CN106841343A - A kind of Tebuconazole molecular engram film electrode, portable sensor and its application method and application - Google Patents
A kind of Tebuconazole molecular engram film electrode, portable sensor and its application method and application Download PDFInfo
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- CN106841343A CN106841343A CN201710207535.XA CN201710207535A CN106841343A CN 106841343 A CN106841343 A CN 106841343A CN 201710207535 A CN201710207535 A CN 201710207535A CN 106841343 A CN106841343 A CN 106841343A
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- tebuconazole
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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
- G01N27/28—Electrolytic cell components
- G01N27/30—Electrodes, e.g. test electrodes; Half-cells
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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
- G01N27/28—Electrolytic cell components
- G01N27/30—Electrodes, e.g. test electrodes; Half-cells
- G01N27/333—Ion-selective electrodes or membranes
- G01N27/3335—Ion-selective electrodes or membranes the membrane containing at least one organic component
Abstract
The invention provides a kind of Tebuconazole molecular engram film electrode, including base electrode, modify Prussian blue in the gold nano grain of described matrix electrode surface, sulfydryl Graphene and gold successively, be attached to the Tebuconazole molecular engram film on the golden Prussian blue surface；The Tebuconazole molecular engram film is the o-aminophenol and arofene with Tebuconazole as template molecule.The Tebuconazole molecular engram film electrode provided using the present invention carries out quantitative determination to Tebuconazole, and test limit can reach 1.63 × 10‑8Mol/L, sensitivity is high.The present invention is fixed on probe molecule is Prussian blue on Tebuconazole molecular engram film electrode, it is possible to achieve the direct measure of electrically inactive target compound in sample, is made the operation of sensor more easy and is suitable to field quick detection.
Description
Technical field
The present invention relates to Pesticides Testing technical field, and in particular to a kind of Tebuconazole molecular engram film electrode, portable sensing
Device and its application method and application.
Background technology
Tebuconazole is a kind of high efficiency triazole bactericidal agent, is widely used in the crops such as peanut, barley, paddy rice, apple
Disease control, frequent use can cause soil pollution, and jeopardize the ecosystem, underground water and human health.
At present, the method for detection Tebuconazole is main based on chromatographic technique, with sensitivity it is high, the degree of accuracy is good, qualitative fixed
The advantages of amount analysis is splendid.But these analysis methods are limited in that：Required analytical instrument is typically placed in away from scene
In standard analysis laboratory, and instrument price is expensive, and complex operation is, it is necessary to the operation of professional；Time-consuming for sample pre-treatments,
Difficulty meets the demand of Residual Pesticides in Farm Produce field quick detection.
Prior art, but the quantitative determination sensitivity of electrochemical sensor although residues of pesticides easy to carry is relatively low, and
And electrochemical sensor needs electron mediator that the power of electrochemical signals is indicated as probe, and these probes can contaminated samples
And then interference is produced to testing result, so as to cause testing result inaccurate.Therefore, a kind of portable, price of development is needed badly low
Honest and clean and accuracy in detection Fast Determination of Pesticide Residue means high.
The content of the invention
In view of this, it is an object of the invention to provide a kind of device that can be applied to Tebuconazole quantitative determination, portable
Band, the degree of accuracy, sensitivity are high.
In order to realize foregoing invention purpose, the present invention provides following technical scheme：
The invention provides a kind of Tebuconazole molecular engram film electrode, including base electrode, modify successively in described matrix
The gold nano grain of electrode surface, sulfydryl Graphene and gold-Prussian blue, it is attached to the penta of the gold-Prussian blue surface
Azoles alcohol molecular engram film；
The Tebuconazole molecular engram film is the o-aminophenol and arofene with Tebuconazole as template molecule.
The invention provides the preparation method of Tebuconazole molecular engram film electrode described in above-mentioned technical proposal, including following step
Suddenly：
(1) base electrode is placed in tetrachloro alloy acid solution, electro-deposition is carried out using potentiostatic method, in described matrix electricity
Pole surface deposits gold nano grain, obtains gold nano particle modification electrode；
(2) the gold nano particle modification electrode for obtaining the step (1) stands in sulfydryl graphene aqueous solution, makes mercapto
Base graphene modified obtains sulfydryl Graphene-gold nano particle modification electrode on the gold nano grain surface of the electrode；
(3) the sulfydryl Graphene-gold nano particle modification electrode for obtaining the step (2) is placed in and contains potassium nitrate, four
In the mixed solution of the acid of chlorine alloy and potassium ferrocyanide, gold-Prussian blue particle is deposited using cyclic voltammetry, obtain Jin-general
Shandong scholar indigo plant-sulfydryl Graphene-gold nano particle modification electrode；
(4) gold for obtaining the step (3)-Prussian blue-sulfydryl Graphene-gold nano particle modification electrode is placed in and contains
Having in the phosphate buffer of Tebuconazole, o-aminophenol and resorcinol carries out electropolymerization, obtains polymer film modified electrode；
(5) polymer film modified electrode of the step (4) is placed in and polymerization is removed in the mixed solution of methyl alcohol and acetic acid
Tebuconazole molecule in thing film, obtains Tebuconazole molecular engram film electrode.
Preferably, the concentration of tetrachloro alloy acid solution described in step (1) is 2.5~3.5mmol/L, during the electro-deposition
Between be 80~150s.
Preferably, the concentration of step (2) the sulfydryl graphene aqueous solution is 0.25~0.5mg/mL, the time of repose
It is 2~6h.
Preferably, the concentration of potassium nitrate is 0.05~0.2mol/L, tetrachloro alloy acid in step (3) described mixed solution
Concentration is 0.5~1.5mmol/L and ferrocyanide potassium concn is 0.5~1.5mmol/L；The cyclic voltammetry condition is：
0~1.0V of potential range, sweep speed is 50mV/s, and scanning 15~30 is enclosed.
Preferably, in step (4) the phosphoric acid mixed solution, the concentration of o-aminophenol and resorcinol independently is
2.0~2.5mmol/L, the concentration of Tebuconazole is 0.5~1mmol/L, and the concentration of phosphate buffer is 0.01~0.07mmol/L；
The electropolymerizatioconditions conditions are：Potential range -0.4~1.0V, sweep speed is 50mV/s, and scanning 8~10 is enclosed.
Preferably, in the mixed solution of step (5) methyl alcohol and acetic acid, the volume ratio of methyl alcohol and acetic acid is 1:7~1:
11。
Present invention also offers it is a kind of for Tebuconazole quantitative determination portable sensor, including working electrode, to electrode,
Reference electrode and electrolyte solution, the working electrode are Tebuconazole molecular engram film electrode or above-mentioned described in preceding solution
The Tebuconazole molecular engram film electrode that preparation method described in technical scheme is obtained, the electrolyte solution be pH value be 5.0~
8.0th, concentration is 0.08~0.14mol/L potassium nitrate solutions.
The invention provides described in the Tebuconazole molecular engram film electrode or above-mentioned technical proposal described in preceding solution
Application of the portable sensor in Tebuconazole residues of pesticides in determining agricultural product.
Preferably, the method for determining Tebuconazole residues of pesticides in agricultural product is comprised the following steps：
1) Tebuconazole molecular engram film electrode is suspended in sample solution, adsorbs 10~20min；
2) by the Tebuconazole molecular engram film electrode in the step (1) after absorption as working electrode, and to electrode, ginseng
Three-electrode system is constituted than electrode, electro-chemical test is carried out in electrolyte solution, the differential pulse voltammetry volt-ampere that record test is obtained
Scanning curve and peak response current value；
3) the peak response current value of the sample solution obtained according to standard curve and the step (2), obtains sample
The content of Tebuconazole in solution；
The standard curve is linear between the peak response current value and Tebuconazole concentration of differential pulse volt-ampere test
Curve.
Compared with prior art, the present invention has advantages below to the present invention：
The Tebuconazole molecular engram film electrode that the present invention is provided by modifying gold nano grain, mercapto successively on base electrode
Base Graphene and gold-Prussian blue, in conjunction with Tebuconazole molecular engram film, effectively raise the sensitivity to Tebuconazole detection
And the degree of accuracy.The Tebuconazole molecular engram film electrode provided using the present invention is detected that test limit can reach 1.63 × 10- 8Mol/L, it is seen that the Tebuconazole molecular engram film electrode that the present invention is provided has high sensitivity, can be used in quantifying for Tebuconazole
Detection.
One layer of gold nano grain first is deposited on base electrode surface in the Tebuconazole molecular engram film electrode that the present invention is provided,
Recycling parent's gold ability of sulphur atom makes gold nano grain be connected by the golden sulfide linkage of stabilization with sulfydryl Graphene, modifies sulfydryl stone
Black alkene can expand electrode specific surface area, amplify sensor response signal, then significantly improve the sensitivity of electrode.
The Tebuconazole molecular engram film electrode that the present invention is provided is co-deposited golden-Prussian blue in sulfydryl graphenic surface,
So that probe molecule is Prussian blue being fixed on electrode, just simplify real without adding probe molecule in the electrolytic solution during detection
Operation is tested, the sensitivity and the degree of accuracy for directly determining is improved.The Tebuconazole molecular engram film electrode that the present invention is provided is especially suitable
In field quick detection so that Residual Pesticides in Farm Produce Site Detection is more quick and accurate.
The present invention is co-deposited golden-Prussian blue in sulfydryl Graphene-gold nano particle modification electrode surface, additionally it is possible to improve
The electric conductivity of electrode, detection time can also be shortened while electrode detection sensitivity is further improved.In conjunction with penta azoles
The Tebuconazole molecular engram film that alcohol is template molecule, is constituted as polymerized functional monomer with resorcinol and o-aminophenol, can
Specific recognition Tebuconazole molecule, so as to get Tebuconazole molecular engram film electrode there are good sensitivity and specificity, can
With the identification Tebuconazole molecule of precise and high efficiency.Experiment shows the Tebuconazole molecular engram film of present invention offer to Triadimenol, penta bacterium
The analogue response such as azoles is low, can effectively differentiate the Tebuconazole agricultural chemicals similar with other structures, it is to avoid Tebuconazole knot
Influence of the similar agricultural chemicals of structure to measurement result.
Provided by the present invention for the portable sensor of Tebuconazole quantitative determination, including above-mentioned Tebuconazole molecular engram film electricity
Pole as working electrode, to electrode, reference electrode and electrolyte solution, relative to existing chromatogram or chromatograph-mass spectrometer coupling
For detection method, detecting instrument small volume is convenient to carry out, not examined place limitation, can be used for Site Detection.And
And the portable sensor that the present invention is provided quantitative determines 15.5~17.5min of Tebuconazole content used time in sample, greatly shortens
Detection time, improves the detection efficiency of Tebuconazole.
When the portable sensor provided using the present invention is quantitative determined to Tebuconazole in agricultural product, the recovery of Tebuconazole
Rate can reach 77.9~118.69%, show that the degree of accuracy of the portable sensor quantitative determination of present invention offer is high, disclosure satisfy that
The demand of Residual Pesticides in Farm Produce Site Detection.
Provided by the present invention for the portable sensor simple structure of Tebuconazole quantitative determination, small volume is easy to operate, phase
Low, the easily operated and outgoing carryings of instrument cost such as the chromatograph used for existing chromatographic detection method, are particularly suitable for
Field quick detection.
Brief description of the drawings
Fig. 1 is the preparation flow schematic diagram of Tebuconazole molecular engram film electrode；
Wherein, AuNPs is gold nano grain, and SH-G is sulfydryl Graphene, and Au-PB is golden-Prussian blue, and Teb is penta azoles
Alcohol molecule, analogue is Tebuconazole molecular mimics, and p (AP-DHB) is Tebuconazole molecular engram film；
Fig. 2 is the cyclic voltammogram of voltolisation alloy-Prussian blue-sulfydryl Graphene-gold nano particle modification electrode process；
Illustration be voltolisation alloy-Prussian blue electrode remove it is Prussian blue after the cyclic voltammogram that obtains；
Fig. 3 is the cyclic voltammogram of electropolymerization polymer membrane electrode process；
Fig. 4 is the cyclic voltammogram of the modification of Tebuconazole molecular engram film electrode and detection process；
Fig. 5 is the differential pulse voltammetry voltammetric scan curve that Tebuconazole portable sensor determines various concentrations Tebuconazole sample；Insert
Figure is the standard curve of the logarithm value-current-responsive changing value of the sensor determination sample of the working electrode composition of different modifying；
Fig. 6 is the selective evaluation figure of Tebuconazole and its analogue.
Specific embodiment
The invention provides a kind of Tebuconazole molecular engram film electrode, including base electrode, modify successively in described matrix
The gold nano grain of electrode surface, sulfydryl Graphene and gold-Prussian blue, it is attached to the penta of the gold-Prussian blue surface
Azoles alcohol molecular engram film；
The Tebuconazole molecular engram film is the o-aminophenol and arofene with Tebuconazole as template molecule.
The present invention to the type of base electrode without any restriction, using commercially available electrode, such as platinum electrode, gold electrode, glass
Carbon electrode, carbon fiber microelectrodes with micro pipette tips or chemically modified electrode, preferably glass-carbon electrode.
In the present invention, specific surface area can be increased after the gold nano particle modification base electrode, so that pass through
Current strength increases, and then improves the detection sensitivity of electrode.Meanwhile, gold nano grain can also be by covalent bond and sulfydryl stone
Black alkene is combined, for the fixation of sulfydryl Graphene provides basis.
In the present invention, the sulfydryl Graphene is the Graphene with sulfydryl modification.The present invention is to sulfydryl Graphene
Source using commercially available prod, preferably uses Suzhou carbon Feng Shi without any restriction in some embodiments of the invention
Mo Xi Science and Technology Ltd.s sell sulfydryl Graphene.
In the present invention, the gold-Prussian blue is in sulfydryl Graphene by the Prussian blue co-precipitation with gold nano grain
Prussian blue as probe molecule in surface, the gold-Prussian blue, being co-deposited with gold nano grain can be visited with effective guarantee
Pin molecule is firmly bonded on electrode, and gold nano grain can also be by forming covalent bond gold sulfide linkage jail with sulfydryl Graphene
Consolidation is closed；Gold-Prussian blue the electric conductivity that can further improve electrode, so that the conduction of velocity of electric signal is faster,
Minute effectively is shortened, while the detection sensitivity of electrode can also be strengthened.
The invention provides the preparation method of Tebuconazole molecular engram film electrode described in above-mentioned technical proposal, including following step
Suddenly：
(1) base electrode is placed in tetrachloro alloy acid solution, electro-deposition is carried out using potentiostatic method, in described matrix electricity
Pole surface deposits gold nano grain, obtains gold nano particle modification electrode；
(2) the gold nano particle modification electrode for obtaining the step (1) stands in sulfydryl graphene aqueous solution, makes mercapto
Base graphene modified obtains sulfydryl Graphene-gold nano particle modification electrode on the gold nano grain surface of the electrode；
(3) the sulfydryl Graphene-gold nano particle modification electrode for obtaining the step (2) is placed in and contains potassium nitrate, four
In the mixed solution of the acid of chlorine alloy and potassium ferrocyanide, gold-Prussian blue particle is deposited using cyclic voltammetry, obtain Jin-general
Shandong scholar indigo plant-sulfydryl Graphene-gold nano particle modification electrode；
(4) gold for obtaining the step (3)-Prussian blue-sulfydryl Graphene-gold nano particle modification electrode is placed in and contains
Having in the phosphate buffer of Tebuconazole, o-aminophenol and resorcinol carries out electropolymerization, obtains polymer film modified electrode；
(5) polymer film modified electrode of the step (4) is placed in the mixed solution containing methyl alcohol and acetic acid and is removed
Tebuconazole molecule in polymer film, obtains Tebuconazole molecular engram film electrode.
The preparation process of Tebuconazole molecular engram film electrode of the present invention is as shown in Figure 1.
The present invention before base electrode is placed in into tetrachloro alloy acid solution, preferred pair described matrix electrode carry out pretreatment and
Cleaning.In the present invention, the method for the pretreatment and cleaning preferably includes following steps：
A, base electrode is placed in the mixed solution of hydrogen peroxide and the concentrated sulfuric acid 10~30min of immersion, with 0.03~0.10 μ
The Al of m2O3Carry out sanding and polishing；
B, the base electrode after sanding and polishing in the step a is cleaned, 8~15min of ultrasound in water；
C, will in the step b ultrasound after base electrode be placed in 0.1~1.0mol/L dilution heat of sulfuric acid, using circulation
Voltammetry scanning 15~30 is enclosed, cleaning drying.
Base electrode is placed in 10~30min for the treatment of in the mixed solution of hydrogen peroxide and the concentrated sulfuric acid by the present invention.Specifically, this
Be soaked in base electrode in the mixed solution of hydrogen peroxide and the concentrated sulfuric acid by invention.In the present invention, the hydrogen peroxide and the concentrated sulfuric acid
Volume ratio be 1:2~5, preferably 1:3.Soak time of the present invention is preferably 15~25min, more preferably 20min.This
The volumetric concentration for inventing the hydrogen peroxide is preferably 20~50%, more preferably 30%；The concentrated sulfuric acid is using commercial goods
Can.
The volume that the present invention is used when processing base electrode to the mixed solution of hydrogen peroxide and the concentrated sulfuric acid is without any restriction, energy
It is enough to immerse base electrode.The present invention is using the mixed solution of hydrogen peroxide and the concentrated sulfuric acid to base electrode treatment, Neng Gouyou
Organic impurities on the removal base electrode of effect.
The present invention mixed solution is processed after base electrode with 0.03~0.10 μm of Al2O3Carry out sanding and polishing.At this
In invention, the Al2O3Particle diameter be preferably 0.05 μm.The present invention uses Al2O3Sanding and polishing is to electrode surface to minute surface degree
When stop sanding and polishing.Sanding and polishing can remove the oxide layer on base electrode surface, inert layer.
After sanding and polishing, the present invention cleans base electrode, 8~15min of ultrasound in water.Specifically, the present invention will beat
Base electrode after grinding and polishing light is washed, and removes the Al of base electrode remained on surface2O3.In the present invention, the ultrasonic time
Preferably 9~12min, more preferably 10min.
After ultrasound, be placed in base electrode in 0.1~1.0mol/L dilution heat of sulfuric acid by the present invention, is swept using cyclic voltammetry
Retouch 15~30 circle, cleaning drying after both pretreated base electrode.The concentration of dilution heat of sulfuric acid of the present invention is preferably
0.4~0.8mol/L, more preferably 0.5mol/L.In the present invention, the voltage range of the cyclic voltammetry be -0.2~
1.6V；The cyclic voltammetry scanning number of turns is preferably 18~25 circles, more preferably 20 circles；The cyclic voltammetry sweep speed
Preferably 50mV/s.
The present invention makes electrode polarization using cyclic voltammetry scanning base electrode, and base electrode table is made by electrochemical means
Clean in face.
Be placed in base electrode in tetrachloro alloy acid solution by the present invention, using potentiostatic method electro-deposition, obtains gold nano
Grain modified electrode.The concentration of tetrachloro alloy acid solution of the present invention is preferably 2.5~3.5mmol/L, more preferably 3mmol/
L.In the present invention, the electrodeposition time is preferably 80~150s, more preferably 100s.During potentiostatic electrodeposition of the present invention
Current potential be -0.3~-0.1V, preferably -0.2V.The present invention is by by electric current using potentiostatic method deposition gold nano grain
The gold ion in tetrachloro alloy acid is set to be reduced to gold nano grain so as to be deposited on base electrode surface.
After obtaining gold nano particle modification electrode, the present invention is by gold nano particle modification electrode in sulfydryl graphene aqueous solution
Middle standing, obtains sulfydryl Graphene-gold nano particle modification electrode.In the present invention, using parent's gold ability of sulphur atom, it then follows
Hard and soft acid and base action principle, sulfydryl Graphene is connected with gold nano grain by polar covalent bond gold sulfide linkage, so that sulfydryl stone
Black alkene modification is on gold nano grain surface.
Sulfydryl Graphene of the present invention can be completed at normal temperatures with the reaction of gold nano grain.In the present invention, institute
The concentration for stating sulfydryl graphene aqueous solution is 0.25~0.5mg/mL, more preferably 0.25mg/mL.Time of repose of the present invention
Preferably 2~6h, more preferably 4h.
The present invention improves Tebuconazole molecular engram film electricity by gold nano grain and the dual sensitization of sulfydryl Graphene
The detection sensitivity of pole, makes test limit lower, in can be used in actual Tebuconazole quantitative determination.
It is of the invention by sulfydryl Graphene-gold nano particle modification after obtaining sulfydryl Graphene-gold nano particle modification electrode
Electrode is placed in the mixed solution containing potassium nitrate, tetrachloro alloy acid and potassium ferrocyanide, using cyclic voltammetry in sulfydryl stone
Black alkene surface deposition gold-Prussian blue, obtains gold-Prussian blue-sulfydryl Graphene-gold nano particle modification electrode.The present invention
In the mixed solution, the concentration of potassium nitrate is preferably 0.05~0.2mol/L, more preferably 0.1mol/L；Tetrachloro alloy acid
Concentration is preferably 0.5~1.5mmol/L, more preferably 1mmol/L；The concentration of potassium ferrocyanide is preferably 0.5~1.5mmol/
L, more preferably 1mmol/L.In the present invention, the condition of the cyclic voltammetry is preferably：0~1.0V of potential range, scanning
Speed is 50mV/s, and scanning 15~30 is enclosed；The scanning number of turns is more preferably 17 circles.
In the present invention, there is following chemical reaction when depositing golden-Prussian blue using cyclic voltammetry：
Tetrachloro alloy acid reaction generation gold nano grain in the mixed solution：
HAuCl4→H++AuCl4 -
AuCl4 -+3e-→Au(0)+4Cl-
Au(0)+3HOH→Au(OH)3+3H+
Ferrocyanide nak response generation in the mixed solution is Prussian blue：
[Fe(CN)6]3-+6H+→Fe3++6HCN
Fe3++e-→Fe2+
Fe2++[Fe(CN)6]3-→[Fe3+Fe2+(CN)6]-
Generation gold nano grain and it is Prussian blue after, be co-deposited in the presence of cyclic voltammetry in sulfydryl Graphene table
Face, obtains gold-Prussian blue-sulfydryl Graphene-gold nano particle modification electrode.
Gold-Prussian blue-sulfydryl Graphene-gold nano particle modification electrode that the present invention will be obtained is placed in and contains penta azoles
Electropolymerization is carried out in the phosphate buffer of alcohol, o-aminophenol and resorcinol, polymer film modified electrode is obtained.Institute of the present invention
State electropolymerization preferably carries out electropolymerization with cyclic voltammetry, and the condition of the cyclic voltammetry is preferably：Potential range -0.4
~1.0V, sweep speed is 50mV/s, and scanning 8~10 is enclosed；The scanning number of turns is preferably 9 circles.
The concentration of phosphate buffer of the present invention is preferably 0.01~0.07mmol/L, more preferably 0.05mmol/L；
Tebuconazole concentration in the phosphate buffer is preferably 0.5~1mmol/L, more preferably 0.7mmol/L；The phosphoric acid buffer
The concentration of o-aminophenol and resorcinol in liquid is preferably independently 2.0~2.5mmol/L, more preferably 2.1mmol/L；
The pH of the phosphate buffer is preferably 5~9, more preferably 7.
The present invention with Tebuconazole molecule as template, with o-aminophenol and resorcinol as polymerized functional monomer, in voltolisation
Cooperation is polymerized to the Tebuconazole molecular engram film containing template molecule under using, and Tebuconazole molecular engram is film modified in Jin-general
Shandong Shi Lan surfaces.
It is currently preferred to obtain polymer film modified electrode after 3~16h of standing after electropolymerization.The time of repose is more
Preferably 5h.The present invention stands in atmosphere to standing environment without any restriction.The present invention is after electropolymerization to poly-
It is in order that polymer film is firmly bonded to electrode surface, mould directly to be carried out after preventing electropolymerization that the electrode of compound film carries out standing
Polymer film is damaged caused by plate molecule is removed.
After obtaining polymer modified electrode, polymer modified electrode is placed in the present invention mixed solution of methyl alcohol and acetic acid
In, the template molecule in removing polymer film obtains Tebuconazole molecular engram film electrode.Methyl alcohol of the present invention and acetic acid it is mixed
Close in solution, the volume ratio of methyl alcohol and acetic acid is preferably 1:7~1:11, more preferably 1:9.In the present invention, described removal is gathered
Preferably mixed solution is stirred during template molecule in compound film, the speed of agitator is preferably 100~
150rpm, more preferably 120rpm；The mixing time is preferably 20~40min, more preferably 30min.Acetic acid and methyl alcohol
Mixed solution by with polymer film competitive Adsorption Tebuconazole molecule, make Tebuconazole molecule from polymer film be removed so that
Obtain the molecular engram film with Tebuconazole molecular cavities recognition site.
Present invention also offers it is a kind of for Tebuconazole quantitative determination portable sensor, including working electrode, to electrode,
Reference electrode and electrolyte solution, the working electrode are Tebuconazole molecular engram film electrode or above-mentioned described in preceding solution
The Tebuconazole molecular engram film electrode that preparation method described in technical scheme is obtained, the electrolyte solution be pH value be 5.0~
8.0th, concentration is 0.08~0.14mol/L potassium nitrate solutions.
In the present invention, the reference electrode is preferably calomel electrode, described to be preferably platinum electrode to electrode.
In the present invention, the pH value of the electrolyte solution is preferably 7.0；The potassium nitrate solution concentration is preferably
0.1mol/L.In the portable sensor that the present invention is provided, because working electrode Tebuconazole molecular engram film electrode is fixed with probe
Molecule is Prussian blue, thus probe molecule need not be added in electrolyte solution can be directly used for target compound in sample
Determine.
The invention provides described in the Tebuconazole molecular engram film electrode or above-mentioned technical proposal described in preceding solution
Application of the portable sensor in Tebuconazole residues of pesticides in determining agricultural product.
Preferably, the method for determining Tebuconazole residues of pesticides in agricultural product is comprised the following steps：
1) Tebuconazole molecular engram film electrode is suspended in sample solution, adsorbs 10~20min；
2) using the step 1) in Tebuconazole molecular engram film electrode after absorption as working electrode, and to electrode, ginseng
Three-electrode system is constituted than electrode, electro-chemical test is carried out in electrolyte solution, the differential pulse voltammetry volt-ampere that record test is obtained
Scanning curve and peak response current value；
3) according to standard curve and the step 2) the peak response current value of sample solution that obtains, obtain sample molten
The content of Tebuconazole in liquid；
The standard curve is linear between the peak response current value and Tebuconazole concentration of differential pulse voltammetry volt-ampere test
Curve.
Be suspended in Tebuconazole molecular engram film electrode in sample solution by the present invention, adsorbs 10~20min.It is of the present invention
Adsorption time is preferably 15min.Sample solution of the present invention obtains test substance homogenate, the preferred determinand
Matter includes green vegetables, cucumber, fresh kidney beans, radish.The present invention to the homogenate mode without any restriction, using the conventional homogenate side in this area
Formula, such as manual homogenization, mechanical homogenisation, ultrasound homogenate, multigelation.
The currently preferred Tebuconazole molecular engram film electrode by after the completion of absorption carries out electrochemistry survey after being cleaned with water
Examination.
After absorption, the present invention constitutes three with Tebuconazole molecular engram film electrode as working electrode with to electrode, reference electrode
Electrode system, carries out electro-chemical test, record electro-chemical test gained differential pulse voltammetry voltammetric scan curve in electrolyte solution
And peak response current value.In the present invention, the Differential Pulse Voltammetry condition is preferably：0.5~-0.1V of voltage, arteries and veins
Rush width 50ms, time interval 0.5s, jump rank current potential 5mV, modulated amplitude 50mV.
Because probe molecule is fixed on working electrode, thus Tebuconazole and penta azoles in electro-chemical test in sample
The gold that curent change produced by alcohol molecular engram film reaction is directly coated under Tebuconazole molecular engram film-Prussian blue connects
By so produce electrochemical signals change so that the peak response current value in influenceing electro-chemical test, by calculating maximum sound
The change of induced current value can characterize the Tebuconazole content that sample contains.The present invention is obtained according to standard curve and electro-chemical test
The peak response current value of the sample solution for arriving, is calculated the content of Tebuconazole in sample solution.Specifically, the present invention is not with
The difference of peak response current value during absorption and the maximum corresponding current value after absorption as ordinate, with the right of Tebuconazole concentration
Numerical value is that abscissa draws standard curve.The preferred range of linearity of standard curve of the present invention is 0~0.4mmol/L.
Specifically, it is 0,0.00005,0.0002,0.0005,0.001 that standard curve of the present invention is selection concentration,
The tebuconazole solution of 0.006,0.03,0.1,0.2 and 0.4mmol/L, using the Tebuconazole molecule in Tebuconazole portable sensor
Each standard series sample of blotting membrane electrode pair is adsorbed, and peak response current value is determined using Differential Pulse Voltammetry, will be surveyed
Fixed peak response current value and the difference of unadsorbed preceding peak response current value are used as ordinate, corresponding Tebuconazole standard system
The logarithm value of row sample concentration is that abscissa draws standard curve.Differential Pulse Voltammetry condition of the present invention is to be measured with measure
The condition of sample is identical.
Below in conjunction with the embodiment in the present invention, the technical scheme in the present invention is clearly and completely described.It is aobvious
So, described embodiment is only a part of embodiment of the invention, rather than whole embodiments.Based on the reality in the present invention
Example is applied, the every other embodiment that those of ordinary skill in the art are obtained under the premise of creative work is not made all belongs to
In the scope of protection of the invention.
Embodiment 1
It is 1 with 30% hydrogen peroxide and concentrated sulfuric acid volume ratio:3 mixed solution immersion glassy carbon electrode 20min, with 0.05 μm
Al2O3Sanding and polishing to electrode surface is washed in after minute surface degree, the ultrasound 10min in water.Electrode after ultrasound is used
Nitrogen is dried up, and is placed in the dilution heat of sulfuric acid of 0.5mol/L, and 20 are scanned in -0.2~1.6V voltage ranges with cyclic voltammetry
Circle.Use water cleaning electrode after the end of scan, nitrogen drying, both pretreated base electrode.
Pretreated base electrode is placed in the tetrachloro alloy acid solution of 3mmol/L, using potentiostatic method in -0.2V
Electro-deposition 100s under voltage, makes gold nano grain be deposited on base electrode surface, obtains gold nano particle modification electrode.
Gold nano particle modification electrode is placed in 0.25mg/mL sulfydryl graphene aqueous solutions, 4h is stood and is obtained sulfydryl stone
Black alkene-gold nano particle modification electrode.
Sulfydryl Graphene-gold nano particle modification electrode is placed in mixed solution, using cyclic voltammetry in current potential model
Enclose 0~1.0V, sweep speed 50mV/s, scanning 17 circle under conditions of deposit gold-it is Prussian blue, obtain gold-Prussian blue-sulfydryl
Graphene-gold nano particle modification electrode.The mixed solution be 0.1mol/L potassium nitrate, 1mmol/L tetrachloro alloys acid and
1mmol/L potassium ferrocyanides.
Gold-Prussian blue-sulfydryl Graphene-gold nano particle modification electrode is placed in and contains Tebuconazole, o-aminophenol
In the phosphate buffer of resorcinol, using cyclic voltammetry in potential range -0.4~1.0V, sweep speed 50mV/s, sweep
Retouch and be polymerized under conditions of 9 circles the Tebuconazole molecular engram film containing template molecule and modify in the gold-Prussia of the electrode
Blue surface, nitrogen drying stands 5h after water is rinsed, and obtains polymer membrane electrode.The concentration of the phosphate buffer is
0.05mmol/L, pH value is 7.0；Tebuconazole concentration is 0.7mmol/L in phosphate buffer, and o-aminophenol and resorcinol are dense
Degree is 2.1mmol/L.
It is 1 that polymer membrane electrode is placed in into volume ratio:Template molecule is removed in 9 methyl alcohol and acetic acid mixed solution,
120rpm rotating speeds stir 30min, and Tebuconazole molecular engram film electrode is obtained after being cleaned with water.
The Tebuconazole molecular engram film electrode preparation used time is short, and preparation method is simple, takes few, high financial profit.
Embodiment 2
Base electrode is placed in the tetrachloro alloy acid solution of 2.5mmol/L, it is electric under -0.1V voltages using potentiostatic method
Deposition 80s, makes gold nano grain be deposited on base electrode surface, obtains gold nano particle modification electrode.
Gold nano particle modification electrode is placed in 0.25mg/mL sulfydryl graphene aqueous solutions, 2h is stood and is obtained sulfydryl stone
Black alkene-gold nano particle modification electrode.
Sulfydryl Graphene-gold nano particle modification electrode is placed in mixed solution, using cyclic voltammetry in current potential model
Enclose 0~1.0V, sweep speed 50mV/s, scanning 15 circle under conditions of deposit gold-it is Prussian blue, obtain gold-Prussian blue-sulfydryl
Graphene-gold nano particle modification electrode.The mixed solution be 0.05mol/L potassium nitrate, 0.5mmol/L tetrachloro alloys acid with
And 0.5mmol/L potassium ferrocyanides.
Gold-Prussian blue-sulfydryl Graphene-gold nano particle modification electrode is placed in and contains Tebuconazole, o-aminophenol
In the phosphate buffer of resorcinol, using cyclic voltammetry in potential range -0.4~1.0V, sweep speed 50mV/s, sweep
Retouch and be polymerized under conditions of 8 circles the Tebuconazole molecular engram film containing template molecule and modify in the gold-Prussia of the electrode
Blue surface, obtains polymer membrane electrode.The concentration of the phosphate buffer is 0.01mmol/L, and Tebuconazole is dense in phosphate buffer
It is 0.5mmol/L to spend, and pH value is 5.0；O-aminophenol and resorcinol concentration are 2.0mmol/L.
It is 1 that polymer membrane electrode is placed in into volume ratio:Template molecule is removed in 7 methyl alcohol and acetic acid mixed solution,
100rpm rotating speeds stir 20min, and Tebuconazole molecular engram film electrode is obtained after being cleaned with water.
Embodiment 3
It is 1 with 20% hydrogen peroxide and concentrated sulfuric acid volume ratio:2 mixed solution immersion glassy carbon electrode 15min, with 0.05 μm
Al2O3Sanding and polishing to electrode surface is washed in after minute surface degree, the ultrasound 8min in water.Electrode after ultrasound is used
Nitrogen is dried up, and is placed in the dilution heat of sulfuric acid of 0.4mol/L, and 15 are scanned in -0.2~1.6V voltage ranges with cyclic voltammetry
Circle.Use water cleaning electrode after the end of scan, nitrogen drying, both pretreated base electrode.
Pretreated base electrode is placed in the tetrachloro alloy acid solution of 3.5mmol/L, using potentiostatic method-
Electro-deposition 150s under 0.3V voltages, makes gold nano grain be deposited on base electrode surface, obtains gold nano particle modification electrode.
Gold nano particle modification electrode is placed in 0.5mg/mL sulfydryl graphene aqueous solutions, 6h is stood and is obtained sulfydryl graphite
Alkene-gold nano particle modification electrode.
Sulfydryl Graphene-gold nano particle modification electrode is placed in mixed solution, using cyclic voltammetry in current potential model
Enclose 0~1.0V, sweep speed 50mV/s, scanning 30 circle under conditions of deposit gold-it is Prussian blue, obtain gold-Prussian blue-sulfydryl
Graphene-gold nano particle modification electrode.The mixed solution be 0.2mol/L potassium nitrate, 1.5mmol/L tetrachloro alloys acid with
And 1.5mmol/L potassium ferrocyanides.
Gold-Prussian blue-sulfydryl Graphene-gold nano particle modification electrode is placed in and contains Tebuconazole, o-aminophenol
In the phosphate buffer of resorcinol, using cyclic voltammetry in potential range -0.4~1.0V, sweep speed 50mV/s, sweep
Retouch and be polymerized under conditions of 10 circles the Tebuconazole molecular engram film containing template molecule and modify in the gold-Prussia of the electrode
Blue surface, nitrogen drying stands 16h after water is rinsed, and obtains polymer membrane electrode.The concentration of the phosphate buffer is
0.07mmol/L, pH value is 6.0；Tebuconazole concentration is 1mmol/L, o-aminophenol and resorcinol concentration in phosphate buffer
It is 2.5mmol/L.
It is 1 that polymer membrane electrode is placed in into volume ratio:Template molecule is removed in 11 methyl alcohol and acetic acid mixed solution,
150rpm rotating speeds stir 40min, and Tebuconazole molecular engram film electrode is obtained after being cleaned with water.
Embodiment 4
It is 1 with 30% hydrogen peroxide and concentrated sulfuric acid volume ratio:3 mixed solution immersion glassy carbon electrode 20min, with 0.05 μm
Al2O3Sanding and polishing to electrode surface is washed in after minute surface degree, the ultrasound 10min in water.Electrode after ultrasound is used
Nitrogen is dried up, and is placed in the dilution heat of sulfuric acid of 0.5mol/L, and 20 are scanned in -0.2~1.6V voltage ranges with cyclic voltammetry
Circle.Use water cleaning electrode after the end of scan, nitrogen drying, both pretreated base electrode.
Pretreated base electrode is placed in the tetrachloro alloy acid solution of 3mmol/L, using potentiostatic method in -0.2V
Electro-deposition 100s under voltage, makes gold nano grain be deposited on base electrode surface, obtains gold nano particle modification electrode.
Gold nano particle modification electrode is placed in 0.25mg/mL sulfydryl graphene aqueous solutions, 4h is stood and is obtained sulfydryl stone
Black alkene-gold nano particle modification electrode.
Sulfydryl Graphene-gold nano particle modification electrode is placed in mixed solution, using cyclic voltammetry in current potential model
Enclose 0~1.0V, sweep speed 50mV/s, scanning 17 circle under conditions of deposit gold-it is Prussian blue, obtain gold-Prussian blue-sulfydryl
Graphene-gold nano particle modification electrode.The mixed solution be 0.1mol/L potassium nitrate, 1mmol/L tetrachloro alloys acid and
1mmol/L potassium ferrocyanides.The cyclic voltammogram of voltolisation alloy-Prussian blue-sulfydryl Graphene-gold nano particle modification electrode
See Fig. 2.
As seen from Figure 2, Fig. 2 is that gold-Prussian blue-sulfydryl Graphene-gold nano particle modification electrode is followed
The characteristic peak obtained during the circle of ring scanning 1~17, continuously strengthens in the presence of a pair in figure with the increase of the scan round number of turns
Redox peaks, this is Prussian blue to peak and the white mutual conversion peaks in Prussia, be it is Prussian blue success modified electrode
Characteristic feature, gold-Prussian blue co-deposition mode can successfully fix general Shandong in showing the preparation method provided using the present invention
Scholar is blue.
At the same time, in order to during verifying gold-Prussian blue modified electrode, gold grain is also successfully modified in electrode table
Face.Pretreated glass-carbon electrode is placed in mixed solution, using cyclic voltammetry in 0~1.0V of potential range, scanning speed
Rate 50mV/s, scanning 17 circle under conditions of deposit gold-it is Prussian blue, obtain gold-Prussian blue modified electrode.The mixed solution
It is 0.1mol/L potassium nitrate, the acid of 1mmol/L tetrachloro alloys and 1mmol/L potassium ferrocyanides.Again by gold-Prussian blue modification
Electrode is placed in 0.1mol/L sodium hydrate aqueous solutions and removes Prussian blue, and the cyclic voltammogram of electrode is shown in figure after the removal for obtaining
2 illustration.By Fig. 2 illustrations it will be evident that Prussian blue redox peaks disappear, the characteristic peak of gold nano grain clearly may be used
See.Show that Prussian blue being with gold nano grain is individually present in the present invention, modified in mercapto by way of being co-deposited
Base graphenic surface.
Embodiment 5
Base electrode is placed in the tetrachloro alloy acid solution of 3mmol/L, using potentiostatic method, electricity is heavy under -0.3V voltages
Product 100s, makes gold nano grain be deposited on base electrode surface, obtains gold nano particle modification electrode.
Gold nano particle modification electrode is placed in 0.25mg/mL sulfydryl graphene aqueous solutions, 4h is stood and is obtained sulfydryl stone
Black alkene-gold nano particle modification electrode.
Sulfydryl Graphene-gold nano particle modification electrode is placed in mixed solution, using cyclic voltammetry in current potential model
Enclose 0~1.0V, sweep speed 50mV/s, scanning 17 circle under conditions of deposit gold-it is Prussian blue, obtain gold-Prussian blue-sulfydryl
Graphene-gold nano particle modification electrode.The mixed solution be 0.1mol/L potassium nitrate, 1mmol/L tetrachloro alloys acid and
1mmol/L potassium ferrocyanides.
Gold-Prussian blue-sulfydryl Graphene-gold nano particle modification electrode is placed in and contains Tebuconazole, o-aminophenol
In the phosphate buffer of resorcinol, using cyclic voltammetry in potential range -0.4~1.0V, sweep speed 50mV/s, sweep
Retouch and be polymerized under conditions of 9 circles the Tebuconazole molecular engram film containing template molecule and modify in the gold-Prussia of the electrode
Blue surface, nitrogen drying stands 5h after water is rinsed, and obtains polymer membrane electrode.The concentration of the phosphate buffer is
0.05mmol/L, pH value is 7.0；Tebuconazole concentration is 0.7mmol/L in phosphate buffer, and o-aminophenol and resorcinol are dense
Degree is 2.1mmol/L.The cyclic voltammogram of polymer membrane electrode process is referring to Fig. 3.
As seen from Figure 3, when cyclic voltammetry carries out electropolymerization 1~10 circle of scanning, the 1st circle is in 0.3V and 0.72V
There is irreversible oxidation peak in place, is the irreversible oxidation peak of o-aminophenol and resorcinol, with the increase oxygen of the scanning number of turns
Change peak drastically to decline, until leveling off to 0, show the polymer film successful polymerization with Tebuconazole molecule in electrode surface, and
Hinder current signal.Meanwhile, it is Prussian blue peak at 0.1V and 0.02V, carry out Prussian blue peak-to-peak signal with electropolymerization
Gradually reduce, show that the polymer film with Tebuconazole molecule hinders Prussian blue electrochemical signals, Jin Er after being formed
Can be by the strong and weak content for characterizing Tebuconazole molecule of Prussian blue electrochemical signals in detection process.
Embodiment 6
This experiment characterizes sulfydryl Graphene-gold nano particle modification electrode, gold-Prussia using cyclic voltammetry respectively
Indigo plant-sulfydryl Graphene-gold nano particle modification electrode, polymer membrane electrode, Tebuconazole molecular engram film electrode and absorption
The Tebuconazole molecular engram film electrode of 0.1mmol/L Tebuconazoles, obtains Tebuconazole molecular engram film electrode modification and inspection
The cyclic voltammogram of survey.
It is prepared by electrode to be measured：The preparation method of the Tebuconazole molecular engram film electrode recorded according to embodiment is prepared respectively：
Sulfydryl Graphene-gold nano particle modification electrode, gold-Prussian blue-sulfydryl Graphene-gold nano particle modification electrode, polymerization
Thing membrane electrode, Tebuconazole molecular engram film electrode.The Tebuconazole molecular engram film electrode of the absorption 0.1mmol/L Tebuconazoles is
The Tebuconazole molecular engram film electrode that embodiment 1 is obtained is placed in 0.1mmol/L tebuconazole solutions and stirs what 30min was obtained.
Electrode to be measured will be measured using cyclic voltammetry respectively, 0.5~-0.1V of potential range, electrolyte are
0.1mol L-1Potassium nitrate solution, the cyclic voltammogram for obtaining is shown in Fig. 4.
Measurement result is as shown in figure 4, in figure：A is the cyclic voltammogram of sulfydryl Graphene-gold nano particle modification electrode, b
It is the cyclic voltammogram of gold-Prussian blue-sulfydryl Graphene-gold nano particle modification electrode, c is the circulation of polymer membrane electrode
Voltammogram, d is the cyclic voltammogram of Tebuconazole molecular engram film electrode, and e is the Tebuconazole molecule for adsorbing 0.1mmol/L Tebuconazoles
Trace membrane electrode.
Curve b is significantly increased relative to the peak point current of curve a, and electronics is increased after showing to have modified gold-Prussian blue
Transfer efficiency, that is, modify the gold-Prussian blue sensitivity that can improve electrode.
Curve c is to have modified with the gold after template molecule polymer film-Prussian blue-sulfydryl Graphene-gold nano
Grain modified electrode, the current value relative to curve b is significantly reduced, closure degree increase, shows modification with template molecule polymerization
Prussian blue electric signal reduces after thing film, mainly due to polymer film structure closely, has blocked probe molecule Prussian blue
Electronic signal is shifted.
Curve d occurs in that redox peaks again relative to curve c, show through methyl alcohol and acetic acid mixed solution process after into
Work(removes the Tebuconazole molecule in polymer film, leaves imprinted cavity on Tebuconazole molecular engram film electrode surface and can know
Other site, enables the specific combination of Tebuconazole molecule in testing sample on imprinted cavity, so as to realize to Tebuconazole
The specific detection of molecule.
Curve e is the Tebuconazole molecular engram film electrode for adsorbing 0.1mmol/L Tebuconazoles, because part imprinted sites are by penta
Azoles alcohol is occupied so that Prussian blue electric signal is stopped by part imprinted sites, so that peak current of the peak current relative to curve d
Reduce, show that the present invention can adsorb the change calculations Tebuconazole molecular engram film electrode of front and rear peak point current by determination sample
The Tebuconazole content of middle absorption, and then can be used for the quantitative determination of Tebuconazole.
Embodiment 7
The Tebuconazole molecular engram film electrode prepared using embodiment 1 as working electrode, platinum electrode as to electrode,
Calomel electrode constitutes three-electrode system as reference electrode；Electrolyte solution is the potassium nitrate solution of pH7.0,0.1mol/L.Will
Above-mentioned material composition is made Tebuconazole portable sensor.
Embodiment 8
The Tebuconazole molecular engram film electrode prepared using embodiment 2 as working electrode, platinum electrode as to electrode,
Calomel electrode constitutes three-electrode system as reference electrode；Electrolyte solution is the potassium nitrate solution of pH5.0,0.08mol/L.Will
Above-mentioned material composition is made Tebuconazole portable sensor.
Embodiment 9
The Tebuconazole molecular engram film electrode prepared using embodiment 3 as working electrode, platinum electrode as to electrode,
Calomel electrode constitutes three-electrode system as reference electrode；Electrolyte solution is the potassium nitrate solution of pH8.0,0.14mol/L.Will
Above-mentioned material composition is made Tebuconazole portable sensor.
Comparative example 1
It is 1 with 30% hydrogen peroxide and concentrated sulfuric acid volume ratio:3 mixed solution immersion glassy carbon electrode 20min, with 0.05 μm
Al2O3Sanding and polishing to electrode surface is washed in after minute surface degree, the ultrasound 10min in water.Electrode after ultrasound is used
Nitrogen is dried up, and is placed in the dilution heat of sulfuric acid of 0.5mol/L, and 20 are scanned in -0.2~1.6V voltage ranges with cyclic voltammetry
Circle.Water cleaning electrode is used after the end of scan, nitrogen drying obtains final product pretreated base electrode.
Pretreated base electrode is placed in the tetrachloro alloy acid solution of 3mmol/L, using potentiostatic method in -0.2V
Electro-deposition 100s under voltage, makes gold nano grain be deposited on base electrode surface, obtains gold nano particle modification electrode.
Sulfydryl Graphene-gold nano particle modification electrode is placed in mixed solution, using cyclic voltammetry in current potential model
Enclose 0~1.0V, sweep speed 50mV/s, scanning 17 circle under conditions of deposit gold-it is Prussian blue, obtain gold-Prussian blue-sulfydryl
Graphene-gold nano particle modification electrode.The mixed solution be 0.1mol/L potassium nitrate, 1mmol/L tetrachloro alloys acid and
1mmol/L potassium ferrocyanides.
Gold-Prussian blue-sulfydryl Graphene-gold nano particle modification electrode is placed in and contains Tebuconazole, o-aminophenol
In the phosphate buffer of resorcinol, using cyclic voltammetry in potential range -0.4~1.0V, sweep speed 50mV/s, sweep
Retouch and be polymerized under conditions of 9 circles the Tebuconazole molecular engram film containing template molecule and modify in the gold-Prussia of the electrode
Blue surface, nitrogen drying stands 5h after water is rinsed, and obtains polymer membrane electrode.The concentration of the phosphate buffer is
0.05mmol/L, pH value is 7.0；Tebuconazole concentration is 0.7mmol/L in phosphate buffer, and o-aminophenol and resorcinol are dense
Degree is 2.1mmol/L.
It is 1 that polymer membrane electrode is placed in into volume ratio:Template molecule is removed in 9 methyl alcohol and acetic acid mixed solution,
120rpm rotating speeds stir 30min, and comparison electrode 1 is obtained after being cleaned with water.
Using comparison electrode 1 as working electrode, used as to electrode, calomel electrode is used as the electricity of reference electrode composition three for platinum electrode
Polar body system；Electrolyte solution is the potassium nitrate solution of pH7.0,0.1mol/L.Above-mentioned material composition is made contrast sensor 1.
Contrast sensor 1 is to compare the work that sensor 1 is used with the difference of Tebuconazole portable sensor described in embodiment 7
Make the unmodified sulfydryl Graphene of electrode.
Comparative example 2
It is 1 with 30% hydrogen peroxide and concentrated sulfuric acid volume ratio:3 mixed solution immersion glassy carbon electrode 20min, with 0.05 μm
Al2O3Sanding and polishing to electrode surface is washed in after minute surface degree, the ultrasound 10min in water.Electrode after ultrasound is used
Nitrogen is dried up, and is placed in the dilution heat of sulfuric acid of 0.5mol/L, and 20 are scanned in -0.2~1.6V voltage ranges with cyclic voltammetry
Circle.Water cleaning electrode is used after the end of scan, nitrogen drying obtains final product pretreated base electrode.
Pretreated base electrode is placed in the tetrachloro alloy acid solution of 3mmol/L, using potentiostatic method in -0.2V
Electro-deposition 100s under voltage, makes gold nano grain be deposited on base electrode surface, obtains gold nano particle modification electrode.
Gold nano particle modification electrode is placed in 0.25mg/mL sulfydryl graphene aqueous solutions, 4h is stood and is obtained sulfydryl stone
Black alkene-gold nano particle modification electrode.
Sulfydryl Graphene-gold nano particle modification electrode is placed in mixed solution, using cyclic voltammetry in current potential model
Enclose 0~1.0V, sweep speed 50mV/s, scanning 17 circle under conditions of deposit gold-it is Prussian blue, obtain gold-Prussian blue-sulfydryl
Graphene-gold nano particle modification electrode.The mixed solution be 0.1mol/L potassium nitrate, 1mmol/L tetrachloro alloys acid and
1mmol/L potassium ferrocyanides.
Gold-Prussian blue-sulfydryl Graphene-gold nano particle modification electrode is placed in and contains o-aminophenol and isophthalic two
In the phosphate buffer of phenol, enclosed in potential range -0.4~1.0V, sweep speed 50mV/s, scanning 9 using cyclic voltammetry
Under the conditions of electropolymerization in situ prepare non-imprinted membrane (NIP), and modify on the gold-Prussian blue surface of the electrode, water punching
Wash rear nitrogen drying and stand 5h, obtain NIP polymer film modified electrodes.The concentration of the phosphate buffer is 0.05mmol/L,
PH value is 7.0；O-aminophenol and resorcinol concentration are independently 2.1mmol/L in phosphate buffer.
It is 1 that polymer membrane electrode is placed in into volume ratio:Template molecule is removed in 9 methyl alcohol and acetic acid mixed solution,
120rpm rotating speeds stir 30min, and comparison electrode 2 is obtained after being cleaned with water.
Using comparison electrode 2 as working electrode, used as to electrode, calomel electrode is used as the electricity of reference electrode composition three for platinum electrode
Polar body system；Electrolyte solution is the potassium nitrate solution of pH7.0,0.1mol/L.Above-mentioned material composition is made contrast sensor 2.
Contrast sensor 2 is to compare the work that sensor 2 is used with the difference of Tebuconazole portable sensor described in embodiment 7
That make to modify in electrode is non-imprinted membrane NIP.
Embodiment 10
This experiment determines the range of linearity of portable sensor and draws standard curve using Differential Pulse Voltammetry, and right
The detection of contrast sensor 1, contrast sensor 2 that the portable sensor obtained than embodiment 7 is obtained with comparative example 1, comparative example 2
Sensitivity.
It is prepared by standard series：It is 0,0.00005,0.0002,0.0005 to take Tebuconazole standard items compound concentration respectively,
The standard series of 0.001,0.006,0.03,0.1,0.2 and 0.4mmol/L.
Detection object：Contrast sensor 1 that portable sensor that embodiment 7 is obtained, comparative example 1 are obtained, comparative example 2 are obtained
Contrast sensor 2.
Detection method：The working electrode of each detection object is suspended in testing sample, 15min is adsorbed, after the completion of absorption
Cleaned with water.Three-electrode system is constituted in working electrode, platinum electrode and calomel electrode using Differential Pulse Voltammetry,
Detected in the potassium nitrate solution of pH7.0,0.1mol/L, the Differential Pulse Voltammetry condition is preferably：Voltage 0.5~-
0.1V, pulse width 50ms, time interval 0.5s, jump rank current potential 5mV, modulated amplitude 50mV.What record test was obtained shows poor arteries and veins
Voltammetric scan curve and peak response current value are rushed, the electrochemical response time is 1.5min.
Result is as shown in figure 5, in figure：
It is 0 that curve is followed successively by uses the Tebuconazole portable sensor measure concentration described in embodiment 7 from top to bottom,
What the standard series of 0.00005,0.0002,0.0005,0.001,0.006,0.03,0.1,0.2 and 0.4mmol/L was obtained shows difference
Pulse Voltammetry scanning curve.
The illustration of Fig. 5 is obtained for the Tebuconazole portable sensor bioassay standard series of samples that the working electrode of different modifying is constituted
The standard curve of the sample concentration logarithm value-current-responsive changing value for arriving, in figure：
■ is that portable sensor of the Tebuconazole molecular engram film electrode prepared with embodiment 1 as working electrode is obtained
Standard curve, curvilinear equation is as follows：
△ I=4.95LogC+26.64,
In formula, △ I represent that specimen current values respond changing value, and unit is μ A；
C represents the concentration of Tebuconazole in sample, unit mmol/L；
The coefficient R of curvilinear equation2=0.971；
● it is standard curve that portable sensor of the comparison electrode 1 prepared with comparative example 1 as working electrode is obtained,
Curvilinear equation is as follows：
△ I=3.86LogC+9.11
In formula, △ I represent that specimen current values respond changing value, and unit is μ A；
C represents the concentration of Tebuconazole in sample, unit mmol/L；
The coefficient R of curvilinear equation2=0.996；
▲ it is mark that portable sensor of the non-imprinted membrane electrode prepared with comparative example 2 as working electrode is obtained
Directrix curve, curvilinear equation is as follows：
△ I=1.23LogC+6.20,
In formula, △ I represent that specimen current values respond changing value, and unit is μ A；
C represents the concentration of Tebuconazole in sample, unit mmol/L；
The coefficient R of curvilinear equation2=0.976.
As shown in Figure 5, the Tebuconazole portable sensor that embodiment 7 is obtained penta azoles in the range of 0.0005~0.4mmol/L
Determining alcohol is linear with current-responsive changing value, and working electrode when current-responsive changing value is with adsorption sample is determined and obtained
The difference of the peak response current value that the working electrode after peak response current value and adsorption sample is obtained when determining.
From Fig. 5 illustrations, ■ curves with ● curve, ▲ curve are compared, and slope is higher, show penta azoles of present invention offer
Alcohol portable sensor relative to unmodified sulfydryl Graphene working electrode or modified the working electrode group of non-imprinted membrane
Into sensor detection sensitivity it is higher.It can be seen that, the present invention modifies sulfydryl Graphene and Tebuconazole point on molecular engram film
Sub- blotting membrane can effectively improve the sensitivity of quantitative determination, be computed the Tebuconazole portable sensor detection of present invention offer
Limit can reach 1.63 × 10-8mol/L。
Embodiment 11
This experiment is respectively adopted Tebuconazole portable sensor and contrast sensor 2 to Tebuconazole and Tebuconazole structure class
Quantitative determined like thing, to detect the selectivity of Tebuconazole portable sensor.
Detection object：The contrast sensor 2 that Tebuconazole portable sensor that embodiment 7 is obtained, comparative example 2 are obtained, the two
Difference be whether to have modified Tebuconazole molecular engram film.
Sample determination：The standard of Tebuconazole, Triadimenol, bitertanol, penconazole, nitrile bacterium azoles and Acetamiprid is taken respectively
Product, are configured to the sample solution of 0.1mmol/L, and the Triadimenol, bitertanol, penconazole, nitrile bacterium azoles and Acetamiprid are penta
The analogue of azoles alcohol.
Experimental technique：Working electrode is suspended in testing sample solution, 15min is adsorbed, is cleaned with water after the completion of absorption.
Using Differential Pulse Voltammetry to entering in the working electrode after adsorption sample, platinum electrode, the three-electrode system of calomel electrode composition
Row is determined, and the electrolyte solution for using is the potassium nitrate solution of pH7.0,0.1mol/L, and the Differential Pulse Voltammetry condition is excellent
Elect as：0.5~-0.1V of voltage, pulse width 50ms, time interval 0.5s, jump rank current potential 5mV, modulated amplitude 50mV..Record
Each sample, each sensor determine the peak response current value for obtaining.The electrochemical response time is 1.5min.
Test result is as shown in fig. 6, in figure：
MIP represents the portable sensor described in embodiment 7, and NIP represents the contrast sensor 2 that comparative example 2 is obtained；
△ I are to determine the peak response current value of the peak response current value and unadsorbed preceding measure for obtaining after adsorption sample
Difference；
△IMIt is the △ I values determined with MIP, △ INIt is the △ I values determined with NIP；
IF is △ IMWith △ INRatio, be mainly used in evaluating the working electrode in portable sensor to target compound and
The selectivity of its analogue.
As seen from Figure 6, the △ I values of MIP measure Tebuconazole are significantly higher than Triadimenol, bitertanol, penconazole, nitrile
The △ I values of bacterium azoles and Acetamiprid, illustrate that the Tebuconazole portable sensor of present invention offer determines the peak response of Tebuconazole sample
Current variation value has significantly with the peak response current variation value of Triadimenol, bitertanol, penconazole, nitrile bacterium azoles and Acetamiprid
Difference；And NIP determines the △ I values of Tebuconazole and the △ I value nothings of Triadimenol, bitertanol, penconazole, nitrile bacterium azoles and Acetamiprid
Significant difference, illustrates to approach the response of Tebuconazole and its analogue using contrast sensor 2, it is impossible to clearly distinguish penta
Azoles alcohol and its analogue, the content of Tebuconazole analogue may produce interference to Tebuconazole quantified results.
As can be seen here, the electrode pair penta of the electrode relative to modification non-imprinted membrane of Tebuconazole molecular engram film has been modified
It is specific stronger that azoles alcohol is detected, i.e., the Tebuconazole molecular engram film electrode that the present invention is provided is special to the quantitative determination of Tebuconazole
Property is stronger, effectively avoids influence of the Tebuconazole analogue to quantified results.
Meanwhile, the IF values of Tebuconazole are significantly higher than Triadimenol, bitertanol, penconazole, nitrile bacterium azoles and pyridine worm in Fig. 6
Amidine, IF values are △ IMWith △ INRatio, IF values are more big, show the choosing of electrode pair target compound in Tebuconazole portable sensor
Selecting property is stronger.It can be seen that, the Tebuconazole molecular engram film electrode that the present invention is provided is strong to the selectivity of Tebuconazole, being capable of effective area
Divide Tebuconazole and its analogue.
Embodiment 12
The Tebuconazole portable sensor that this experiment is obtained using any one of embodiment 7~9 in cucumber, green vegetables to containing
Tebuconazole be measured, to check the accuracy of Tebuconazole portable sensor.
Sample preparation：After by 500g cucumber or the broken homogenate of green vegetables, 25g (being accurate to 0.01g) homogenised sample is weighed, respectively
Tebuconazole standard items are added, the concentration of Tebuconazole in homogenised sample is respectively：0.020mg/kg, 0.100mg/kg and
0.500mg/kg.Stand 30min, add 50mL acetonitrile extractions, by mixed solution with high-shear homogenizer homogeneous after, be transferred to centrifugation
Guan Zhong, 5000rpm are centrifuged 5min, take 1mL supernatant extracts, add 3mL water, and sample test is carried out after mixing.
Experimental technique：Tebuconazole molecular engram film electrode is suspended in testing sample, 15min is adsorbed, after the completion of absorption
Cleaned with water.Time difference pulse voltammetry is used in three electricity constituted with Tebuconazole molecular engram film electrode, platinum electrode, calomel electrode
It is measured in polar body system, electrolyte solution is the potassium nitrate solution of pH7.0,0.1mol/L, the Differential Pulse Voltammetry bar
Part is preferably：0.5~-0.1V of voltage, pulse width 50ms, time interval 0.5s, jump rank current potential 5mV, modulated amplitude 50mV.Note
Differential pulse voltammetry voltammetric scan curve and peak response current value that record test is obtained.The electrochemical response time is 1.5min.
The peak response current value that test is obtained is counted using the standard curve (Fig. 5 illustrations) obtained in embodiment 10
Calculate, multiplied by with after extension rate both the content of Tebuconazole in sample, and calculate the rate of recovery of Tebuconazole in sample and relative
Standard deviation, concrete outcome is shown in Table 1.
The content and the rate of recovery of Tebuconazole in the cucumber of table 1 and green vegetables
As shown in Table 1, the Tebuconazole portable sensor for being provided using the present invention is determined the Tebuconazole in cucumber, green vegetables and contained
Amount, the rate of recovery can reach 77.90~118.69%, RSD values less than 10%, show the portable sensing of Tebuconazole of present invention offer
The accuracy of measurement of device is high, disclosure satisfy that residues of pesticides Site Detection requirement.
The above is only the preferred embodiment of the present invention, it is noted that for the ordinary skill people of the art
For member, under the premise without departing from the principles of the invention, some improvements and modifications can also be made, these improvements and modifications also should
It is considered as protection scope of the present invention.
Claims (10)
1. a kind of Tebuconazole molecular engram film electrode, including base electrode, modifies the Jenner in described matrix electrode surface successively
Rice grain, sulfydryl Graphene and gold-Prussian blue, it is attached to the Tebuconazole molecular engram film on the gold-Prussian blue surface；
The Tebuconazole molecular engram film is the o-aminophenol and arofene with Tebuconazole as template molecule.
2. a kind of preparation method of Tebuconazole molecular engram film electrode, comprises the following steps：
(1) base electrode is placed in tetrachloro alloy acid solution, electro-deposition is carried out using potentiostatic method, in described matrix electrode table
Face deposits gold nano grain, obtains gold nano particle modification electrode；
(2) the gold nano particle modification electrode for obtaining the step (1) stands in sulfydryl graphene aqueous solution, makes sulfydryl stone
Black alkene modification obtains sulfydryl Graphene-gold nano particle modification electrode on the gold nano grain surface of the electrode；
(3) the sulfydryl Graphene-gold nano particle modification electrode for obtaining the step (2) is placed in and is closed containing potassium nitrate, tetrachloro
In the mixed solution of auric acid and potassium ferrocyanide, gold-Prussian blue particle is deposited using cyclic voltammetry, obtain gold-Prussia
Indigo plant-sulfydryl Graphene-gold nano particle modification electrode；
(4) gold for obtaining the step (3)-Prussian blue-sulfydryl Graphene-gold nano particle modification electrode is placed in and contains penta
Electropolymerization is carried out in the phosphate buffer of azoles alcohol, o-aminophenol and resorcinol, polymer film modified electrode is obtained；
(5) polymer film modified electrode of the step (4) is placed in removing polymer film in the mixed solution of methyl alcohol and acetic acid
In Tebuconazole molecule, obtain Tebuconazole molecular engram film electrode.
3. preparation method according to claim 2, it is characterised in that tetrachloro alloy acid solution is dense described in step (1)
It is 2.5~3.5mmol/L to spend, and the electrodeposition time is 80~150s.
4. the preparation method according to Claims 2 or 3, it is characterised in that step (2) the sulfydryl graphene aqueous solution
Concentration is 0.25~0.5mg/mL, and the time of repose is 2~6h.
5. preparation method according to claim 2, it is characterised in that potassium nitrate is dense in step (3) described mixed solution
Spend for 0.05~0.2mol/L, tetrachloro alloy acid concentration for 0.5~1.5mmol/L and ferrocyanide potassium concn be 0.5~
1.5mmol/L；The cyclic voltammetry condition is：0~1.0V of potential range, sweep speed is 50mV/s, and scanning 15~30 is enclosed.
6. preparation method according to claim 2, it is characterised in that in step (4) the phosphoric acid mixed solution, adjacent amino
The concentration of phenol and resorcinol independently is 2.0~2.5mmol/L, and the concentration of Tebuconazole is 0.5~1mmol/L, and phosphoric acid delays
The concentration of fliud flushing is 0.01~0.07mmol/L；The electropolymerizatioconditions conditions are：Potential range -0.4~1.0V, sweep speed is
50mV/s, scanning 8~10 is enclosed.
7. preparation method according to claim 2, it is characterised in that the mixed solution of step (5) methyl alcohol and acetic acid
In, the volume ratio of methyl alcohol and acetic acid is 1:7~1:11.
8. it is a kind of for Tebuconazole quantitative determination portable sensor, including working electrode, to electrode, reference electrode and electrolyte
Solution, it is characterised in that the working electrode is the Tebuconazole molecular engram film electrode or claim 2 described in claim 1
The Tebuconazole molecular engram film electrode that preparation method described in~8 any one is obtained, the electrolyte solution be pH value be 5.0~
8.0th, concentration is 0.08~0.14mol/L potassium nitrate solutions.
9. the portable sensor described in the Tebuconazole molecular engram film electrode or claim 8 described in claim 1 is determining agriculture
Application in product in Tebuconazole residues of pesticides.
10. application according to claim 9, the method for Tebuconazole residues of pesticides includes following step in the measure agricultural product
Suddenly：
1) Tebuconazole molecular engram film electrode is suspended in sample solution, adsorbs 10~20min；
2) it is electric with to electrode, reference using the Tebuconazole molecular engram film electrode after absorption in the step (1) as working electrode
Pole constitutes three-electrode system, and electro-chemical test, the differential pulse voltammetry voltammetric scan that record test is obtained are carried out in electrolyte solution
Curve and peak response current value；
3) the peak response current value of the sample solution obtained according to standard curve and the step (2), is calculated sample
The content of Tebuconazole in solution；
The standard curve is the linearity curve between the peak response current value and Tebuconazole concentration of differential pulse voltammetry volt-ampere test.
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