrodepositing gold nanoparticles on the carbon fiber microelectrode obtained in the step (1);
(3) Modifying a molecular wire on the carbon fiber microelectrode on which the gold nanoparticles are electrodeposited in the step (2);
(4) On the carbon fiber microelectrode of electrodeposited gold nano particles after modifying the molecular wire in the step (3), the two-dimensional conductive MOF material Ni shown in the step (a) is modified again 3 HHTP 2 Obtaining an electrochemical sensor:
in the step (1), the outer diameter of the capillary tube of the carbon fiber microelectrode is 1.0mm-1.5mm, preferably 1.5mm; the inner diameter is 0.7mm to 1.1mm, preferably 1.1mm.
In the step (1), the capillary is made of quartz glass capillary or borosilicate glass capillary, preferably borosilicate glass capillary.
In the step (1), the pore diameter of the capillary of the carbon fiber microelectrode is 100-200 μm; preferably 100 μm.
In the step (2), the method for electrodepositing gold nano particles on the carbon fiber electrode is an electrochemical deposition method, the carbon fiber electrode is firstly put into 0.1M NaOH, and 1.5V electrochemical pretreatment is carried out for 80s; then the gold nano particles are electroplated in chloroauric acid solution.
Wherein the concentration of the chloroauric acid solution is 5mM-50mM; preferably 10mM.
Wherein, the voltage of the electro-deposition is-0.1V to-0.2V; preferably 0.2V.
Wherein the electrodeposition time is 30s-100 s; preferably 40s.
In the step (3), the method for modifying the molecular wire on the carbon fiber microelectrode on which the gold nano-particles are electrodeposited comprises the following steps: immersing the gold-plated carbon fiber microelectrode into a molecular wire solution, taking out, washing away the free molecular wire solution, and airing at room temperature.
Wherein the molecular wire solution specifically refers to the molecular wires shown in the formulas (b), (c) and (d) dissolved in THF solution.
Wherein the concentration of the molecular wire is 1mM-2mM; preferably, it is 2mM.
Wherein, the time for immersing the molecular wire is 8-12 h; preferably 12h.
Wherein the molecular wire has a structure as shown in the above formulas (b), (c) and (d).
In the step (4), the two-dimensional conductive MOF material Ni shown in the modification formula (a) 3 HHTP 2 Before Ni is added 3 HHTP 2 Dispersed in H 2 O to obtain Ni 3 HHTP 2 -H 2 O dispersion;then immersing the carbon fiber microelectrode of the electrodeposited gold nanoparticle after the modification of the molecular wire in the step (3) into Ni 3 HHTP 2 -H 2 And (3) dispersing the O in the liquid for a period of time to obtain the electrochemical sensor.
Wherein, the concentration of the dispersion liquid is 1 mg/mL-5 mg/mL; preferably 1mg/mL.
Wherein, the time for immersing the dispersion liquid is 1 h-5 h; preferably 5h.
The invention also provides an electrochemical sensor prepared by the method.
The invention also provides application of the electrochemical sensor in detecting uric acid.
The invention also provides a method for detecting in-vitro uric acid by using the electrochemical sensor through an electrochemical analysis method.
The invention also provides an application of the electrochemical sensor in detecting uric acid in mouse brain by an electrochemical analysis method.
The invention utilizes the interaction between gold and sulfur to modify molecular wires on the gold-plated electrode and then modifies the two-dimensional conductive MOF material. On one hand, the synthesized MOF has large specific surface area, high porosity and more active sites, and effectively enriches molecules and simultaneously drives the oxidation process; on the other hand, the rigid molecules connect the electrode surface and the MOF material, so that electrons are more orderly transferred from the MOF material to the electrode surface, the energy internal consumption is reduced, and meanwhile, the electron transfer rate is improved, and the analysis performance of the electrochemical sensor is further improved. The electrochemical sensor provided by the invention has high selectivity, high sensitivity and low detection limit for identifying uric acid, and has excellent performance.
Specifically, the method for detecting uric acid in vitro by using the electrochemical sensor comprises the following steps:
(1) Gold plating is performed on the carbon fiber electrode, and the concentration of chloroauric acid solution is 5mM-50mM, preferably 10mM.
Wherein the voltage of the electrodeposition is-0.1V to-0.2V, preferably 0.2V.
Wherein the electrodeposition time is 30s-100s, preferably 40s.
(2) And (3) modifying the molecular wire on the gold-plated carbon fiber electrode obtained in the step (1). Taking out, washing off free molecular wire solution, and air drying at normal temperature.
Wherein the concentration of the molecular wire is 1mM-2mM, preferably 2mM.
Wherein, the time for immersing the molecular wire is 8h-24h, preferably 12h.
(3) Modifying a two-dimensional conductive MOF material Ni on the gold-plated carbon fiber electrode modified with rigid molecules obtained in the step (2) 3 HHTP 2 And obtaining the electrochemical sensor, namely the required electrode.
(4) Building a three-electrode working system: setting up a three-electrode working system in an electrochemical workstation, wherein the electrode obtained in the step (3) is used as a working electrode, the Ag/AgCl electrode is used as a reference electrode, and the Pt electrode is used as a counter electrode. The voltage recording range is 0V-0.8V and the voltage step amplitude is 80mV.
(5) And (3) making a standard curve:
recording differential pulse voltammetry curves of uric acid with different concentrations on the electrochemical workstation constructed in the step (4), and then making a relation curve of peak current and uric acid concentration to obtain a linear range of 0.2 mu M-150 mu M;
(6) Determination of uric acid content in a sample
Uric acid in the sample is measured in an electrochemical workstation and the uric acid content in the sample is calculated from a standard curve.
The invention also provides a method for detecting uric acid content in the brain of a mouse by using the prepared carbon fiber microelectrode, which comprises the following steps:
(1) Preparing a required carbon fiber microelectrode;
(2) Determination of uric acid in hippocampal tissue in hyperuricic and normal mice.
And (2) measuring peak current, and calculating to obtain uric acid content in the brain according to a standard curve.
The invention has the beneficial effects that the modification state of the two-dimensional conductive MOF material at the electrode interface is effectively regulated and controlled through the molecular wire, and the high-efficiency sensor for detecting uric acid is developed. The electrochemical sensor has good selectivity and low detection limit, the linear range is 0.2 mu M-150 mu M, the lowest detection line is 80nM (S/N=3), and the detection of uric acid in vitro or in vivo can be well satisfied, and the electrochemical sensor has important significance for diagnosis, drug treatment and other basic researches of diseases.
Drawings
Fig. 1: scanning electron microscope SEM and transmission electron microscope TEM of the two-dimensional conductive MOF material synthesized by the invention. Wherein, graph A is an SEM graph of the MOF material, and graphs B and C are a TEM graph of the MOF and a corresponding XRD graph, indicating that the MOF material contains Ni element; panel D is the XRD pattern. Combining the four figures can demonstrate successful synthesis of two-dimensional conductive MOF materials.
Fig. 2: characterization graphs of scanning electron microscope SEM for different modification steps of the carbon fiber microelectrode prepared by the invention. Wherein A is an SEM image of a carbon fiber microelectrode purely plated with gold, B and C are SEM images of a modified molecular wire and a two-dimensional conductive MOF material, and D is a corresponding XRD image, which further indicates that the two-dimensional conductive MOF is indeed successfully modified on the surface of the carbon fiber microelectrode.
Fig. 3: the electrochemical sensor designed by the invention detects a differential pulse voltammogram of uric acid and a linear relation diagram of uric acid concentration and peak current. Wherein, the graph A, E is a DPV graph of a pure gold-plated electrode and a corresponding linear relation graph, the detection limit is 1.0 mu M, and the graph is not linear; FIG. B, F is a DPV pattern and a corresponding linear relationship pattern obtained by modifying a flexible molecule FP1 of formula (b) on a gold-plated electrode, the detection limit being 5.0. Mu.M, and not being linear; FIG. C, G is a DPV pattern and a corresponding linear relationship pattern obtained by modifying a short-chain rigid molecule RP1 represented by the formula (c) on a gold-plated electrode, wherein the detection limit is 0.5. Mu.M, and the linear range is 0.5. Mu.M to 150.0. Mu.M; FIG. D, H shows a DPV pattern obtained by modifying a long-chain rigid molecule RP2 represented by the formula (d) on a gold-plated electrode, and a corresponding linear relationship pattern, wherein the detection limit is 0.2. Mu.M and the linear range is 0.2. Mu.M to 150.0. Mu.M. Experimental results show that the probe modified with the long-chain rigid molecule has optimal analysis performance, so that the probe is selected as a target probe.
Fig. 4: the electrochemical sensor provided by the invention detects the selectivity and competition experimental diagram of UA. Experimental patterns (a-D) of selectivity of amino groups, neurochemical substances, metal ions, and active oxygen for 10 μm UA, which are common in living bodies. Wherein A is amino acid, B is neurochemical substance, C is metal ion, and D is active oxygen.
Fig. 5: the electrochemical sensor provided by the invention detects the reproducibility experimental graph of UA.
Fig. 6: the electrochemical sensor provided by the invention detects the experimental results of UA in the brain of a normal mouse and the brain of a hyperuricemia mouse, and the learning and memory behaviors of the normal mouse and the hyperuricemia mouse. From the figure, the learning and memory ability of the hyperuricemia mice is obviously inferior to that of normal mice, and the hyperuricemia mice can be further used for exploring the influence of the hyperuricemia on the cognitive dysfunction.
FIG. 7 shows the assembly of rigid molecular wires RP2 and two-dimensional conductive MOF material Ni on a gold interface 3 HHTP 2 Is a schematic diagram of (a).
Detailed Description
The present invention will be described in further detail with reference to the following specific examples and drawings. The procedures, conditions, experimental methods, etc. for carrying out the present invention are common knowledge and common knowledge in the art, except for the following specific references, and the present invention is not particularly limited.
Example 1: two-dimensional conductive MOF material Ni 3 HHTP 2 Is synthesized by (a)
200mg 2,3,6,7,10,11-hexahydroxybenzo (HHTP), 456mg nickel (II) acetate tetrahydrate were added to 28mL deionized water and sonicated for 10min. Subsequently, heating and refluxing were carried out at 85℃for 24 hours. After natural cooling to room temperature, the product was washed with deionized water (3X 50 mL) and acetone (3X 50 mL). Finally, the product was collected after drying in a vacuum oven at 49 ℃ for 24h. FIG. 2 is Ni 3 HHTP 2 The morphology of the Ni-based alloy is a nano rod-shaped structure, the diameter is about 50nm, and the XRD pattern further shows that the Ni-based alloy successfully prepares Ni 3 HHTP 2 。
Example 2: preparation of electrochemical sensor
(1) Gold plating was performed on the carbon fiber electrode, and the concentration of chloroauric acid solution was 10mM.
(2) And (3) modifying the molecules FP1, RP1 or RP2 on the gold-plated carbon fiber electrode obtained in the step (1). Taking out, washing to remove free molecular solution, and air drying at normal temperature.
(3) Modifying the two-dimensional conductive MOF material Ni prepared in the embodiment 1 of the invention on the gold-plated carbon fiber electrode modified with rigid molecules and obtained in the step (2) 3 HHTP 2 Then Ni is modified on the gold-plated carbon fiber electrode 3 HHTP 2 And drying at normal temperature to obtain the electrochemical sensor, namely the required electrode. As shown in FIG. 3, the SEM image of the electrode morphology is that Ni is modified on the gold-plated carbon fiber electrode 3 HHTP 2 。
Example 3: in-vitro detection UA (UA) of electrochemical sensor designed by molecular wire regulated nano interface
A three-electrode working system was set up in an electrochemical workstation, the electrode obtained in example 2 of the present invention was used as a working electrode, an Ag/AgCl electrode was used as a reference electrode, and a Pt electrode was used as a counter electrode. The voltage recording range is 0V-0.8V and the voltage step amplitude is 80mV. In a three electrode system, DPV curves are swept in UA solutions with different concentrations to obtain a curve relationship between peak current and concentration, and a linear range of 0.2 mu M to 150.0 mu M is obtained (figure 3). Wherein, FIG. 3A is a control group, unmodified molecule, detection limit is 1.0. Mu.M, no linearity; FIG. 3B modifies flexible molecule FP1 with a detection limit of 5.0. Mu.M, which is not linear; FIG. 3C is a modified short-chain rigid molecule RP1 with a detection limit of 0.5. Mu.M and a linear range of 0.5. Mu.M to 150.0. Mu.M; FIG. 3D is a modified long-chain rigid molecule RP2 with a detection limit of 0.2. Mu.M and a linear range of 0.2. Mu.M to 150.0. Mu.M. It can be seen from the figure that the electrode detection UA modified with the long-chain rigid molecule RP2 has lower detection limit and higher sensitivity.
Example 4: the selectivity and the competitiveness of different amino acids, neurochemical substances, metal ions and active oxygen to UA are measured by adopting a DPV method, and as shown in figure 4, the electrode detection UA prepared in the embodiment 2 of the invention has better selectivity.
Example 5: the reproducibility of the electrode modified with MOF and RP2 was examined by DPV method, as shown in FIG. 5, which shows that the electrode prepared in example 2 of the present invention has excellent stability.
Example 6: detection of UA in rat brain using electrochemical sensor modified with long-chain rigid molecules RP2 and MOF
The uric acid content in the hippocampus of normal and hyperuricemic mice was measured by needle (fig. 6A). Hyperuricemia mice and control mice walk Morris water maze, and the learning ability and memory ability of the mice are judged. The time for the mouse to find the subsurface platform is recorded through a positioning navigation test: for five days, normal and hyperuricemia mice were placed into the water from four water entry points (the pool was divided into four quadrants, southeast, northwest, and north, respectively, with four water entry points set up, with a platform placed in the center of one quadrant) each day, the time for the rats to find the platform hidden under the water was recorded, training four times a day, and the average value was recorded (fig. 6B). The UA content in the hippocampus of the mice detected as normal was about 1.3. Mu.M, and the UA concentration in the hippocampus of the hyperuricemia mice was about 5.0. Mu.M. In addition, normal and hyperuricemic mice had a decrease in maze time following the next day, but hyperuricemic mice had a slower maze time than normal mice.
The protection of the present invention is not limited to the above embodiments. Variations and advantages that would occur to one skilled in the art are included in the invention without departing from the spirit and scope of the inventive concept, and the scope of the invention is defined by the appended claims.
Claims (8)
1. A method of manufacturing an electrochemical sensor, the method comprising the steps of:
(1) Preparing a carbon fiber microelectrode;
(2) Electrodepositing gold nanoparticles on the carbon fiber microelectrode prepared in the step (1);
(3) Modifying a molecular wire on the carbon fiber microelectrode on which the gold nanoparticles have been electrodeposited in the step (2);
(4) On the carbon fiber microelectrode of electrodeposited gold nano particles after modifying the molecular wire in the step (3), modifying a two-dimensional conductive MOF material Ni shown in the formula (a) 3 HHTP 2 Obtaining an electrochemical sensor;
the structure of the modified molecular line is shown as a formula (c):
2. the method of claim 1, wherein in step (1), the glass capillary of the carbon fiber microelectrode has an outer diameter of 1.0mm to 1.5mm; the inner diameter is 0.7mm-1.1mm;
in the step (2), the specific steps of electrodepositing gold nanoparticles on the carbon fiber microelectrode are as follows: putting the carbon fiber electrode into 0.1M NaOH, and carrying out electrochemical pretreatment for 80s by using 1.5V; then the gold nano particles are electroplated in chloroauric acid solution.
3. The method of claim 2, wherein the chloroauric acid solution has a concentration of 5mM to 50mM; and/or the voltage of the electrodeposition is-0.1V to-0.2V; and/or the electrodeposition time is 30s-100s.
4. The method of claim 1, wherein in step (3), the concentration of the molecular wire is 1mM to 2mM; and/or the time for modifying the molecular line is 8-12 h.
5. The method of claim 1, wherein in step (4), in the two-dimensional conductive MOF material Ni represented by modification (a) 3 HHTP 2 Before Ni is added 3 HHTP 2 Dispersed in H 2 O to obtain Ni 3 HHTP 2 -H 2 O dispersion; wherein the Ni 3 HHTP 2 -H 2 The concentration of the O dispersion liquid is 1mg/mL-2mg/mL.
6. An electrochemical sensor prepared by the method of any one of claims 1-5.
7. Use of the electrochemical sensor according to claim 6 for detecting UA.
8. The application of claim 7, wherein the method of detecting UA comprises the steps of:
the electrochemical sensor according to claim 6 is used for detecting UA with different concentrations, and the linear relation between the concentration of UA and the peak current is established by measuring the peak current.
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