CN112147195B - Construction method of electrochemical sensor for rapidly and quantitatively detecting pesticide residues - Google Patents
Construction method of electrochemical sensor for rapidly and quantitatively detecting pesticide residues Download PDFInfo
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- CN112147195B CN112147195B CN202010986116.2A CN202010986116A CN112147195B CN 112147195 B CN112147195 B CN 112147195B CN 202010986116 A CN202010986116 A CN 202010986116A CN 112147195 B CN112147195 B CN 112147195B
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- G01N27/00—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means
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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
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Abstract
The invention discloses a construction method of an electrochemical sensor for rapidly and quantitatively detecting pesticide residues, which relates to the technical field of food safety detection and analysis, overcomes the defects of the existing various methyl parathion detection technologies, and has the advantages of low detection limit, rapid and accurate detection, convenient carrying, less required equipment, low cost and the like, and the specific scheme is as follows: the method comprises the following steps: s1, self-assembling 4-aminothiophenol on the sulfhydrylation graphene modification screen printing electrochemical sensor; s2, self-assembly of methyl parathion on the sulfhydrylation graphene modification screen printing electrochemical sensor; s3, preparing the thiolated graphene-loaded gold platinum nanoparticle modified molecular imprinting screen printing electrochemical sensor: an electrochemical sensor of the methyl parathion molecularly imprinted polymer is prepared by adopting an electropolymerization method. The construction method of the electrochemical sensor for quickly and quantitatively detecting pesticide residues provided by the invention provides a miniature pesticide residue detection chip which is quick, sensitive, portable, low in cost and easy to operate.
Description
Technical Field
The invention relates to the technical field of food safety detection and analysis, in particular to a construction method of an electrochemical sensor for quickly and quantitatively detecting pesticide residues.
Background
The conventional detection methods for pesticide residues at present comprise: chromatography, spectroscopy, biochemistry, and the like. Gas chromatography, high performance liquid chromatography and gas-mass spectrometry are widely applied to laboratory detection, although the detection result is accurate, the required instruments are expensive, the sample treatment and detection period is long, the operation is complex and time-consuming, the technical level requirement on an analyst is high, and the method is not suitable for field detection. The method for detecting organophosphorus pesticides by spectroscopy has the advantages of limited range, background light source, low sensitivity, narrow range of measured concentration and poor selectivity, and is generally used as a qualitative detection means. The enzyme inhibition method is used for detecting pesticide residues by detecting the activity inhibition effect of acetylcholinesterase (AChE) or carboxylesterase, is widely applied at present, but has the disadvantages of complex operation steps, low automation degree, capability of only detecting organophosphorus and carbamate pesticides and incapability of detecting other pesticides, low sensitivity and false positive sometimes. In addition, some existing rapid detection methods, such as an agricultural residue detection card, an agricultural residue rapid screening mass spectrum mobile platform, a portable raman spectrum agricultural residue detector and the like, are based on an enzyme inhibition method and a spectrum method, are mainly used for qualitative detection and rapid screening of agricultural residues, and cannot realize rapid and accurate quantitative detection.
In contrast, the electrochemical sensor technology is gradually becoming one of the most viable means in the field detection of pesticide residues by virtue of the advantages of simple operation, high sensitivity, rapid detection, low equipment requirement, easy miniaturization and integration, and the like. However, the kinds of pesticides are various, and the oxidation-reduction peak potentials are usually very close, so that the electrochemical sensor cannot accurately perform specific identification and analysis on the pesticides. Therefore, the method has the defects of poor selectivity, more interference factors, poor stability, troublesome post-treatment of the electrode and the like. Detection methods such as an electrochemiluminescence method, an electrochemical enzyme-linked immunosorbent assay and the like are reported to be developed by combining an electrochemical method with a photochemical method or a biochemical method, and although some defects of the spectroscopic method and the biochemical method are overcome, optical detection equipment is required besides an electrochemical workstation, so that the detection cost is increased, and the detection is inconvenient to carry.
As a big agricultural country, China urgently needs to establish a rapid, high-sensitivity, high-selectivity and low-cost pesticide large-scale field inspection and monitoring technology.
Disclosure of Invention
In order to solve the technical problems, the invention provides a construction method of an electrochemical sensor for rapidly and quantitatively detecting pesticide residues, which overcomes the defects of the existing various methyl parathion detection technologies and has the advantages of low detection limit, rapid and accurate detection, convenience in carrying, less required equipment, low cost and the like.
The technical purpose of the invention is realized by the following technical scheme:
a construction method of an electrochemical sensor for rapidly and quantitatively detecting pesticide residues comprises the following steps:
self-assembling S1 and 4-aminothiophenol on a sulfhydrylation graphene modification screen printing electrochemical sensor: the method comprises the following steps of (1) immersing a sulfhydrylation graphene-loaded gold platinum nanoparticle modified screen printing electrochemical sensor into an absolute ethyl alcohol solution of 4-aminothiophenol, enabling gold nanoparticles and-SH in the 4-aminothiophenol to form Au-S bonds through strong coordination, self-assembling the Au-S bonds on the surface, and directionally arranging the Au-S bonds into an ordered compact monomolecular layer;
s2, self-assembly of methyl parathion on the sensor: soaking the self-assembled sensor in S1 in methyl parathion solution to make-NO in methyl parathion molecule 2 O atom and-NH in 4-aminothiophenol on sensor surface 2 Are bound by means of hydrogen bonds;
s3, preparing the thiolated graphene loaded gold platinum nanoparticle modified molecularly imprinted screen printing electrochemical sensor: an electrochemical sensor of the methyl parathion molecularly imprinted polymer is prepared by adopting an electropolymerization method.
As a preferable scheme, the methyl parathion molecularly imprinted polymer electrochemical sensor is prepared in the S3 process, and the following steps are required to be carried out before electropolymerization:
firstly introducing N into the polymerization solution 2 Deoxidizing, immersing the assembled sensor of 4-amino thiophenol and methyl parathion as working electrode in the absolute alcohol polymerizing solution of 4-amino thiophenol, methyl parathion and tetrabutyl ammonium perchlorate, scanning by cyclic voltammetry to obtain molecular engram polymer of methyl parathion, immersing the electropolymerized sensor in HCl for eluting to remove methyl parathion template molecule, washing with water, and N 2 And drying for later use.
As a preferable scheme, in the S1 process, the preparation of the screen-printed electrochemical sensor modified by thiolated graphene-loaded gold platinum nanoparticles includes the following steps:
k1, preparation of a screen printing electrochemical sensor: the screen printing electrochemical sensor comprises a working electrode, a reference electrode and a counter electrode three-electrode system; the substrate layer is made of PET material; the carbon layer is formed on the basal layer in a silk-screen printing mode, the diameter of the working electrode is 3mm, the reference electrode and the counter electrode are annular, the three electrodes are respectively positioned on the outer sides of the reference electrode to form three silk-screen printing electrodes, the lower end interface is a data transmission interface, and pins corresponding to the interfaces are communicated;
k2, preparation of diazonium salt modified screen printing sensor: firstly, placing the prepared screen printing electrochemical sensor in K1 in N 2 Scanning in 4-nitrobenzene diazonium tetrafluoroborate and tetrabutylammonium tetrafluoroborate acetonitrile solutions in a saturated environment by adopting a cyclic voltammetry method; after electrodeposition, repeatedly washing the electrode with acetonitrile and water; then scanning in an ethanol solution containing KCl by using a cyclic voltammetry method, reducing nitro groups into amino groups to prepare a diazonium salt modified silk-screen printing sensor, washing with water, and drying for later use;
k3, preparation of a sulfhydrylation graphene modified screen printing sensor: soaking the diazonium salt modified sensor prepared by K2 in a thiolated graphene aqueous dispersion to obtain a thiolated graphene modified sensor, washing with water, and drying for later use;
k4, preparing the electrochemical sensor modified by the thiolated graphene-loaded gold platinum nanoparticles through screen printing: and dropwise coating the dispersed liquid of the gold and platinum nanoparticles loaded with the ionic liquid on the surface of the sulfhydrylation graphene modified sensor prepared in K3, and drying under an infrared lamp to obtain the sulfhydrylation graphene loaded gold and platinum nanoparticle modified screen printing electrochemical sensor.
As a preferred scheme, the data interface is a Type-C interface.
As a preferable scheme, the K1 process also needs to carry out the following steps before the sensor is prepared:
the polyethylene terephthalate substrate is put into ethanol solution for ultrasonic treatment to remove surface grease and dust, and then is put into an oven for baking.
In a preferred embodiment, in the K1 process, the printing process of the screen printing electrochemical sensor is completed on a screen printer, and the manufacturing process comprises the following steps:
firstly, manufacturing Type-C specification double-sided pins, copper leads and double-sided bonding pads; then, printing a three-electrode conductive line by silver paste, and thermally curing; printing the working electrode and the counter electrode by using conductive carbon paste in sequence, and thermally curing again; then printing a reference electrode layer by using Ag/AgCl slurry, and thermally curing again; and finally, printing the sensor insulating layer by using light-cured insulating paste, exposing the front end working area and the rear wire area, and curing by using ultraviolet light.
As a preferred scheme, the preparation of the nano particles comprises the following steps:
t1, preparation of gold nanosheet dispersion liquid: adding 1-butyl-3-methylimidazolium tetrafluoroborate ionic liquid into chloroauric acid trihydrate, heating by microwave, and naturally cooling to room temperature to obtain a gold nanosheet dispersion;
t2 and preparation of Pt nanoparticles: adding KOH and ascorbic acid into H 2 Adding chloroplatinic acid into the mixed solution, oscillating, and carrying out water bath; obtaining platinum nano particles after centrifugal separation and water washing;
t3, preparation of ionic liquid supported gold platinum nanoparticle dispersion liquid: adding the platinum nanoparticles into the ionic liquid loaded gold nanosheets for ultrasonic dispersion.
A rapid quantitative pesticide residue detection electrochemical sensor is prepared by applying the construction method of the rapid quantitative pesticide residue detection electrochemical sensor.
In conclusion, the invention has the following beneficial effects:
the invention provides a quick, sensitive, portable, low-cost and easy-to-operate miniature pesticide residue detection chip. The electrochemical sensor constructed based on the molecular imprinting-graphene composite nano material is an optimal method for field quantitative detection. The method solves the problems that in the existing pesticide residue analysis, such as chromatographic detection, instruments are expensive, complex to operate, long in detection period and not beneficial to field detection; the spectrum detection specificity is poor and the sensitivity is low; the biochemical method is only used for qualitative screening and the like.
Drawings
FIG. 1 is a schematic structural diagram of a screen printed electrochemical sensor according to an embodiment of the present invention;
wherein:
A. a sensor finished product diagram; B. a sensor front side; C. a sensor back; D. an insulating layer; 1. a reaction zone; 2. a carbonaceous counter electrode; 3. a carbonaceous working electrode; 4. an Ag/AgCl reference electrode; 5. a double-sided peer-to-peer Type-C interface;
FIG. 2 is a flow chart of a screen printed electrochemical sensor of an embodiment of the present invention;
wherein:
A. manufacturing a pin and a bonding pad; B. an electrode lead layer; C. a working electrode and a counter electrode layer; D. an Ag/AgCl reference electrode layer; E. an insulating layer.
Detailed Description
This specification and claims do not intend to distinguish between components that differ in name but not function. In the following description and in the claims, the terms "include" and "comprise" are used in an open-ended fashion, and thus should be interpreted to mean "include, but not limited to. "substantially" means within an acceptable error range, within which a person skilled in the art can solve the technical problem to substantially achieve the technical result.
The terms in upper, lower, left, right and the like in the description and the claims are combined with the drawings to facilitate further explanation, so that the application is more convenient to understand and is not limited to the application.
The present invention will be described in further detail with reference to the accompanying drawings.
1. Preparing nano particles:
(1) preparing an ionic liquid loaded gold nanosheet dispersion:
50mg of chloroauric acid trihydrate (HAuCl) are taken 4 ·3H 2 O) adding 1mL of 1-butyl-3-methylimidazole tetrafluoroborate ionic liquid into a test tube, heating for 10min by microwave (126W), and naturally cooling to room temperature to obtain the ionic liquid loaded gold nanosheet dispersion.
(2) Preparing Pt nano particles:
1 mol. L is taken -1 KOH 0.05mL、10mmol·L -1 Ascorbic Acid (AA)3mL was added to 2mL H 2 In O, take 2 mmol. L -1 Chloroplatinic acid (CPP)(H 2 PtCl 6 )4mL of the solution was added to the mixture, and the mixture was reacted in a water bath at 60 ℃ for 1 hour with gentle shaking. And obtaining the product platinum nano particles after centrifugal separation and water washing.
(3) Preparing an ionic liquid loaded gold-platinum nanoparticle dispersion liquid:
and adding 3.0mg of platinum nanoparticles into 0.3mL of ionic liquid loaded gold nanoplates, and performing ultrasonic dispersion for 30min to obtain the nano-platinum-gold nanoparticle.
2. Preparing a screen-printing electrochemical sensor modified by sulfhydrylation graphene-loaded gold platinum nanoparticles:
(1) preparation of screen-printed electrochemical sensor
The screen-printed electrochemical sensor comprises a three-electrode system of a Working Electrode (WE), a Reference Electrode (RE) and a Counter Electrode (CE). Adobe Illustrator is used to design the hydrophobic area model and sensor wiring pattern of the sensor, see FIG. 1. Polyethylene terephthalate (PET) is used as a sensor substrate, the size is 1cm x 4cm, the WE diameter is 3mm, and RE and CE are annular and are respectively positioned on the outer side of RE to form a screen printing three-electrode. The lower end interface adopts a double-sided equal Type-C interface, and two sides of the interface are communicated with corresponding pins, so that the portable electrochemical workstation is convenient to connect.
Before the sensor is prepared, the PET substrate is placed in an ethanol solution for 2 hours of ultrasonic treatment to remove surface grease and dust, and then the PET substrate is placed in a 120 ℃ oven for baking for 15 minutes, so that the influence of deformation generated during high-temperature curing on the precision of the sensor is prevented.
The screen printing electrochemical sensor printing process is completed on a screen printer. The manufacturing process is shown in figure 2. Firstly, manufacturing a Type-C specification double-sided pin, a copper lead and a double-sided bonding pad. Then, printing a three-electrode conductive line by silver paste, and thermally curing at 120 ℃ for 10 min; sequentially printing WE and CE with conductive carbon paste, and thermally curing at 60 deg.C for 30 min; then printing an RE layer by Ag/AgCl slurry, and thermally curing for 5min at 110 ℃; and finally, printing the sensor insulating layer by using light-cured insulating paste, exposing the front end working area and the rear wire area, and curing by using ultraviolet light.
(2) Preparing a diazonium salt modified silk-screen printing electrochemical sensor:
firstly, the sensor prepared in the step (1) is placed in N 2 Saturation (with N) 2 2 mmol. L under oxygen removal for 15 min) -1 4-Nitrobenzene diazo tetrafluoroborate, 0.1 mol. L -1 In the tetrabutylammonium tetrafluoroborate acetonitrile solution, a Cyclic Voltammetry (CV) is adopted for scanning for 5 circles, the scanning range is-0.5 to-1.8V, and the scanning speed is 50 mV.s -1 . After electrodeposition, the sensor was repeatedly rinsed with acetonitrile and water. Then at-0.4 to-1.6V at a sweep rate of 50 mV. multidot.s -1 In the presence of 1 mol. L -1 Scanning KCl in 10% ethanol solution for 3 circles by using a CV method, reducing nitro into amino to prepare the diazonium salt modified silk-screen printing electrochemical sensor, washing the sensor with water, and drying for later use.
(3) Preparing a sulfhydrylation graphene modified silk-screen printing electrochemical sensor:
the sensor prepared in the step (2) is added at 1.0 mg.mL -1 And soaking the sulfhydrylation graphene aqueous dispersion for 4 hours to obtain the sulfhydrylation graphene modified silk-screen printing electrochemical sensor, washing with water, and drying for later use.
(4) Preparing a screen printing electrochemical sensor modified by sulfhydrylation graphene loaded gold platinum nano particles:
and (4) dropwise coating 5 mu L of ionic liquid loaded gold platinum nanoparticle dispersion liquid on the surface of the sensor prepared in the step (3), and drying under an infrared lamp to obtain the sulfhydrylation graphene loaded gold platinum nanoparticle modified screen printing electrochemical sensor.
3. Preparing a sulfhydrylation graphene-loaded gold platinum nanoparticle modified molecularly imprinted electrochemical sensor:
(1) self-assembling 4-aminothiophenol on a sulfhydrylation graphene modification screen printing electrochemical sensor:
immersing the sulfhydrylation graphene-loaded gold platinum nanoparticle modified silk-screen printing electrochemical sensor prepared in the step 2 into 10 mmol.L -1 And (2) in an absolute ethanol solution of 4-aminothiophenol for 24 hours, so that the ionic liquid loaded gold nano-sheet and-SH in the 4-aminothiophenol form Au-S bonds through strong coordination, are self-assembled on the surface of the sensor, and are directionally arranged into an ordered compact monomolecular layer.
(2) Self-assembly of methyl parathion on the sensor:
soaking the sensor self-assembled in the step (1) in 1 mmol.L -1 And (4) dissolving methyl parathion in the solution for 6 hours. NO in methyl parathion molecule 2 O atom, etc. and-NH in 4-aminothiophenol on the sensor surface 2 Are bound together by means of hydrogen bonds.
(3) Preparing a sulfhydrylation graphene-loaded gold platinum nanoparticle modified molecular imprinting screen printing electrochemical sensor:
an electrochemical sensor of the methyl parathion molecularly imprinted polymer is prepared by an electropolymerization method in an experiment.
Before electropolymerization, introducing N into the polymerization solution 2 And deoxidizing in 15 min. Then the sensor assembled by 4-aminothiophenol and methyl parathion is used as a working electrode and is immersed into 10 mmol.L -1 4-aminothiophenol, 1 mmol. L -1 Methyl parathion, 50 mmol.L -1 In the anhydrous ethanol polymerization solution of tetrabutylammonium perchlorate, cyclic voltammetry is adopted for scanning, the potential range is-0.2-0.6V, and the scanning speed is 50 mV.s -1 And scanning for 10 circles to obtain the methyl parathion molecularly imprinted polymer. Then the sensor which is well electropolymerized is immersed into 0.5 mol.L -1 Eluting in HCl for 30min to remove methyl parathion template molecule, and washing with water, N 2 And drying for later use.
(4) Preparation of non-imprinted electrochemical sensors:
and under the same condition, the methyl parathion template molecule is not added into the polymerization solution to prepare the non-imprinted electrochemical sensor.
5. Performance test of graphene composite nanomaterial modified molecularly imprinted electrochemical sensor
The thiolated graphene loaded gold platinum nanoparticle modified molecular imprinting screen printing electrochemical sensor is prepared under the optimal experimental conditions, and various performance indexes of the sensor are examined.
The electrochemical detection of methyl parathion is carried out by Cyclic Voltammetry (CV) and Differential Pulse Voltammetry (DPV). Adopting a screen printing three-electrode system, and respectively using thiolated graphene loaded gold platinum nanoparticle modified molecular imprinting screen printing electrochemistryThe sensor is a working electrode, the Ag/AgCl is a reference electrode, and the carbon is a counter electrode. Wherein CV determination conditions are as follows: containing 0.1 mol. L - 1 5 mmol. L of KCl -1 K 3 [Fe(CN) 6 ]Scanning in the solution, wherein the voltage range is-0.8-0.4V, and the scanning speed is 100mV s -1 . DPV measurement conditions: at 0.1 mol. L -1 A standard solution of methyl parathion prepared from PBS buffer solution with pH 6.0, the scanning voltage is-0.8-0.4V, and the scanning speed is 50 mV.s -1 Pulse amplitude of 50mV, pulse width of 0.05s, sample width of 0.05s, pulse period of 0.2s, and standing time of 2 s.
The linear range, the lower detection limit, the stability, the repeatability, the selectivity, the actual sample standard adding recovery rate and other indexes of the sensor are examined through experiments, and the results show that various performance indexes of the sensor are good, and the rapid and quantitative analysis of actual samples can be met.
The electrochemical biosensor is constructed by taking electrochemical detection as a main body and combining a high-selectivity molecular imprinting biotechnology and a nano material with excellent performance, has the advantages of high sensitivity, strong specificity and easiness in automation, and can meet the requirements of rapid screening and field quantitative detection of pesticide residues. The molecular imprinting technology is also called as molecular template technology, is a technology capable of customizing binding sites, has memory effect on the shape, size and functional groups of template molecules, has high selectivity, and is widely applied to preparation of molecular recognition polymer materials. The molecular imprinting electrochemical sensor mainly utilizes artificial synthetic holes of a molecular imprinting polymer to carry out specific binding on a target test object, so as to carry out high-selectivity detection on the analyte. The method has the advantages of low cost, simple preparation, high strength, strong selectivity, suitability for various template molecules, rich groups and the like. The nano material is known to have good optical, electrical and catalytic effects, the graphene nano material with high electron conduction, good adsorption performance and high electrocatalytic activity is introduced in the construction of the sensor, and the three-dimensional nano net is loaded on the surface of the graphene nano material to prepare the molecularly imprinted polymer film, so that more effective imprinted sites are obtained, the loading capacity and the electron transmission capacity of the sensor are improved, and the sensitivity and the selectivity of the sensor are improved.
The invention makes the core element of the electrochemical sensor, namely the working electrode, into a chip, and utilizes the screen printing technology to prepare the disposable, low-price and disposable sensor by adopting the screen printing technology to deposit and print on the insulating support substrate in sequence.
The present embodiment is only for explaining the present invention, and it is not limited to the present invention, and those skilled in the art can make modifications of the present embodiment without inventive contribution as needed after reading the present specification, but all of them are protected by patent law within the scope of the claims of the present invention.
Claims (8)
1. A construction method of an electrochemical sensor for rapidly and quantitatively detecting pesticide residues is characterized by comprising the following steps:
self-assembling S1 and 4-aminothiophenol on a sulfhydrylation graphene modification screen printing electrochemical sensor: the method comprises the following steps of (1) immersing a sulfhydrylation graphene-loaded gold platinum nanoparticle modified screen printing electrochemical sensor into an absolute ethyl alcohol solution of 4-aminothiophenol, enabling gold nanoparticles and-SH in the 4-aminothiophenol to form Au-S bonds through strong coordination, self-assembling the Au-S bonds on the surface, and directionally arranging the Au-S bonds into an ordered compact monomolecular layer;
s2, self-assembly of methyl parathion on the sensor: soaking the self-assembled sensor in S1 in methyl parathion solution to make-NO in methyl parathion molecule 2 O atom and-NH in 4-aminothiophenol on sensor surface 2 Are bound by means of hydrogen bonds;
s3, preparing the thiolated graphene-loaded gold platinum nanoparticle modified molecular imprinting screen printing electrochemical sensor: an electrochemical sensor of the methyl parathion molecularly imprinted polymer is prepared by adopting an electropolymerization method.
2. The construction method of the electrochemical sensor for rapid quantitative pesticide residue detection as claimed in claim 1, wherein the electrochemical sensor for molecularly imprinted polymer of methyl parathion is prepared in the process of S3, and the following steps are required before electropolymerization:
firstly introducing N into the polymerization solution 2 Deoxidizing, immersing the assembled sensor of 4-amino thiophenol and methyl parathion as working electrode in the absolute alcohol polymerizing solution of 4-amino thiophenol, methyl parathion and tetrabutyl ammonium perchlorate, scanning by cyclic voltammetry to obtain molecular engram polymer of methyl parathion, immersing the electropolymerized sensor in HCl for eluting to remove methyl parathion template molecule, washing with water, and N 2 And drying for later use.
3. The construction method of the electrochemical sensor for rapid quantitative pesticide residue detection according to claim 1 or 2, wherein in the S1 process, the preparation of the electrochemical sensor modified by the thiolated graphene-loaded gold platinum nanoparticles through screen printing comprises the following steps:
k1, preparation of a screen printing electrochemical sensor: the screen printing electrochemical sensor comprises a working electrode, a reference electrode and a counter electrode three-electrode system; the substrate layer is made of PET material; the carbon layer is formed on the basal layer in a silk-screen printing mode, the diameter of the working electrode is 3mm, the reference electrode and the counter electrode are annular, the three electrodes are respectively positioned on the outer sides of the reference electrode to form three silk-screen printing electrodes, the lower end interface is a data transmission interface, and pins corresponding to the interfaces are communicated;
k2, preparation of diazonium salt modified screen printing sensor: firstly, placing the prepared screen printing electrochemical sensor in K1 in N 2 Scanning in 4-nitrobenzene diazo tetrafluoroborate and tetrabutylammonium tetrafluoroborate acetonitrile solutions in a saturated environment by adopting a cyclic voltammetry method; after electrodeposition, repeatedly washing the electrode with acetonitrile and water; then scanning in an ethanol solution containing KCl by using a cyclic voltammetry method, reducing nitro groups into amino groups to prepare a diazonium salt modified silk-screen printing sensor, washing with water, and drying for later use;
k3, preparation of a sulfhydrylation graphene modified screen printing sensor: soaking the diazonium salt modified sensor prepared by K2 in a thiolated graphene aqueous dispersion to obtain a thiolated graphene modified sensor, washing with water, and drying for later use;
k4, preparing the electrochemical sensor modified by the thiolated graphene-loaded gold platinum nanoparticles through screen printing: and dropwise coating the dispersed liquid of the gold and platinum nanoparticles loaded with the ionic liquid on the surface of the sulfhydrylation graphene modified sensor prepared in K3, and drying under an infrared lamp to obtain the sulfhydrylation graphene loaded gold and platinum nanoparticle modified screen printing electrochemical sensor.
4. The construction method of the electrochemical sensor for rapid quantitative pesticide residue detection as claimed in claim 3, wherein the data interface is a Type-C interface.
5. The construction method of the electrochemical sensor for rapid quantitative pesticide residue detection as claimed in claim 4, wherein in the K1 process, before the sensor is prepared, the following steps are required:
the polyethylene terephthalate substrate is put into ethanol solution for ultrasonic treatment to remove surface grease and dust, and then is put into an oven for baking.
6. The construction method of the electrochemical sensor for rapid quantitative pesticide residue detection as claimed in claim 5, wherein in the K1 process, the screen printing electrochemical sensor printing process is completed on a screen printer, and the manufacturing process comprises the following steps:
firstly, manufacturing Type-C specification double-sided pins, copper leads and double-sided bonding pads; then, printing a three-electrode conductive line by silver paste, and thermally curing; printing the working electrode and the counter electrode by using conductive carbon paste in sequence, and thermally curing again; then printing a reference electrode layer by using Ag/AgCl slurry, and thermally curing again; and finally, printing the sensor insulating layer by using light-cured insulating paste, exposing the front end working area and the rear wire area, and curing by using ultraviolet light.
7. The construction method of the electrochemical sensor for rapid quantitative pesticide residue detection according to claim 6, wherein the preparation of the ionic liquid loaded gold platinum nanoparticle dispersion liquid comprises the following steps:
t1, preparation of gold nanosheet dispersion liquid: adding 1-butyl-3-methylimidazolium tetrafluoroborate ionic liquid into chloroauric acid trihydrate, heating by microwave, and naturally cooling to room temperature to obtain a gold nanosheet dispersion;
t2, preparation of platinum nanoparticles: adding KOH and ascorbic acid into H 2 Adding chloroplatinic acid into the mixed solution, oscillating, and carrying out water bath; obtaining platinum nano particles after centrifugal separation and water washing;
t3, preparation of ionic liquid supported gold platinum nanoparticle dispersion liquid: adding the platinum nanoparticles into the ionic liquid loaded gold nanosheets for ultrasonic dispersion.
8. An electrochemical sensor for rapidly and quantitatively detecting pesticide residues, which is characterized by being prepared by applying the construction method of the electrochemical sensor for rapidly and quantitatively detecting pesticide residues as claimed in any one of claims 1 to 7.
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