CN106841343B - 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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- CN106841343B CN106841343B CN201710207535.XA CN201710207535A CN106841343B CN 106841343 B CN106841343 B CN 106841343B CN 201710207535 A CN201710207535 A CN 201710207535A CN 106841343 B CN106841343 B CN 106841343B
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- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N27/00—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means
- G01N27/26—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating electrochemical variables; by using electrolysis or electrophoresis
- G01N27/28—Electrolytic cell components
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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 present invention provides a kind of Tebuconazole molecular engram film electrode, including base electrode, the gold nano grain, sulfydryl graphene and gold-successively modified in described matrix electrode surface are Prussian blue, are attached to the gold-Prussian blue surface Tebuconazole molecular engram film；The Tebuconazole molecular engram film is using Tebuconazole as the o-aminophenol of template molecule and arofene.Quantitative detection is carried out to Tebuconazole using Tebuconazole molecular engram film electrode provided by the invention, detection limit can reach 1.63 × 10‑8Mol/L, high sensitivity.The present invention is fixed on probe molecule is Prussian blue on Tebuconazole molecular engram film electrode, and the direct measurement of electrically inactive target compound in sample may be implemented, and is kept the operation of sensor more easy and is suitable for field quick detection.
Description
Technical field
The present invention relates to Pesticides Testing technical fields, and in particular to a kind of Tebuconazole molecular engram film electrode, portable sensing
Device and its application method and application.
Background technique
Tebuconazole is a kind of high efficiency triazole bactericidal agent, is widely used in the crops such as peanut, barley, rice, apple
Disease control, frequent use will cause soil pollution, and jeopardize the ecosystem, underground water and human health.
Currently, the method for detection Tebuconazole has high sensitivity, accuracy good, qualitative fixed mainly based on chromatographic technique
The advantages that amount analysis is splendid.However these analysis methods are limited in that: required analysis instrument is typically placed in far from scene
In standard analysis laboratory, and instrument price is expensive, complicated for operation, needs the operation of professional；Time-consuming for sample pre-treatments,
Difficulty meets the needs of Residual Pesticides in Farm Produce field quick detection.
The prior art, electrochemical sensor is although easy to carry but the quantitative detection sensitivity of pesticide residue is lower, and
And electrochemical sensor needs electron mediator as the power of probe instruction electrochemical signals, and these probes can contaminated samples
And then interference is generated to testing result, to cause testing result inaccurate.Therefore, need to develop it is a kind of it is portable, price is low
Honest and clean and high accuracy in detection Fast Determination of Pesticide Residue means.
Summary of the invention
In view of this, the purpose of the present invention is to provide a kind of device that can be applied to Tebuconazole quantitative determination, it is portable
Band, accuracy, high sensitivity.
In order to achieve the above-mentioned object of the invention, the present invention the following technical schemes are provided:
The present invention provides a kind of Tebuconazole molecular engram film electrodes, including base electrode, successively modify in described matrix
The gold nano grain of electrode surface, sulfydryl graphene and gold-are Prussian blue, are attached to the gold-Prussian blue surface penta
Azoles alcohol molecular engram film；
The Tebuconazole molecular engram film is using Tebuconazole as the o-aminophenol of template molecule and arofene.
The present invention provides the preparation methods of Tebuconazole molecular engram film electrode described in above-mentioned technical proposal, including following step
It is rapid:
(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 that the step (1) obtains is stood 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) sulfydryl graphene-gold nano particle modification electrode that the step (2) obtains is placed in containing potassium nitrate, four
In the mixed solution of chlorine alloy acid and potassium ferrocyanide, using cyclic voltammetry deposition gold-Prussian blue particle, it is general to obtain Jin-
Shandong scholar indigo plant-sulfydryl graphene-gold nano particle modification electrode；
(4) by gold-that the step (3) obtains it is Prussian blue-sulfydryl graphene-gold nano particle modification electrode is placed in and contains
Have and carry out electropolymerization in the phosphate buffer of Tebuconazole, o-aminophenol and resorcinol, obtains polymer film modified electrode；
(5) polymer film modified electrode of the step (4) is placed in remove in the mixed solution of methanol and acetic acid and is polymerize
Tebuconazole molecule in object 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, when 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
For 2~6h.
Preferably, in step (3) described mixed solution potassium nitrate concentration be 0.05~0.2mol/L, tetrachloro alloy acid
Concentration is 0.5~1.5mmol/L and ferrocyanide potassium concn is 0.5~1.5mmol/L；The cyclic voltammetry condition are as follows:
0~1.0V of potential range, sweep speed 50mV/s, 15~30 circle of scanning.
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 are 0.5~1mmol/L, and the concentration of phosphate buffer is 0.01~0.07mmol/L；
The electropolymerizatioconditions conditions are as follows: potential range -0.4~1.0V, sweep speed 50mV/s, 8~10 circle of scanning.
Preferably, in the mixed solution of step (5) methanol and acetic acid, the volume ratio of methanol and acetic acid is 1:7~1:
11。
The present invention also provides 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 solution obtains, the electrolyte solution be pH value be 5.0~
8.0, concentration is 0.08~0.14mol/L potassium nitrate solution.
The present invention provides described in preceding solution Tebuconazole molecular engram film electrode or above-mentioned technical proposal described in
Application of the portable sensor in measurement agricultural product in Tebuconazole pesticide residue.
Preferably, it is described measurement agricultural product in Tebuconazole pesticide residue method the following steps are included:
1) Tebuconazole molecular engram film electrode is suspended in sample solution, adsorbs 10~20min；
2) regard the Tebuconazole molecular engram film electrode after absorption in the step (1) as working electrode, with to electrode, join
Three-electrode system is formed than electrode, electro-chemical test, the differential pulse voltammetry volt-ampere that record test obtains are carried out in electrolyte solution
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 the test of differential pulse volt-ampere
Curve.
Compared with prior art, the present invention the invention has the following advantages that
Tebuconazole molecular engram film electrode provided by the invention on base electrode by successively modifying gold nano grain, mercapto
Base graphene and gold-are Prussian blue, in conjunction with Tebuconazole molecular engram film, effectively raise the sensitivity to Tebuconazole detection
And accuracy.It is detected using Tebuconazole molecular engram film electrode provided by the invention, detection limit can reach 1.63 × 10- 8Mol/L, it is seen that Tebuconazole molecular engram film electrode provided by the invention 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 Tebuconazole molecular engram film electrode provided by the invention,
It recycles the golden ability of the parent of sulphur atom to connect gold nano grain by stable golden sulfide linkage 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.
Tebuconazole molecular engram film electrode provided by the invention is co-deposited golden-Prussian blue in sulfydryl graphene surface,
To make probe molecule is Prussian blue to be fixed on electrode, when detection, is just not necessarily to that probe molecule is added in the electrolytic solution, simplifies real
Operation is tested, the sensitivity and accuracy directly measured is improved.Tebuconazole molecular engram film electrode provided by the invention is especially suitable
Quickly detection on site, so that Residual Pesticides in Farm Produce on-site test 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 can also shorten detection time while further increasing electrode detection sensitivity.In conjunction with penta azoles
The Tebuconazole molecular engram film that alcohol is template molecule, is constituted using resorcinol and o-aminophenol as polymerized functional monomer, can
Specific recognition Tebuconazole molecule, the Tebuconazole molecular engram film electrode made have good sensitivity and specificity, can
With the identification Tebuconazole molecule of precise and high efficiency.Experiments have shown that Tebuconazole molecular engram film provided by the invention is to Triadimenol, penta bacterium
The analogues response such as azoles is low, can effectively differentiate the Tebuconazole pesticide similar with other structures, avoid Tebuconazole knot
Influence of the similar pesticide 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 chromatography or chromatograph-mass spectrometer coupling
For detection method, detecting instrument is small in size, convenient to carry out, and not examined place limitation can be used for on-site test.And
And 15.5~17.5min of Tebuconazole content used time in portable sensor quantitative determination sample provided by the invention, greatly shorten
Detection time, improves the detection efficiency of Tebuconazole.
When being quantitative determined using portable sensor provided by the invention to Tebuconazole in agricultural product, the recycling of Tebuconazole
Rate can reach 77.9~118.69%, shows that the accuracy of portable sensor quantitative determination provided by the invention is high, can satisfy
The demand of Residual Pesticides in Farm Produce on-site test.
Simple, small in size, easy to operate, the phase provided by the present invention for the portable sensor structure of Tebuconazole quantitative determination
The instrument costs such as chromatograph used for existing chromatographic detection method are low, easily operated and outgoing carrying, are particularly suitable for
Field quick detection.
Detailed description of the invention
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 that gold-is Prussian blue, and Teb is penta azoles
Alcohol molecule, analogue are Tebuconazole molecular mimics, and p (AP-DHB) is Tebuconazole molecular engram film；
Fig. 2 be voltolisation alloy-it is Prussian blue-sulfydryl graphene-gold nano particle modification electrode process cyclic voltammogram；
Illustration be the Prussian blue electrode of voltolisation alloy-remove it is Prussian blue after obtained cyclic voltammogram；
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 measures various concentration Tebuconazole sample；It inserts
Figure is logarithm-current-responsive changing value standard curve of the sensor measurement sample of the working electrode composition of different modifying；
Fig. 6 is the selective evaluation figure of Tebuconazole and its analogue.
Specific embodiment
The present invention provides a kind of Tebuconazole molecular engram film electrodes, including base electrode, successively modify in described matrix
The gold nano grain of electrode surface, sulfydryl graphene and gold-are Prussian blue, are attached to the gold-Prussian blue surface penta
Azoles alcohol molecular engram film；
The Tebuconazole molecular engram film is using Tebuconazole as the o-aminophenol of template molecule and arofene.
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, be capable of increasing specific surface area after the gold nano particle modification base electrode, thus make by
Current strength increases, and then improves the detection sensitivity of electrode.Meanwhile gold nano grain can also pass through covalent bond and sulfydryl stone
Black alkene combines, and the fixation for sulfydryl graphene provides basis.
In the present invention, the sulfydryl graphene is with mercapto-modified graphene.The present invention is to sulfydryl graphene
Source does not have any restriction, using commercial product, preferably uses Suzhou carbon Feng Shi in some embodiments of the invention
The sold sulfydryl graphene of Mo Xi Science and Technology Ltd..
In the present invention, it is with gold nano grain co-precipitation by Prussian blue in sulfydryl graphene that the gold-is Prussian blue
Surface, it is described gold-it is Prussian blue in it is Prussian blue be used as probe molecule, with gold nano grain co-deposition can be visited with effective guarantee
Needle molecule is firmly combined on the electrode, and gold nano grain and sulfydryl graphene can also be by forming covalent bond gold sulfide linkage jail
Consolidation is closed；Gold-Prussian blue the electric conductivity that can further increase electrode, thus make the conduction of velocity of electric signal faster,
Minute effectively is shortened, while the detection sensitivity of electrode can also be enhanced.
The present invention provides the preparation methods of Tebuconazole molecular engram film electrode described in above-mentioned technical proposal, including following step
It is rapid:
(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 that the step (1) obtains is stood 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) sulfydryl graphene-gold nano particle modification electrode that the step (2) obtains is placed in containing potassium nitrate, four
In the mixed solution of chlorine alloy acid and potassium ferrocyanide, using cyclic voltammetry deposition gold-Prussian blue particle, it is general to obtain Jin-
Shandong scholar indigo plant-sulfydryl graphene-gold nano particle modification electrode；
(4) by gold-that the step (3) obtains it is Prussian blue-sulfydryl graphene-gold nano particle modification electrode is placed in and contains
Have and carry out electropolymerization in the phosphate buffer of Tebuconazole, o-aminophenol and resorcinol, obtains polymer film modified electrode；
(5) polymer film modified electrode of the step (4) is placed in the mixed solution containing methanol and acetic acid and is removed
Tebuconazole molecule in polymer film, obtains Tebuconazole molecular engram film electrode.
The preparation step 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 tetrachloro alloy acid solution, preferably to described matrix electrode carry out pretreatment and
Cleaning.In the present invention, the pretreatment and clean method preferably include following steps:
A, base electrode is placed in 10~30min of immersion in the mixed solution of hydrogen peroxide and the concentrated sulfuric acid, 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, in water 8~15min of ultrasound；
C, the base electrode after ultrasound in the step b is placed in 0.1~1.0mol/L dilution heat of sulfuric acid, using circulation
15~30 circle of voltammetry scanning, cleaning drying.
Base electrode is placed in 10~30min of processing in the mixed solution of hydrogen peroxide and the concentrated sulfuric acid by the present invention.Specifically, this
Base electrode is soaked 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.Soaking 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%, and more preferably 30%；The concentrated sulfuric acid is using commercial goods
It can.
The volume that the present invention uses when handling 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 processing, Neng Gouyou
Organic impurities on the removal base electrode of effect.
The present invention is by mixed solution treated base electrode with 0.03~0.10 μm of Al2O3Carry out sanding and polishing.At this
In invention, the Al2O3Partial size be preferably 0.05 μm.The present invention uses Al2O3Sanding and polishing is to electrode surface to mirror 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, in water 8~15min of ultrasound.Specifically, the present invention will be beaten
Base electrode after grinding and polishing light is eluted with water, and removes base electrode Al remained on surface2O3.In the present invention, the ultrasonic time
Preferably 9~12min, more preferably 10min.
After ultrasound, base electrode is placed 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 circle number is preferably 18~25 circles, more preferably 20 circles；The cyclic voltammetry scanning speed
Preferably 50mV/s.
The present invention makes electrode polarization using cyclic voltammetry scanning base electrode, makes base electrode table by electrochemical means
Face cleaning.
Base electrode is placed 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.When potentiostatic electrodeposition of the present invention
Current potential be -0.3~-0.1V, preferably -0.2V.The present invention is that will pass through 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 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, the close Jin Nengli of sulphur atom is utilized, it then follows
Hard and soft acid and base action principle, sulfydryl graphene is connect with gold nano grain by polar covalent bond gold sulfide linkage, to make sulfydryl stone
Black alkene modification is on gold nano grain surface.
Sulfydryl graphene of the present invention can be completed at normal temperature with reacting for 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 keeps detection limit lower, can be used in actual Tebuconazole quantitative detection.
After obtaining sulfydryl graphene-gold nano particle modification electrode, the present invention is by sulfydryl graphene-gold nano particle modification
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-is 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 preferred are as follows: 0~1.0V of potential range, scanning
Rate is 50mV/s, 15~30 circle of scanning；The scanning circle number is more preferably 17 circles.
In the present invention, following chemical reaction occurs when Prussian blue using cyclic voltammetry deposition gold-:
Tetrachloro alloy acid reaction in the mixed solution generates gold nano grain:
HAuCl4→H++AuCl4 -
AuCl4 -+3e-→Au(0)+4Cl-
Au(0)+3HOH→Au(OH)3+3H+
Ferrocyanide nak response in the mixed solution generates Prussian blue:
[Fe(CN)6]3-+6H+→Fe3++6HCN
Fe3++e-→Fe2+
Fe2++[Fe(CN)6]3-→[Fe3+Fe2+(CN)6]-
Generate gold nano grain and it is Prussian blue after, under the action of cyclic voltammetry be co-deposited in sulfydryl graphene table
Face obtains gold-Prussian blue-sulfydryl graphene-gold nano particle modification electrode.
The present invention by obtained gold-it is Prussian blue-sulfydryl graphene-gold nano particle modification electrode is placed in containing penta azoles
Electropolymerization is carried out in the phosphate buffer of alcohol, o-aminophenol and resorcinol, and polymer film modified electrode is made.Institute of the present invention
It states electropolymerization and electropolymerization is preferably carried out with cyclic voltammetry, the condition of the cyclic voltammetry is preferred are as follows: potential range -0.4
~1.0V, sweep speed 50mV/s, 8~10 circle of scanning；The scanning circle number 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, and more preferably 7.
The present invention is using Tebuconazole molecule as template, using o-aminophenol and resorcinol as polymerized functional monomer, in voltolisation
Cooperation is polymerized to the Tebuconazole molecular engram film containing template molecule under, and Tebuconazole molecular engram is film modified general in Jin-
The Shandong surface Shi Lan.
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 is stood in air to environment is stood without any restriction.The present invention is after electropolymerization to poly-
It is directly to carry out mould after preventing electropolymerization to make polymer film be firmly bonded to electrode surface that the electrode of compound film, which stand,
Polymer film caused by plate molecule removes is damaged.
After obtaining polymer modified electrode, polymer modified electrode is placed in the mixed solution of methanol and acetic acid by the present invention
In, the template molecule in removing polymer film obtains Tebuconazole molecular engram film electrode.Methanol and acetic acid of the present invention mix
It closes in solution, the volume ratio of methanol and acetic acid is preferably 1:7~1:11, more preferably 1:9.In the present invention, described remove 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 methanol
Mixed solution by with polymer film competitive Adsorption Tebuconazole molecule, make Tebuconazole molecule from polymer film be removed, thus
Obtain the molecular engram film with Tebuconazole molecular cavities recognition site.
The present invention also provides 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 solution obtains, the electrolyte solution be pH value be 5.0~
8.0, concentration is 0.08~0.14mol/L potassium nitrate solution.
In the present invention, the reference electrode is preferably calomel electrode, and described is 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 portable sensor provided by the invention, since working electrode Tebuconazole molecular engram film electrode is fixed with probe
Molecule is Prussian blue, thus can be directly used for target compound in sample without adding probe molecule i.e. in electrolyte solution
Measurement.
The present invention provides described in preceding solution Tebuconazole molecular engram film electrode or above-mentioned technical proposal described in
Application of the portable sensor in measurement agricultural product in Tebuconazole pesticide residue.
Preferably, it is described measurement agricultural product in Tebuconazole pesticide residue method the following steps are included:
1) Tebuconazole molecular engram film electrode is suspended in sample solution, adsorbs 10~20min；
2) regard the Tebuconazole molecular engram film electrode after absorption in the step 1) as working electrode, with to electrode, join
Three-electrode system is formed than electrode, electro-chemical test, the differential pulse voltammetry volt-ampere that record test obtains are carried out in electrolyte solution
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), it is molten to obtain sample
The content of Tebuconazole in liquid；
The standard curve is linear between the peak response current value and Tebuconazole concentration of the test of differential pulse voltammetry volt-ampere
Curve.
Tebuconazole molecular engram film electrode is suspended 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 is to be homogenized test substance, the preferred determinand
Matter includes green vegetables, cucumber, long bean, radish.The present invention to the homogenate mode without any restriction, using the conventional homogenate side in this field
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 washing with water
Examination.
After absorption, the present invention forms three using Tebuconazole molecular engram film electrode as working electrode, with to electrode, reference electrode
Electrode system carries out electro-chemical test, differential pulse voltammetry voltammetric scan curve obtained by record electro-chemical test in electrolyte solution
And peak response current value.In the present invention, the Differential Pulse Voltammetry condition is preferred are as follows: 0.5~-0.1V of voltage, arteries and veins
Width 50ms, time interval 0.5s are rushed, jump rank current potential 5mV, modulated amplitude 50mV.
Since probe molecule is fixed on the working electrode (s, thus Tebuconazole and penta azoles in electro-chemical test in sample
The gold-that curent change caused by alcohol molecular engram film reaction is directly coated under Tebuconazole molecular engram film is Prussian blue to be connect
By electrochemical signals variation is generated in turn, so that the peak response current value in electro-chemical test is influenced, by calculating maximum sound
Answer the variation of current value that 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 arrived, is calculated the content of Tebuconazole in sample solution.Specifically, the present invention is not with
The difference of the maximum corresponding current value after peak response current value and absorption when absorption is as ordinate, with pair 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, which 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
Trace membrane electrode adsorbs each standard series sample, measures peak response current value using Differential Pulse Voltammetry, will survey
The difference of fixed peak response current value and unadsorbed preceding peak response current value is as ordinate, corresponding Tebuconazole standard system
The logarithm of column sample concentration is that abscissa draws standard curve.Differential Pulse Voltammetry condition of the present invention and measurement are to be measured
The condition of sample is identical.
Below in conjunction with the embodiment in the present invention, the technical solution in the present invention is clearly and completely described.It is aobvious
So, described embodiments are only a part of the embodiments of the present invention, instead of all the embodiments.Based on the reality in the present invention
Example is applied, every other embodiment obtained by those of ordinary skill in the art without making creative efforts all belongs to
In the scope of protection of the invention.
Embodiment 1
With 30% hydrogen peroxide and concentrated sulfuric acid volume than impregnating glassy carbon electrode 20min for the mixed solution of 1:3, with 0.05 μm
Al2O3Sanding and polishing to electrode surface in being eluted with water after mirror surface degree, ultrasound 10min in water.Electrode after ultrasound is used
It is dried with nitrogen, is placed in the dilution heat of sulfuric acid of 0.5mol/L, scan 20 in -0.2~1.6V voltage range with cyclic voltammetry
Circle.Wash with water electrode after the end of scan, be dried with nitrogen, 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 solution, 4h is stood and obtains 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
Deposition gold-is Prussian blue under conditions of enclosing 0~1.0V, sweep speed 50mV/s, 17 circle of scanning, obtains gold-Prussian blue-sulfydryl
Graphene-gold nano particle modification electrode.The mixed solution be 0.1mol/L potassium nitrate, 1mmol/L tetrachloro alloy acid and
1mmol/L potassium ferrocyanide.
Gold-Prussian blue-sulfydryl graphene-gold nano particle modification electrode is placed in containing Tebuconazole, o-aminophenol
In the phosphate buffer of resorcinol, using cyclic voltammetry in potential range -0.4~1.0V, sweep speed 50mV/s, sweep
It retouches and is polymerized to the Tebuconazole molecular engram film containing template molecule under conditions of 9 circles and modifies in gold-Prussia of the electrode
Blue surface, water is dried with nitrogen after rinsing stands 5h, obtains polymer membrane electrode.The concentration of the phosphate buffer is
0.05mmol/L, pH value 7.0；Tebuconazole concentration is 0.7mmol/L in phosphate buffer, and o-aminophenol and resorcinol are dense
Degree is 2.1mmol/L.
Polymer membrane electrode is placed in the methanol and acetic acid mixed solution that volume ratio is 1:9 and removes template molecule,
120rpm revolving speed stirs 30min, and Tebuconazole molecular engram film electrode is obtained after washing with water.
The Tebuconazole molecular engram film electrode preparation used time is short, and preparation method is simple, and time-consuming is 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 voltage using potentiostatic method
80s is deposited, so that gold nano grain is 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 solution, 2h is stood and obtains 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
Deposition gold-is Prussian blue under conditions of enclosing 0~1.0V, sweep speed 50mV/s, 15 circle of scanning, obtains gold-Prussian blue-sulfydryl
Graphene-gold nano particle modification electrode.The mixed solution be 0.05mol/L potassium nitrate, 0.5mmol/L tetrachloro alloy acid with
And 0.5mmol/L potassium ferrocyanide.
Gold-Prussian blue-sulfydryl graphene-gold nano particle modification electrode is placed in containing Tebuconazole, o-aminophenol
In the phosphate buffer of resorcinol, using cyclic voltammetry in potential range -0.4~1.0V, sweep speed 50mV/s, sweep
It retouches and is polymerized to the Tebuconazole molecular engram film containing template molecule under conditions of 8 circles and modifies in 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
Degree is 0.5mmol/L, pH value 5.0；O-aminophenol and resorcinol concentration are 2.0mmol/L.
Polymer membrane electrode is placed in the methanol and acetic acid mixed solution that volume ratio is 1:7 and removes template molecule,
100rpm revolving speed stirs 20min, and Tebuconazole molecular engram film electrode is obtained after washing with water.
Embodiment 3
With 20% hydrogen peroxide and concentrated sulfuric acid volume than impregnating glassy carbon electrode 15min for the mixed solution of 1:2, with 0.05 μm
Al2O3Sanding and polishing to electrode surface in being eluted with water after mirror surface degree, ultrasound 8min in water.Electrode after ultrasound is used
It is dried with nitrogen, is placed in the dilution heat of sulfuric acid of 0.4mol/L, scan 15 in -0.2~1.6V voltage range with cyclic voltammetry
Circle.Wash with water electrode after the end of scan, be dried with nitrogen, 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 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 0.5mg/mL sulfydryl graphene aqueous solution, 6h is stood and obtains 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
Deposition gold-is Prussian blue under conditions of enclosing 0~1.0V, sweep speed 50mV/s, 30 circle of scanning, obtains gold-Prussian blue-sulfydryl
Graphene-gold nano particle modification electrode.The mixed solution be 0.2mol/L potassium nitrate, 1.5mmol/L tetrachloro alloy acid with
And 1.5mmol/L potassium ferrocyanide.
Gold-Prussian blue-sulfydryl graphene-gold nano particle modification electrode is placed in containing Tebuconazole, o-aminophenol
In the phosphate buffer of resorcinol, using cyclic voltammetry in potential range -0.4~1.0V, sweep speed 50mV/s, sweep
It retouches and is polymerized to the Tebuconazole molecular engram film containing template molecule under conditions of 10 circles and modifies in gold-Prussia of the electrode
Blue surface, water is dried with nitrogen after rinsing stands 16h, obtains polymer membrane electrode.The concentration of the phosphate buffer is
0.07mmol/L, pH value 6.0；Tebuconazole concentration is 1mmol/L, o-aminophenol and resorcinol concentration in phosphate buffer
It is 2.5mmol/L.
Polymer membrane electrode is placed in the methanol and acetic acid mixed solution that volume ratio is 1:11 and removes template molecule,
150rpm revolving speed stirs 40min, and Tebuconazole molecular engram film electrode is obtained after washing with water.
Embodiment 4
With 30% hydrogen peroxide and concentrated sulfuric acid volume than impregnating glassy carbon electrode 20min for the mixed solution of 1:3, with 0.05 μm
Al2O3Sanding and polishing to electrode surface in being eluted with water after mirror surface degree, ultrasound 10min in water.Electrode after ultrasound is used
It is dried with nitrogen, is placed in the dilution heat of sulfuric acid of 0.5mol/L, scan 20 in -0.2~1.6V voltage range with cyclic voltammetry
Circle.Wash with water electrode after the end of scan, be dried with nitrogen, 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 solution, 4h is stood and obtains 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
Deposition gold-is Prussian blue under conditions of enclosing 0~1.0V, sweep speed 50mV/s, 17 circle of scanning, obtains gold-Prussian blue-sulfydryl
Graphene-gold nano particle modification electrode.The mixed solution be 0.1mol/L potassium nitrate, 1mmol/L tetrachloro alloy acid and
1mmol/L potassium ferrocyanide.Voltolisation alloy-Prussian blue-sulfydryl graphene-gold nano particle modification electrode cyclic voltammogram
See Fig. 2.
As seen from Figure 2, Fig. 2 is to follow to gold-Prussian blue-sulfydryl graphene-gold nano particle modification electrode
Ring scans characteristic peak obtained in 1~17 circle process, and there is a pair in figure continuously enhances with the increase of scan round circle number
Redox peaks, this to peak be it is Prussian blue and white Prussia mutually convert peak, be Prussian blue success modified electrode
Characteristic feature shows successfully fix general Shandong using gold in preparation method provided by the invention-Prussian blue co-deposition mode
Scholar is blue.
At the same time, during in order to verify gold-Prussian blue modified electrode, gold particle 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
It is Prussian blue that gold-is deposited under conditions of rate 50mV/s, 17 circle of scanning, obtains gold-Prussian blue modified electrode.The mixed solution
For 0.1mol/L potassium nitrate, 1mmol/L tetrachloro alloy acid and 1mmol/L potassium ferrocyanide.Again by gold-Prussian blue modification
Electrode, which is placed in 0.1mol/L sodium hydrate aqueous solution, to be removed Prussian blue, and the cyclic voltammogram of electrode is shown in figure after obtained removal
2 illustration.By Fig. 2 illustration 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 in the present invention with gold nano grain is to be individually present, is to be modified by way of co-deposition in mercapto
Base graphene 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 voltage
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 solution, 4h is stood and obtains 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
Deposition gold-is Prussian blue under conditions of enclosing 0~1.0V, sweep speed 50mV/s, 17 circle of scanning, obtains gold-Prussian blue-sulfydryl
Graphene-gold nano particle modification electrode.The mixed solution be 0.1mol/L potassium nitrate, 1mmol/L tetrachloro alloy acid and
1mmol/L potassium ferrocyanide.
Gold-Prussian blue-sulfydryl graphene-gold nano particle modification electrode is placed in containing Tebuconazole, o-aminophenol
In the phosphate buffer of resorcinol, using cyclic voltammetry in potential range -0.4~1.0V, sweep speed 50mV/s, sweep
It retouches and is polymerized to the Tebuconazole molecular engram film containing template molecule under conditions of 9 circles and modifies in gold-Prussia of the electrode
Blue surface, water is dried with nitrogen after rinsing stands 5h, obtains polymer membrane electrode.The concentration of the phosphate buffer is
0.05mmol/L, pH value 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 scanning circle number
Change peak sharply to decline, until level off to 0, show the polymer film successful polymerization with Tebuconazole molecule in electrode surface, and
Hinder current signal.Meanwhile at 0.1V and 0.02V be Prussian blue peak, with the Prussian blue peak-to-peak signal of carry out of electropolymerization
It gradually decreases, shows to hinder Prussian blue electrochemical signals, Jin Er after the polymer film with Tebuconazole molecule is formed
The content of the strong and weak characterization Tebuconazole molecule of Prussian blue electrochemical signals can be passed through in detection process.
Embodiment 6
This test 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 Tebuconazole, obtains Tebuconazole molecular engram film electrode modification and inspection
The cyclic voltammogram of survey.
Electrode preparation to be measured: the preparation method for the Tebuconazole molecular engram film electrode recorded according to embodiment is prepared respectively:
Sulfydryl graphene-gold nano particle modification electrode, gold-be Prussian blue-sulfydryl graphene-gold nano particle modification electrode, polymerization
Object membrane electrode, Tebuconazole molecular engram film electrode.It is described absorption 0.1mmol/L Tebuconazole Tebuconazole molecular engram film electrode be
The Tebuconazole molecular engram film electrode that embodiment 1 obtains is placed in 0.1mmol/L tebuconazole solution 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, obtained cyclic voltammogram is shown in Fig. 4.
Measurement result is as shown in figure 4, in figure: a is sulfydryl graphene-gold nano particle modification electrode cyclic voltammogram, b
For gold-Prussian blue-sulfydryl graphene-gold nano particle modification electrode cyclic voltammogram, c is the circulation of polymer membrane electrode
Voltammogram, d are the cyclic voltammogram of Tebuconazole molecular engram film electrode, and e is the Tebuconazole molecule for adsorbing 0.1mmol/L Tebuconazole
Trace membrane electrode.
Curve b is significantly increased relative to the peak point current of curve a, show to have modified gold-it is Prussian blue after increase electronics
Transfer efficiency, i.e. modification gold-Prussian blue sensitivity that can be improved electrode.
Curve c be modified with the gold-after template molecule polymer film it is Prussian blue-sulfydryl graphene-gold nano
Grain modified electrode, the current value relative to curve b significantly reduce, and closure degree increases, and show that modification polymerize with template molecule
Prussian blue electric signal reduces after object film, mainly since polymer film structure is close, has blocked probe molecule Prussian blue
Electronic signal transfer.
There are redox peaks relative to curve c again in curve d, show through the mixed solution of methanol and acetic acid processing after at
Function removes the Tebuconazole molecule in polymer film, leaves imprinted cavity on Tebuconazole molecular engram film electrode surface and can know
Other site enables the combination of the Tebuconazole molecule specificity in sample to be tested on imprinted cavity, to realize to Tebuconazole
The specific detection of molecule.
Curve e is the Tebuconazole molecular engram film electrode for adsorbing 0.1mmol/L Tebuconazole, since part imprinted sites are by penta
Azoles alcohol occupies, so that Prussian blue electric signal is stopped by part imprinted sites, to make peak current relative to the peak current of curve d
It reduces, shows that the present invention can calculate Tebuconazole molecular engram film electrode by the variation of measurement sample absorption front and back peak point current
The Tebuconazole content of middle absorption, and then can be used for the quantitative determination of Tebuconazole.
Embodiment 7
Using the Tebuconazole molecular engram film electrode that embodiment 1 is prepared as working electrode, platinum electrode is used as to electrode,
Calomel electrode forms three-electrode system as reference electrode；Electrolyte solution is the potassium nitrate solution of pH7.0,0.1mol/L.It will
Tebuconazole portable sensor is made in above-mentioned material composition.
Embodiment 8
Using the Tebuconazole molecular engram film electrode that embodiment 2 is prepared as working electrode, platinum electrode is used as to electrode,
Calomel electrode forms three-electrode system as reference electrode；Electrolyte solution is the potassium nitrate solution of pH5.0,0.08mol/L.It will
Tebuconazole portable sensor is made in above-mentioned material composition.
Embodiment 9
Using the Tebuconazole molecular engram film electrode that embodiment 3 is prepared as working electrode, platinum electrode is used as to electrode,
Calomel electrode forms three-electrode system as reference electrode；Electrolyte solution is the potassium nitrate solution of pH8.0,0.14mol/L.It will
Tebuconazole portable sensor is made in above-mentioned material composition.
Comparative example 1
With 30% hydrogen peroxide and concentrated sulfuric acid volume than impregnating glassy carbon electrode 20min for the mixed solution of 1:3, with 0.05 μm
Al2O3Sanding and polishing to electrode surface in being eluted with water after mirror surface degree, ultrasound 10min in water.Electrode after ultrasound is used
It is dried with nitrogen, is placed in the dilution heat of sulfuric acid of 0.5mol/L, scan 20 in -0.2~1.6V voltage range with cyclic voltammetry
Circle.Electrode is washed with water after the end of scan, is dried with nitrogen to get 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
Deposition gold-is Prussian blue under conditions of enclosing 0~1.0V, sweep speed 50mV/s, 17 circle of scanning, obtains gold-Prussian blue-sulfydryl
Graphene-gold nano particle modification electrode.The mixed solution be 0.1mol/L potassium nitrate, 1mmol/L tetrachloro alloy acid and
1mmol/L potassium ferrocyanide.
Gold-Prussian blue-sulfydryl graphene-gold nano particle modification electrode is placed in containing Tebuconazole, o-aminophenol
In the phosphate buffer of resorcinol, using cyclic voltammetry in potential range -0.4~1.0V, sweep speed 50mV/s, sweep
It retouches and is polymerized to the Tebuconazole molecular engram film containing template molecule under conditions of 9 circles and modifies in gold-Prussia of the electrode
Blue surface, water is dried with nitrogen after rinsing stands 5h, obtains polymer membrane electrode.The concentration of the phosphate buffer is
0.05mmol/L, pH value 7.0；Tebuconazole concentration is 0.7mmol/L in phosphate buffer, and o-aminophenol and resorcinol are dense
Degree is 2.1mmol/L.
Polymer membrane electrode is placed in the methanol and acetic acid mixed solution that volume ratio is 1:9 and removes template molecule,
120rpm revolving speed stirs 30min, and comparison electrode 1 is obtained after washing with water.
Using comparison electrode 1 as working electrode, platinum electrode is used as to electrode, and calomel electrode is as three electricity of reference electrode composition
Polar body system；Electrolyte solution is the potassium nitrate solution of pH7.0,0.1mol/L.Comparison sensor 1 is made in above-mentioned material composition.
The difference of Tebuconazole portable sensor described in comparison sensor 1 and embodiment 7 is to compare the work of the use of sensor 1
Make the unmodified sulfydryl graphene of electrode.
Comparative example 2
With 30% hydrogen peroxide and concentrated sulfuric acid volume than impregnating glassy carbon electrode 20min for the mixed solution of 1:3, with 0.05 μm
Al2O3Sanding and polishing to electrode surface in being eluted with water after mirror surface degree, ultrasound 10min in water.Electrode after ultrasound is used
It is dried with nitrogen, is placed in the dilution heat of sulfuric acid of 0.5mol/L, scan 20 in -0.2~1.6V voltage range with cyclic voltammetry
Circle.Electrode is washed with water after the end of scan, is dried with nitrogen to get 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 solution, 4h is stood and obtains 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
Deposition gold-is Prussian blue under conditions of enclosing 0~1.0V, sweep speed 50mV/s, 17 circle of scanning, obtains gold-Prussian blue-sulfydryl
Graphene-gold nano particle modification electrode.The mixed solution be 0.1mol/L potassium nitrate, 1mmol/L tetrachloro alloy acid and
1mmol/L potassium ferrocyanide.
Gold-Prussian blue-sulfydryl graphene-gold nano particle modification electrode is placed in containing o-aminophenol and isophthalic two
In the phosphate buffer of phenol, enclosed using cyclic voltammetry in potential range -0.4~1.0V, sweep speed 50mV/s, scanning 9
Under the conditions of in situ electropolymerization prepare non-imprinted membrane (NIP), and modify in the Prussian blue surface of gold-of the electrode, water punching
It is dried with nitrogen after washing and stands 5h, obtain NIP polymer film modified electrode.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.
Polymer membrane electrode is placed in the methanol and acetic acid mixed solution that volume ratio is 1:9 and removes template molecule,
120rpm revolving speed stirs 30min, and comparison electrode 2 is obtained after washing with water.
Using comparison electrode 2 as working electrode, platinum electrode is used as to electrode, and calomel electrode is as three electricity of reference electrode composition
Polar body system；Electrolyte solution is the potassium nitrate solution of pH7.0,0.1mol/L.Comparison sensor 2 is made in above-mentioned material composition.
The difference of Tebuconazole portable sensor described in comparison sensor 2 and embodiment 7 is to compare the work of the use of sensor 2
That make to modify in electrode is non-imprinted membrane NIP.
Embodiment 10
This test measures the range of linearity of portable sensor using Differential Pulse Voltammetry and draws standard curve, and right
The detection of comparison sensor 1, comparison sensor 2 that the portable sensor and comparative example 1, comparative example 2 obtained than embodiment 7 obtains
Sensitivity.
Standard series preparation: taking Tebuconazole standard items compound concentration respectively is 0,0.00005,0.0002,0.0005,
The standard series of 0.001,0.006,0.03,0.1,0.2 and 0.4mmol/L.
Test object: comparison sensor 1 that portable sensor that embodiment 7 obtains, comparative example 1 obtain, comparative example 2 obtain
Comparison sensor 2.
Detection method: the working electrode of each test object is suspended in sample to be tested, 15min is adsorbed, after the completion of absorption
It washes with water.Three-electrode system is formed in working electrode, platinum electrode and calomel electrode using Differential Pulse Voltammetry,
It is detected in the potassium nitrate solution of pH7.0,0.1mol/L, the Differential Pulse Voltammetry condition is preferred are as follows: voltage 0.5~-
0.1V, pulse width 50ms, time interval 0.5s, jump rank current potential 5mV, modulated amplitude 50mV.What record test obtained shows poor arteries and veins
Voltammetric scan curve and peak response current value are rushed, the electrochemical response time is 1.5min.
As a result as shown in figure 5, in figure:
Curve is followed successively by from top to bottom uses the measurement concentration of Tebuconazole portable sensor described in embodiment 7 for 0,
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 obtained shows difference
Pulse Voltammetry scanning curve.
The illustration of Fig. 5 is that the Tebuconazole portable sensor measurement standard series sample that the working electrode of different modifying forms obtains
Sample concentration logarithm-current-responsive changing value the standard curve arrived, in figure:
■ is that the Tebuconazole molecular engram film electrode being prepared using embodiment 1 is obtained as the portable sensor of working electrode
Standard curve, curvilinear equation is as follows:
△ I=4.95LogC+26.64,
In formula, △ I indicates that specimen current values respond changing value, and unit is μ A；
C indicates the concentration of Tebuconazole in sample, unit mmol/L；
The coefficient R of curvilinear equation2=0.971；
● the standard curve that the comparison electrode 1 to be prepared with comparative example 1 obtains for the portable sensor of working electrode,
Curvilinear equation is as follows:
△ I=3.86LogC+9.11
In formula, △ I indicates that specimen current values respond changing value, and unit is μ A；
C indicates the concentration of Tebuconazole in sample, unit mmol/L；
The coefficient R of curvilinear equation2=0.996；
The mark that ▲ non-imprinted membrane the electrode to be prepared using comparative example 2 is obtained as the portable sensor of working electrode
Directrix curve, curvilinear equation are as follows:
△ I=1.23LogC+6.20,
In formula, △ I indicates that specimen current values respond changing value, and unit is μ A；
C indicates 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 obtains penta azoles within the scope of 0.0005~0.4mmol/L
Determining alcohol and current-responsive changing value are linear, what working electrode when current-responsive changing value is with adsorption sample measured
The difference for the peak response current value that working electrode after peak response current value and adsorption sample obtains when measuring.
By Fig. 5 illustration it is found that ■ curve with ● curve, ▲ curve are compared, and slope is higher, show penta azoles provided by the invention
Alcohol portable sensor relative to unmodified sulfydryl graphene working electrode or modified the working electrode group of non-imprinted membrane
At sensor detection sensitivity it is higher.As 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 detection, be computed Tebuconazole portable sensor detection provided by the invention
Limit can achieve 1.63 × 10-8mol/L。
Embodiment 11
Tebuconazole portable sensor and comparison sensor 2 is respectively adopted to Tebuconazole and Tebuconazole structure class in this test
It is quantitative determined like object, to detect the selectivity of Tebuconazole portable sensor.
Test object: the comparison sensor 2 that Tebuconazole portable sensor that embodiment 7 obtains, comparative example 2 obtain, the two
Difference be whether modified Tebuconazole molecular engram film.
Sample measurement: 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 method: working electrode is suspended in testing sample solution, is adsorbed 15min, is washed with water after the completion of absorption.
Using Differential Pulse Voltammetry to after adsorption sample working electrode, platinum electrode, calomel electrode composition three-electrode system in into
Row measurement, the electrolyte solution used are the potassium nitrate solution of pH7.0,0.1mol/L, and the Differential Pulse Voltammetry condition is excellent
Be selected as: 0.5~-0.1V of voltage, pulse width 50ms, time interval 0.5s, jump rank current potential 5mV, modulated amplitude 50mV.Record
The peak response current value that each sample, each sensor measure.The electrochemical response time is 1.5min.
Test results are shown in figure 6, in figure:
MIP indicates that portable sensor described in embodiment 7, NIP indicate the comparison sensor 2 that comparative example 2 obtains；
△ I is the peak response current value of the peak response current value measured and unadsorbed preceding measurement after adsorption sample
Difference；
△IMFor the △ I value measured with MIP, △ INFor the △ I value measured with NIP；
IF is △ IMWith △ INRatio, be mainly used for evaluating the working electrode in portable sensor to target compound and
The selectivity of its analogue.
As seen from Figure 6, the △ I value that MIP measures Tebuconazole is significantly higher than Triadimenol, bitertanol, penconazole, nitrile
The △ I value of bacterium azoles and Acetamiprid illustrates the peak response of Tebuconazole portable sensor measurement Tebuconazole sample provided by the invention
The peak response current variation value of current variation value and Triadimenol, bitertanol, penconazole, nitrile bacterium azoles and Acetamiprid has significantly
Difference；And the △ I value and Triadimenol of NIP measurement Tebuconazole, bitertanol, penconazole, nitrile bacterium azoles and Acetamiprid △ I value without
Significant difference is illustrated to be approached using response of the comparison sensor 2 to Tebuconazole and its analogue, can not clearly distinguish penta
The content of azoles alcohol and its analogue, Tebuconazole analogue may generate interference to Tebuconazole quantified results.
It can be seen that having modified the electrode of Tebuconazole molecular engram film relative to the electrode of modification non-imprinted membrane to penta
The specificity of azoles alcohol detection is stronger, i.e., Tebuconazole molecular engram film electrode provided by the invention is special to the quantitative detection of Tebuconazole
Property is stronger, effectively avoids influence of the Tebuconazole analogue to quantified results.
Meanwhile the IF value of Tebuconazole is significantly higher than Triadimenol, bitertanol, penconazole, nitrile bacterium azoles and pyridine worm in Fig. 6
Amidine, IF value are △ IMWith △ INRatio, the IF value the big, shows choosing of the electrode to target compound in Tebuconazole portable sensor
Selecting property is stronger.As it can be seen that Tebuconazole molecular engram film electrode provided by the invention is strong to the selectivity of Tebuconazole, it being capable of effective area
Divide Tebuconazole and its analogue.
Embodiment 12
The Tebuconazole portable sensor that this test is obtained using 7~9 any one of embodiment in cucumber, green vegetables to containing
Tebuconazole be measured, to examine the accuracy of Tebuconazole portable sensor.
Sample preparation: after 500g cucumber or the broken homogenate of green vegetables, 25g (being accurate to 0.01g) homogenised sample is weighed, respectively
Be added Tebuconazole standard items, make the concentration of Tebuconazole in homogenised sample be respectively as follows: 0.020mg/kg, 0.100mg/kg and
0.500mg/kg.Stand 30min, be added 50mL acetonitrile extraction, by mixed solution with high-shear homogenizer homogeneous after, be transferred to centrifugation
Guan Zhong, 5000rpm are centrifuged 5min, take 1mL supernatant extract liquor, and 3mL water is added, carries out sample test after mixing.
Experimental method: Tebuconazole molecular engram film electrode is suspended in sample to be tested, 15min is adsorbed, after the completion of absorption
It washes with water.Use time difference pulse voltammetry in three electricity formed with Tebuconazole molecular engram film electrode, platinum electrode, calomel electrode
It is measured in polar body system, the potassium nitrate solution of electrolyte solution pH7.0,0.1mol/L, the Differential Pulse Voltammetry item
Part is preferred are as follows: 0.5~-0.1V of voltage, pulse width 50ms, time interval 0.5s, jump rank current potential 5mV, modulated amplitude 50mV.Note
The differential pulse voltammetry voltammetric scan curve and peak response current value that record test obtains.The electrochemical response time is 1.5min.
It is counted using the peak response current value that standard curve obtained in embodiment 10 (Fig. 5 illustration) obtains test
Calculate, multiplied by after extension rate both the content of Tebuconazole in sample, and calculate in sample the rate of recovery of Tebuconazole and opposite
Standard deviation, concrete outcome are shown in Table 1.
The content and the rate of recovery of Tebuconazole in 1 cucumber of table and green vegetables
As shown in Table 1, contained using the Tebuconazole in Tebuconazole portable sensor provided by the invention measurement cucumber, green vegetables
Amount, the rate of recovery can achieve 77.90~118.69%, RSD value less than 10%, show the portable sensing of Tebuconazole provided by the invention
The accuracy of measurement of device is high, can satisfy the requirement of pesticide residue on-site test.
The above is only a preferred embodiment of the present invention, it is noted that for the ordinary skill people of the art
For member, various improvements and modifications may be made without departing from the principle of the present invention, these improvements and modifications are also answered
It is considered as protection scope of the present invention.
Claims (9)
1. a kind of Tebuconazole molecular engram film electrode, including base electrode, successively modify the Jenner in described matrix electrode surface
Rice grain, sulfydryl graphene and gold-are Prussian blue, are attached to the gold-Prussian blue surface Tebuconazole molecular engram film；
The Tebuconazole molecular engram film is using Tebuconazole as the o-aminophenol of template molecule and arofene；
The preparation method of the Tebuconazole molecular engram film electrode, comprising 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 that the step (1) obtains is stood 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) sulfydryl graphene-gold nano particle modification electrode that the step (2) obtains is placed in containing potassium nitrate, tetrachloro conjunction
In the mixed solution of auric acid and potassium ferrocyanide, using cyclic voltammetry deposition gold-Prussian blue particle, gold-Prussia is obtained
Indigo plant-sulfydryl graphene-gold nano particle modification electrode；
(4) by gold-that the step (3) obtains it is Prussian blue-sulfydryl graphene-gold nano particle modification electrode is placed in containing penta
Electropolymerization is carried out in the phosphate buffer of azoles alcohol, o-aminophenol and resorcinol, obtains polymer film modified electrode；
In the phosphoric acid mixed solution, the concentration of o-aminophenol and resorcinol independently is 2.0~2.5mmol/L, penta azoles
The concentration of alcohol is 0.5~1mmol/L, and the concentration of phosphate buffer is 0.01~0.07mmol/L；The electropolymerizatioconditions conditions are as follows: electricity
Position range -0.4~1.0V, sweep speed 50mV/s, 8~10 circle of scanning；
(5) polymer film modified electrode of the step (4) is placed in removing polymer film in the mixed solution of methanol and acetic acid
In Tebuconazole molecule, obtain Tebuconazole molecular engram film electrode.
2. a kind of preparation method of Tebuconazole molecular engram film electrode, comprising 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 that the step (1) obtains is stood 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) sulfydryl graphene-gold nano particle modification electrode that the step (2) obtains is placed in containing potassium nitrate, tetrachloro conjunction
In the mixed solution of auric acid and potassium ferrocyanide, using cyclic voltammetry deposition gold-Prussian blue particle, gold-Prussia is obtained
Indigo plant-sulfydryl graphene-gold nano particle modification electrode；
(4) by gold-that the step (3) obtains it is Prussian blue-sulfydryl graphene-gold nano particle modification electrode is placed in containing penta
Electropolymerization is carried out in the phosphate buffer of azoles alcohol, o-aminophenol and resorcinol, obtains polymer film modified electrode；
In the phosphoric acid mixed solution, the concentration of o-aminophenol and resorcinol independently is 2.0~2.5mmol/L, penta azoles
The concentration of alcohol is 0.5~1mmol/L, and the concentration of phosphate buffer is 0.01~0.07mmol/L；The electropolymerizatioconditions conditions are as follows: electricity
Position range -0.4~1.0V, sweep speed 50mV/s, 8~10 circle of scanning；
(5) polymer film modified electrode of the step (4) is placed in removing polymer film in the mixed solution of methanol and acetic acid
In Tebuconazole molecule, obtain Tebuconazole molecular engram film electrode.
3. preparation method according to claim 2, which is characterized in that tetrachloro alloy acid solution described in step (1) it is dense
Degree is 2.5~3.5mmol/L, and the electrodeposition time is 80~150s.
4. preparation method according to claim 2 or 3, which is characterized 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, which is characterized in that potassium nitrate is dense in step (3) described mixed solution
Degree is 0.05~0.2mol/L, the concentration of tetrachloro alloy acid is 0.5~1.5mmol/L and ferrocyanide potassium concn be 0.5~
1.5mmol/L；The cyclic voltammetry condition are as follows: 0~1.0V of potential range, sweep speed 50mV/s, 15~30 circle of scanning.
6. preparation method according to claim 2, which is characterized in that the mixed solution of step (5) methanol and acetic acid
In, the volume ratio of methanol and acetic acid is 1: 7~1: 11.
7. it is a kind of for Tebuconazole quantitative determination portable sensor, including working electrode, to electrode, reference electrode and electrolyte
Solution, which is characterized in that the working electrode is Tebuconazole molecular engram film electrode described in claim 1 or claim 2
The Tebuconazole molecular engram film electrode that preparation method described in~6 any one obtains, the electrolyte solution be pH value be 5.0~
8.0, concentration is 0.08~0.14mol/L potassium nitrate solution.
8. Tebuconazole molecular engram film electrode described in claim 1 or portable sensor as claimed in claim 7 are in measurement agriculture
Application in product in Tebuconazole pesticide residue.
9. application according to claim 8, the method for measuring Tebuconazole pesticide residue in agricultural product includes following step
It is rapid:
1) Tebuconazole molecular engram film electrode is suspended in sample solution, adsorbs 10~20min；
2) it regard the Tebuconazole molecular engram film electrode after absorption in the step 1) as working electrode, and it is electric to electrode, reference
Pole forms three-electrode system, and electro-chemical test, the differential pulse voltammetry voltammetric scan that record test obtains 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), it is molten to be calculated sample
The content of Tebuconazole in liquid；
The standard curve is the linearity curve between the peak response current value and Tebuconazole concentration of the test of differential pulse voltammetry volt-ampere.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN104764775A (en) * | 2015-02-26 | 2015-07-08 | 河北科技大学 | Method for preparation of triazole molecularly imprinted electrochemical sensor based on electropolymerized OPD/OAP composite membrane and application thereof |
| CN105548314A (en) * | 2016-01-15 | 2016-05-04 | 浙江大学 | Method for preparing Prussian-blue-gold multifunctional surface through magnetic bead electrochemical conversion-electro-deposition |
| WO2016170385A1 (en) * | 2015-04-20 | 2016-10-27 | Tubitak | The use of piezoelectric transducers modified with metal oxide-based thin films for direct detection of amine derivatives in liquid media |
| CN106248756A (en) * | 2016-08-27 | 2016-12-21 | 浙江省农业科学院 | Tebuconazole molecular engram film electrode based on nanometer gold enhanced sensitivity and the preparation of electrochemical sensor, application and method of testing |
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104764775A (en) * | 2015-02-26 | 2015-07-08 | 河北科技大学 | Method for preparation of triazole molecularly imprinted electrochemical sensor based on electropolymerized OPD/OAP composite membrane and application thereof |
| WO2016170385A1 (en) * | 2015-04-20 | 2016-10-27 | Tubitak | The use of piezoelectric transducers modified with metal oxide-based thin films for direct detection of amine derivatives in liquid media |
| CN105548314A (en) * | 2016-01-15 | 2016-05-04 | 浙江大学 | Method for preparing Prussian-blue-gold multifunctional surface through magnetic bead electrochemical conversion-electro-deposition |
| CN106248756A (en) * | 2016-08-27 | 2016-12-21 | 浙江省农业科学院 | Tebuconazole molecular engram film electrode based on nanometer gold enhanced sensitivity and the preparation of electrochemical sensor, application and method of testing |
Non-Patent Citations (1)
| Title |
|---|
| Electrochemical sensor based on molecularly imprinted polymerreduced graphene oxide and gold nanoparticles modified electrodefor detection of carbofuran;Xuecai Tan 等;《Sensors and Actuators B》;20150529;第220卷;第216-220页 * |
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