CN106596681A - Carbofuran molecularly-imprinted membrane electrode, portable sensor and application of portable sensor - Google Patents
Carbofuran molecularly-imprinted membrane electrode, portable sensor and application of portable sensor Download PDFInfo
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- CN106596681A CN106596681A CN201710018369.9A CN201710018369A CN106596681A CN 106596681 A CN106596681 A CN 106596681A CN 201710018369 A CN201710018369 A CN 201710018369A CN 106596681 A CN106596681 A CN 106596681A
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Abstract
The invention provides a carbofuran molecularly-imprinted membrane electrode. The carbofuran molecularly-imprinted membrane electrode comprises a basal electrode body, gold nanoparticles and a carbofuran molecularly-imprinted membrane, wherein the gold nanoparticles are deposited on the surface of the basal electrode body, and the carbofuran molecularly-imprinted membrane is arranged on the surfaces of the gold nanoparticles and is a p-aminobenzoic acid polymer membrane taking carbofuran as a template molecule. The invention further provides a portable sensor comprising the carbofuran molecularly-imprinted membrane electrode. The portable sensor has the advantages that limit of detection is 1.1X10<8> mol/L, a detection range is 4.0X10<4> mol/L-5.0X10<8> mol/L, and accordingly the portable sensor is high in sensitivity and specificity and easy to carry and can be used for onsite quantitative detection of the carbofuran.
Description
Technical field
The present invention relates to Pesticides Testing technical field, and in particular to a kind of carbofuran molecular engram film electrode and be made from it
Portable sensor and its using method.
Background technology
Carbofuran is a kind of efficient, wide spectrum, longevity of residure length, high residue, the carbamate chemicals for agriculture of severe toxicity.Although now
Carbofuran is used on veterinary antibiotics, tealeaves, medicinal material by restriction, but in paddy rice, cotton, tobacco, Soybean and Other Crops so far
Still can apply.Meanwhile, still in widely used carbosulfan and Benfuracard micro carbofuran is also easily degraded at present, it is agriculture
Another main source of the Determination of carbofuran in product and environment.Therefore, long-term and substantial amounts of use, various residual sources and
High toxicity high residue makes the ecology and environmental risk of carbofuran cause highest attention.
Existing Determination of carbofuran detection method mainly based on chromatogram and chromatograph-mass spectrometer coupling method, with high sensitivity,
The advantage of high accuracy, especially chromatograph-mass spectrometer coupling method are to realize the splendid selection of its qualitative and quantitative analysis.But these points
Analysis method is limited in that：Required analytical instrument is typically placed in the standard analysis experiment interior away from scene, and instrument valency
Lattice are expensive, complex operation, need operating personnel trained；It is long that sample pre-treatments expend the time, it is difficult in meeting agricultural product
The demand of residues of pesticides field quick detection.Therefore, need convenient, the cheap and portative residues of pesticides of development badly quickly to examine
Survey means.
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 carbofuran quantitative determination, cost
Low, portable, sensitivity is high.
In order to realize foregoing invention purpose, the present invention provides technical scheme below：
The invention provides a kind of carbofuran molecular engram film electrode, including base electrode, it is deposited on described matrix electrode
The nanogold particle on surface, is arranged on the carbofuran molecular engram film on the nanogold particle surface；
The carbofuran molecular engram film is the p-aminobenzoic acid polymer film with carbofuran as template molecule.
The invention provides a kind of preparation method of carbofuran molecular engram film electrode described in above-mentioned technical proposal, including with
Lower step：
(1) base electrode is placed in tetrachloro alloy acid solution, electro-deposition is carried out using potentiostatic method, in described matrix electricity
The upper nanogold particle of pole surface deposition；
(2) the nanogold particle modified electrode immersion for obtaining the step (1) is containing carbofuran and p-aminobenzoic acid
Phosphate buffer in carry out electropolymerization, obtain polymer film modified electrode；
(3) polymer film modified electrode that step (2) is obtained is placed in the methanol solution of NaOH, removing polymer
Carbofuran molecule in film, obtains carbofuran 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 150～300s.
Preferably, in the phosphate buffer solution of the step (2), carbofuran is 1 with the mol ratio of p-aminobenzoic acid:3
～5.
Preferably, the electropolymerization of the step (2) adopts the condition of cyclic voltammetry, electropolymerization to be：Potential range -0.4
～1.0V, sweep speed is 40～60mV/S, and the scanning number of turns is 8～12 circles.
Present invention also offers it is a kind of for carbofuran quantitative determination portable sensor, including working electrode, to electrode,
Reference electrode and electrolyte solution, the working electrode is carbofuran molecular engram film electrode or utilization described in above-mentioned technical proposal
The carbofuran molecular engram film electrode that above-mentioned preparation method is obtained, the electrolyte solution is the potassium ferricyanide-potassium ferrocyanide
Klorvess Liquid, in the electrolyte solution：The concentration of the potassium ferricyanide and potassium ferrocyanide independently is 0.8～1.2mmol/L,
The concentration of potassium chloride is 0.05～0.2mol/L.
Preferably, described is platinum electrode to electrode, and the reference electrode is saturated calomel electrode.
The invention provides application of the portable sensor described in above-mentioned technical proposal in carbofuran quantitative determination.
Preferably, the application is comprised the following steps：
(1) carbofuran molecular engram film electrode is suspended in sample solution, adsorbs 9～11min；
(2) by the carbofuran molecular engram film electrode after absorption in the step (1), and to electrode, reference electrode composition
Three-electrode system, carries out electro-chemical test in electrolyte solution, differential pulse voltammetry voltammetric scan curve that record test is obtained and
Peak response current value；
(3) sample obtained according to the calibration curve and the step (2) of predetermined response current value and carbofuran concentration
The peak response current value of product solution, obtains the content of carbofuran in sample solution.
Preferably, the portable sensor is used to determine carbofuran residues of pesticides in fruits and vegetables.
Compared with prior art, the present invention has advantages below to the present invention：
The carbofuran molecular engram film electrode that the present invention is provided is printed by the nanogold particle of deposition with reference to carbofuran molecule
Mark film effectively increases the specificity of electrode pair carbofuran molecule and sensitivity.Test shows that the carbofuran that the present invention is provided divides
When sub- trace membrane electrode is used to detect, test limit is only 1.1 × 10-8Mol/L, detection range is 5.0 × 10-8Mol/L～4.0
×10-4Mol/L, the carbofuran molecular engram film electrode for showing present invention offer has high sensitivity, can be used in carbofuran
Quantitative determination.
The present invention provide carbofuran molecular engram film electrode in the preparation with carbofuran as template molecule, with p-aminophenyl
Formic acid is polymerized functional monomer, and using electropolymerization in situ electropolymerization film is made, and reuses methanol-hydrogen sodium hydroxide solution and removes mould
Plate molecule obtains the carbofuran molecular engram film electrode with recognition site and hole.Test is shown, is provided using the present invention
Carbofuran molecular engram film electrode detects the similar agricultural chemicals Mobucin of the structure of carbofuran and carbofuran, Methomyl, Aphox, tears
When prestige of going out and MTMC, carbofuran molecular engram film electrode is far above other structures to the response of carbofuran and selectivity parameter IF
Similar agricultural chemicals.Test shows that the carbofuran molecular engram film electrode preparation method provided by the present invention can obtain specificity
Strong detecting electrode, can effectively differentiate the carbofuran agricultural chemicals similar with other structures, it is to avoid the similar agriculture of carbofuran structure
Impact of the medicine to measurement result.
Present invention also offers a kind of portable sensor including carbofuran molecular engram film electrode, including working electrode,
To electrode, reference electrode and electrolyte solution, the instrument for the detection method of existing chromatogram or chromatograph-mass spectrometer coupling
Small volume, can go out to carry, and not examined place limits, and can be used for Site Detection.And the portable biography that the present invention is provided
10.5～12.5min is only needed during sensor quantitative determination carbofuran, detection time is greatly shortened, quantitative determination efficiency is improved.
When the portable sensor provided using the present invention is quantitative determined to the carbofuran in fruits and vegetables, the rate of recovery of carbofuran can
Reach 83～106%.Show that the quantitative determination degree of accuracy of portable sensor of the present invention is high, disclosure satisfy that agricultural chemicals Site Detection
Demand.
The carbofuran quantitative determination portable sensor composition that the present invention is provided is simple, relative to existing chromatogram or chromatogram-
Chromatograph used, mass spectrometric instrument cost are low during the detection method of mass spectrometry.
Description of the drawings
Fig. 1 is the cyclic voltammogram of Different treatments the electrode obtained；
Fig. 2 is the cyclic voltammogram of Different electrodes modification；
Fig. 3 is the range of linearity current -voltage curve figure for detecting carbofuran content with portable sensor；
Fig. 4 is the calibration curve of the carbofuran log concentration value-current-responsive changing value of different modifying electrode；
Fig. 5 is the selective evaluation figure of carbofuran and its analogue.
Specific embodiment
The invention provides a kind of carbofuran molecular engram film electrode, including base electrode, it is deposited on described matrix electrode
The nanogold particle on surface, is arranged on the carbofuran molecular engram film on the nanogold particle surface；
The carbofuran molecular engram film is the p-aminobenzoic acid polymer film with carbofuran 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, the carbofuran molecular engram film is the p-aminobenzoic acid polymerization with carbofuran as template molecule
Thing film.
The invention provides a kind of preparation method of carbofuran molecular engram film electrode described in above-mentioned technical proposal, including with
Lower step：
(1) base electrode is placed in tetrachloro alloy acid solution, electro-deposition is carried out using potentiostatic method, in described matrix electricity
The upper nanogold particle of pole surface deposition；
(2) the nanogold particle modified electrode immersion for obtaining the step (1) is containing carbofuran and p-aminobenzoic acid
Phosphate buffer in carry out electropolymerization, obtain polymer film modified electrode；
(3) polymer film modified electrode that step (2) is obtained is placed in the methanol solution of NaOH, removing polymer
Carbofuran molecule in film, obtains carbofuran molecular engram film electrode.
The present invention before base electrode to be placed in 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 8～15min of immersion, with 0.03～0.10 μm
Al2O3Carry out sanding and polishing；
B, the base electrode after sanding and polishing in step a is cleaned, 8～15min of ultrasound in water；
C, the base electrode in step b after ultrasound is placed in 0.05～0.2mol/L dilution heat of sulfuric acid, using following
Ring voltammetry scanning 12～18 is enclosed, the base electrode cleaned after both must pre-processing and clean after drying up.
Base electrode is placed in 8～15min of process in the mixed solution of hydrogen peroxide and the concentrated sulfuric acid by the present invention.Specifically, originally
Invention is soaked in the mixed solution by base electrode immersion with hydrogen peroxide and the concentrated sulfuric acid.In the present invention, the hydrogen peroxide with it is dense
The volume ratio of sulfuric acid is 1:2～5, preferably 1:3.Soak time of the present invention is preferably 9～12min, more preferably
10min.The volumetric concentration of hydrogen peroxide of the present invention is preferably 20～50%, more preferably 30%；The concentrated sulfuric acid adopts city
Sell commodity.
In the present invention, the mixed solution preparation method of the hydrogen peroxide and the concentrated sulfuric acid is to add the concentrated sulfuric acid to hydrogen peroxide
In mixed.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 limit
It is fixed, can be by base electrode submergence.The present invention is using the mixed solution of hydrogen peroxide and the concentrated sulfuric acid to base electrode process, energy
Enough organic impurities effectively removed on base electrode.
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 adopts 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, the present invention is placed in base electrode in 0.05～0.2mol/L dilution heat of sulfuric acid, using cyclic voltammetry
Scanning 12～18 enclose, cleaning dry up after both pretreated base electrode.The concentration of dilution heat of sulfuric acid of the present invention is preferred
For 0.08～0.15mol/L, more preferably 0.1mol/L.In the present invention, the voltage range of the cyclic voltammetry is -0.2
～1.6V；The cyclic voltammetry scanning number of turns is preferably 14～17 circles, more preferably 15 circles.
The base electrode that the present invention is obtained after cyclic voltammetry is scanned is with water cleaning, then is dried up with nitrogen, obtains pre- place
Base electrode after reason.The present invention makes electrode polarization using cyclic voltammetry scanning base electrode, and by electrochemical means base is made
Body electrode surface is cleaned.
After obtaining base electrode, the present invention is placed in base electrode in tetrachloro alloy acid solution, and using potentiostatic method base is made
Body electrode surface deposits nanogold particle.The concentration of tetrachloro alloy acid solution of the present invention is 2.5～3.5mmol/L, preferably
For 2.8～3.3mmol/L, more preferably 3.0mmol/L.In the present invention, the electrodeposition time is 150～300s, preferably
For 180～260s, more preferably 200s.Current potential during potentiostatic electrodeposition of the present invention is -0.3～-0.1V, more preferably -
0.2V.It is to be reduced to by electric current the gold ion in tetrachloro alloy acid that the present invention deposits nanogold particle using potentiostatic method
Nm of gold simple substance is so as to being deposited on base electrode surface.
After the constant potential electro-deposition, the present invention is by the nanogold particle modified electrode for obtaining immersion containing carbofuran and right
Electropolymerization is carried out in the phosphate buffer of aminobenzoic acid, polymer film modified electrode is obtained.It is of the present invention containing carbofuran
It is 1 with the mol ratio of carbofuran in the phosphate buffer of p-aminobenzoic acid and p-aminobenzoic acid:3～5, preferably 1:4；Institute
Concentration of the carbofuran in phosphate buffer is stated for 0.5～2mmol/L, preferably 1mmol/L；The p-aminobenzoic acid exists
Concentration in phosphate buffer is 3～5mmol/L, preferably 4mmol/L.In the present invention, phosphate buffer is that electropolymerization is anti-
Reaction environment should be provided, the phosphate buffer density is 0.01～0.2mol/L, preferably 0.05mol/L；Phosphate buffer
PH be 5～9, preferably 7.The present invention is using p-aminobenzoic acid as polymerized monomer, the p-aminophenyl first under electropolymerization effect
Acid is connected to form the molecular engram film containing template with carbofuran molecule by non-covalent bond.
In the present invention, the electropolymerization is preferably carried out using cyclic voltammetry, more preferably using cyclic voltammetry
Electropolymerization in situ prepares molecular engram film.Electropolymerizatioconditions conditions of the present invention are preferably：Potential range -0.4～1.0V, sweeps and hastens
Rate is 40～60mV/S, and the scanning number of turns is 8～12 circles.The rate of hastening of sweeping of the present invention is preferably 50mV/S, the scanning number of turns
Preferably 10 circles.
Currently preferred to clean the polymer film modified electrode that electropolymerization is obtained with water, nitrogen places 0.5 after drying up
～2h carries out again template molecule and removes, and preferred standing time is 1h.
After the electropolymerization, the present invention is placed in the polymer film modified electrode for obtaining in the methanol solution of NaOH,
Carbofuran molecule in removing polymer film, obtains carbofuran molecular engram film electrode.In the present invention, the NaOH
Methanol solution refers to that containing the NaOH that concentration is 0.05～0.15mol/L in methyl alcohol preferred naoh concentration is
0.1mol/L.Specifically, the present invention is placed in polymer film modified electrode in the methanol solution of NaOH by carbofuran molecule
Remove from polymer, obtain the carbofuran molecular engram film electrode with carbofuran recognition site and hole.In the present invention,
It is described to remove the time and be preferably 15～25min, more preferably 20min.The present invention using the methanol solution of NaOH as solvent,
The carbofuran molecule in polymer is set to be removed from polymer by competitive desorption.In the present invention, it is preferred to will remove
Polymer film modified electrode afterwards is cleaned with water, obtains carbofuran molecular engram film electrode.
The invention provides it is a kind of for carbofuran quantitative determination portable sensor, including working electrode, to electrode, ginseng
Than electrode and electrolyte solution.
In the present invention, the working electrode is for carbofuran molecular engram film electrode described in above-mentioned technical proposal or by upper
State the carbofuran molecular engram film electrode that preparation method is obtained.
In the present invention, the electrolyte solution for the potassium ferricyanide-potassium ferrocyanide Klorvess Liquid, the electrolyte
In solution：The concentration of the potassium ferricyanide and potassium ferrocyanide independently is 0.8～1.2mmol/L, and the concentration of potassium chloride is 0.05～
0.2mol/L；Preferably, the concentration of the potassium ferricyanide and potassium ferrocyanide independently is 1mmol/L, and the concentration of potassium chloride is
0.1mol/L。
In the present invention, described is platinum electrode to electrode, and the reference electrode is saturated calomel electrode.
Present invention also offers application of the portable sensor in carbofuran quantitative determination, is preferably determining fruits and vegetables
Application in middle carbofuran residues of pesticides.
Application of the present invention preferably specifically includes following steps：
(1) carbofuran molecular engram film electrode is suspended in sample solution, adsorbs 9～11min；
(2) by the carbofuran molecular engram film electrode after absorption in the step (1), and to electrode, reference electrode composition
Three-electrode system, carries out electro-chemical test in electrolyte solution, differential pulse voltammetry voltammetric scan curve that record test is obtained and
Peak response current value；
(3) sample obtained according to the calibration curve and the step (2) of predetermined response current value and carbofuran concentration
The peak response current value of product solution, obtains the content of carbofuran in sample solution.
Carbofuran molecular engram film electrode is suspended in 9～11min of absorption in sample solution by the present invention.In the present invention,
Adsorption time is preferably 10min.Sample solution of the present invention obtains test substance homogenate.The present invention is to the homogenate
Mode is routinely homogenized mode without any restriction using this area, and such as manual homogenization, mechanical homogenisation, ultrasound is homogenized, freezes repeatedly
Melt.
The currently preferred carbofuran molecular engram film electrode by after the completion of absorption carries out electrochemistry survey after being cleaned with water
Examination.
After the completion of absorption, the present invention constitutes three electrode bodies by carbofuran molecular engram film electrode, to electrode and reference electrode
System, carries out electro-chemical test in electrolyte solution, differential pulse voltammetry voltammetric scan curve and peak response that record test is obtained
Current value.The carbofuran molecule in sample is adsorbed due to carbofuran molecular engram film electrode, molecular engram site is by carbofuran
Molecule occupy and reduce and electrolyte solution in hexacyanoferrate combination, so as to pass through record differential pulse voltammetry voltammetric scan
The change of curve and peak response current value can be quantitative calculate sample in carbofuran content.
Peak response electric current of the calibration curve according to predetermined response current value and carbofuran concentration of the invention to record
Value is calculated, and obtains the content of carbofuran in sample solution.Specifically, response current value of the present invention and carbofuran concentration
Calibration curve be with it is unadsorbed when peak response current value with absorption after peak response current value difference and carbofuran
The logarithm value of concentration carries out linear fit for parameter, it is preferred that the logarithm value with carbofuran concentration as abscissa, with unadsorbed sample
The difference of the peak response current value determined during product and the peak response current value determined after absorption is ordinate.In the present invention
In, the linear concentration of carbofuran ranges preferably from 5.0 × 10 in the linearity curve-8Mol/L～4.0 × 10-4mol/L。
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 the embodiment of whole.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
With 30% hydrogen peroxide and concentrated sulfuric acid volume ratio as 1:3 mixed solution immersion glassy carbon electrode 10min, with 0.05 μm
Al2O3Sanding and polishing to electrode surface is mirrored after degree and washes, the ultrasound 10min in water.Electrode after ultrasound is used
Nitrogen is dried up, and in being placed in the dilution heat of sulfuric acid of 0.1mol/L, 15 is scanned in -0.2～1.6V voltage ranges with cyclic voltammetry
Circle.Use water cleaning electrode, nitrogen to dry up after the end of scan, both pretreated base electrode.
Pretreated base electrode is placed in the tetrachloro alloy acid solution of 3mmol/L, electricity is carried out using potentiostatic method
Deposition 200s, makes nanogold particle be deposited on base electrode surface, obtains nanogold particle modified electrode.Nanogold particle is repaiied
Decorations electrode is placed in the phosphate buffer of carbofuran and p-aminobenzoic acid, and using cyclic voltammetry original position electropolymerization molecule is prepared
Blotting membrane, obtains polymer film modified electrode.The electropolymerizatioconditions conditions are：Potential range -0.4～1.0V, sweeping the rate of hastening is
50mV/S, the scanning number of turns is 10 circles, and the carbofuran in the phosphate buffer is 1 with the molar concentration rate of p-aminobenzoic acid:
4。
Polymer film modified electrode is cleaned with water, nitrogen places 1h after drying up.By the polymer film modification electricity after placement
Pole is placed in the methanol solution of 0.1mol/L NaOH and removes template molecule, described to remove the time for 20min.After being cleaned with water
Obtain carbofuran molecular engram film electrode.
Embodiment 2
With 20% hydrogen peroxide and concentrated sulfuric acid volume ratio as 1:5 mixed solution immersion glassy carbon electrode 8min, with 0.03 μm
Al2O3Sanding and polishing to electrode surface is mirrored after degree and washes, the ultrasound 8min in water.Electrode after ultrasound is used
Nitrogen is dried up, and in being placed in the dilution heat of sulfuric acid of 0.05mol/L, 12 is scanned in -0.2～1.6V voltage ranges with cyclic voltammetry
Circle.Use water cleaning electrode, nitrogen to dry up after the end of scan, obtain final product pretreated base electrode.
Pretreated base electrode is placed in the tetrachloro alloy acid solution of 2mmol/L, electricity is carried out using potentiostatic method
Deposition 300s, makes nanogold particle be deposited on base electrode surface, obtains nanogold particle modified electrode.Nanogold particle is repaiied
Decorations electrode is placed in the phosphate buffer of carbofuran and p-aminobenzoic acid, and using cyclic voltammetry original position electropolymerization molecule is prepared
Blotting membrane, obtains polymer film modified electrode.The electropolymerizatioconditions conditions are：Potential range -0.4～1.0V, sweeping the rate of hastening is
40mV/S, the scanning number of turns is 8 circles, and the carbofuran in the phosphate buffer is 1 with the molar concentration rate of p-aminobenzoic acid:3.
Polymer film modified electrode is cleaned with water, nitrogen places 0.5h after drying up.Polymer film after placement is modified
Electrode is placed in the methanol solution of 0.05mol/L NaOH and removes template molecule, described to remove the time for 15min.It is clear with water
Carbofuran molecular engram film electrode is obtained after washing.
Embodiment 3
With 50% hydrogen peroxide and concentrated sulfuric acid volume ratio as 1:3 mixed solution immersion glassy carbon electrode 15min, with 0.2 μm
Al2O3Sanding and polishing to electrode surface is mirrored after degree and washes, the ultrasound 15min in water.Electrode after ultrasound is used
Nitrogen is dried up, and in being placed in the dilution heat of sulfuric acid of 0.2mol/L, 18 is scanned in -0.2～1.6V voltage ranges with cyclic voltammetry
Circle.Use water cleaning electrode, nitrogen to dry up after the end of scan, obtain final product pretreated base electrode.
Pretreated base electrode is placed in the tetrachloro alloy acid solution of 5mmol/L, electricity is carried out using potentiostatic method
Deposition 150s, makes nanogold particle be deposited on base electrode surface, obtains nanogold particle modified electrode.Nanogold particle is repaiied
Decorations electrode is placed in the phosphate buffer of carbofuran and p-aminobenzoic acid, and using cyclic voltammetry original position electropolymerization molecule is prepared
Blotting membrane, obtains polymer film modified electrode.The electropolymerizatioconditions conditions are：Potential range -0.4～1.0V, sweeping the rate of hastening is
60mV/S, the scanning number of turns is 15 circles, and the carbofuran in the phosphate buffer is 1 with the molar concentration rate of p-aminobenzoic acid:
5。
Polymer film modified electrode is cleaned with water, nitrogen places 2h after drying up.By the polymer film modification electricity after placement
Pole is placed in the methanol solution of 0.2mol/L NaOH and removes template molecule, described to remove the time for 25min.After being cleaned with water
Obtain carbofuran molecular engram film electrode.
Embodiment 4
Base electrode is placed in the tetrachloro alloy acid solution of 3mmol/L, electro-deposition 200s is carried out using potentiostatic method, made
Nanogold particle is deposited on base electrode surface, obtains nanogold particle modified electrode.Nanogold particle modified electrode is placed in
In the phosphate buffer of carbofuran and p-aminobenzoic acid, molecular engram film is prepared using cyclic voltammetry original position electropolymerization, obtained
To polymer film modified electrode.The electropolymerizatioconditions conditions are：Potential range -0.4～1.0V, sweeps the rate of hastening for 50mV/S, scanning
The number of turns is 10 circles, and the carbofuran in the phosphate buffer is 1 with the molar concentration rate of p-aminobenzoic acid:4.
Polymer film modified electrode is placed in the methanol solution of 0.1mol/L NaOH and removes template molecule, the shifting
Except the time is 20min.Carbofuran molecular engram film electrode is obtained after being cleaned with water.
Comparative example 1
With 30% hydrogen peroxide and concentrated sulfuric acid volume ratio as 1:3 mixed solution immersion glassy carbon electrode 10min, with 0.05 μm
Al2O3Sanding and polishing to electrode surface is mirrored after degree and washes, the ultrasound 10min in water.Electrode after ultrasound is used
Nitrogen is dried up, and in being placed in the dilution heat of sulfuric acid of 0.1mol/L, 15 is scanned in -0.2～1.6V voltage ranges with cyclic voltammetry
Circle.Use water cleaning electrode, nitrogen to dry up after the end of scan, obtain final product pretreated base electrode.
Pretreated base electrode is placed in the tetrachloro alloy acid solution of 3mmol/L, electricity is carried out using potentiostatic method
Deposition 200s, makes nanogold particle be deposited on base electrode surface, obtains nanogold particle modified electrode.Nanogold particle is repaiied
Decorations electrode is placed in the phosphate buffer of carbofuran and p-aminobenzoic acid, and using cyclic voltammetry original position electropolymerization molecule is prepared
Blotting membrane, obtains polymer film modified electrode.The electropolymerizatioconditions conditions are：Potential range -0.4～1.0V, sweeping the rate of hastening is
50mV/S, the scanning number of turns is 10 circles, and the carbofuran in the phosphate buffer is 1 with the molar concentration rate of p-aminobenzoic acid:
4。
Polymer film modified electrode is cleaned with water, nitrogen places 1h after drying up.By the polymer film modification electricity after placement
Pole is placed in volume ratio 9:Template molecule is removed in 1 methyl alcohol and alcohol mixed solution, it is described to remove the time for 20min.It is clear with water
Comparison electrode 1 is obtained after washing.
The carbofuran electrode difference that comparison electrode 1 is obtained with embodiment 1 is using volume ratio 9:1 methyl alcohol and ethanol are mixed
Close solution and remove solvent as template.
Comparative example 2
With 30% hydrogen peroxide and concentrated sulfuric acid volume ratio as 1:3 mixed solution immersion glassy carbon electrode 10min, with 0.05 μm
Al2O3Sanding and polishing to electrode surface is mirrored after degree and washes, the ultrasound 10min in water.Electrode after ultrasound is used
Nitrogen is dried up, and in being placed in the dilution heat of sulfuric acid of 0.1mol/L, 15 is scanned in -0.2～1.6V voltage ranges with cyclic voltammetry
Circle.Use water cleaning electrode, nitrogen to dry up after the end of scan, obtain final product pretreated base electrode.
Pretreated base electrode is placed in the tetrachloro alloy acid solution of 3mmol/L, electricity is carried out using potentiostatic method
Deposition 200s, makes nanogold particle be deposited on base electrode surface, obtains nanogold particle modified electrode.Nanogold particle is repaiied
Decorations electrode is placed in the phosphate buffer of carbofuran and p-aminobenzoic acid, and using cyclic voltammetry original position electropolymerization molecule is prepared
Blotting membrane, obtains polymer film modified electrode.The electropolymerizatioconditions conditions are：Potential range -0.4～1.0V, sweeping the rate of hastening is
50mV/S, the scanning number of turns is 10 circles, and the carbofuran in the phosphate buffer is 1 with the molar concentration rate of p-aminobenzoic acid:
4。
Polymer film modified electrode is cleaned with water, nitrogen places 1h after drying up.By the polymer film modification electricity after placement
Pole is placed in 0.1mol/L sulfuric acid and removes template molecule, described to remove the time for 20min.Comparison electrode 2 is obtained after being cleaned with water.
The carbofuran electrode difference that comparison electrode 2 is obtained with embodiment 1 is to be moved as template using 0.1mol/L sulfuric acid
Except solvent.
Embodiment 5
This test determines respectively the base electrode of modified nano gold particle, polymer film modification electricity using cyclic voltammetry
The cyclic voltammogram of the carbofuran molecular engram film electrode that pole, comparison electrode 1, comparison electrode 2 and embodiment 1 are obtained.
It is prepared by electrode to be measured：The preparation method recorded according to embodiment 1 prepares the base electrode of modified nano gold particle, gathers
Compound modified electrode, carbofuran molecular engram film electrode.The preparation method recorded according to comparative example 1, comparative example 2 prepares contrast electricity
Pole 1, comparison electrode 2.
Using electrode to be measured as working electrode, platinum electrode is used as to electrode, and calomel electrode is electric as reference electrode composition three
Polar body system.Electrolyte solution is the Klorvess Liquid containing the potassium ferricyanide and potassium ferrocyanide, wherein the potassium ferricyanide and ferrous cyanogen
The concentration for changing potassium independently is 1.0mmol/L, and the concentration of potassium chloride is 0.1mol/L.Record the electricity that different electrodes to be measured are obtained
Stream-voltage curve, concrete outcome is shown in Fig. 1.
Measurement result is as shown in figure 1, in figure：A is the cyclic voltammogram of the base electrode of modified nano gold particle, and b is poly-
The cyclic voltammogram of compound film modified electrode, c is the cyclic voltammogram of comparison electrode 1, and d is the cyclic voltammogram of comparison electrode 2,
E is the cyclic voltammogram of the carbofuran molecular engram film electrode that embodiment 1 is obtained.
Current -voltage curve when curve b is working electrode for polymer film modified electrode, relative to unmodified polymer
The curve a of film, current value is greatly reduced, closure degree increase, and non-oxidation reduction peak.Because modification is in nm of gold and matrix electricity
The polymer film structure on pole surface closely, includes template molecule, and hexacyanoferrate is unable to reach electrode surface and carries out electronics biography
Pass, thus non-oxidation reduction peak.Current value declines to a great extent and shows that electrode surface has successfully modified polymer film.
Curve c and curve d respectively removes the carbofuran molecular engram film of solvent process using difference, as shown in Figure 1, moves
Current-responsive value is not significantly raised after processing except solvent, does not also reappear redox peaks, shows to use volume ratio 9:1
Methyl alcohol and alcohol mixed solution, the sulfuric acid solution of 0.1mol/L the target molecule in polymer film cannot removed.Curve e
For carbofuran molecular engram film electrode prepared by the embodiment of the present invention 1, through NaOH methanol solution to remove at solvent
After reason, its current-responsive value significantly raises and occurs in that again redox peaks, illustrates the carbofuran molecule print of present invention offer
Mark membrane preparation method removes can template molecule, so as to prepare the carbofuran molecule that can be applied to carbofuran quantitative determination
Trace membrane electrode.
Embodiment 6
This test determines respectively base electrode, the base electrode of modified nano gold particle, polymerization using cyclic voltammetry
Carbofuran molecular engram film electricity after thing modified electrode, carbofuran molecular engram film electrode and absorption 0.1mmol/L carbofurans
Pole is used as cyclic voltammogram during working electrode.
It is prepared by electrode to be measured：Prepared respectively according to the carbofuran molecular engram membrane preparation method that embodiment 1 is recorded：Matrix electricity
Pole, the base electrode of modified nano gold particle, polymer modified electrode, carbofuran molecular engram film electrode.Absorption 0.1mmol/L
Carbofuran molecular engram film electrode after carbofuran is that the carbofuran molecular engram film electrode for obtaining embodiment 1 is placed in
Stir obtained in 30min in 0.1mmol/L carbofuran solution.
Using electrode to be measured as working electrode, platinum electrode is used as to electrode, and calomel electrode is electric as reference electrode composition three
Polar body system.Electrolyte solution is the Klorvess Liquid containing the potassium ferricyanide and potassium ferrocyanide, wherein the potassium ferricyanide and ferrous cyanogen
The concentration for changing potassium independently is 1.0mmol/L, and the concentration of potassium chloride is 0.1mol/L.Record the electricity that different electrodes to be measured are obtained
Stream-voltage curve, concrete outcome is shown in Fig. 2.
Measurement result is as shown in Fig. 2 in figure：The cyclic voltammogram of electrode based on a, the matrix of b modified nano gold particles
The cyclic voltammogram of electrode, c is the cyclic voltammogram of polymer film modified electrode, and d is the carbofuran molecule print that embodiment 1 is obtained
The cyclic voltammogram of mark membrane electrode, e is the carbofuran molecular engram film electrode absorption 0.1mmol/L carbofurans that embodiment 1 is obtained
Cyclic voltammogram afterwards.
Curve b strengthens relative to curve a peak point currents, shows the base electrode modified after nanogold particle relative to not
Modified base electrode increased electron transfer efficiency, that is, modifying gold nano grain can strengthen the sensitivity of electrode.
Curve c is polymer film modified electrode as current -voltage curve during working electrode, and curve current value significantly drops
It is low, closure degree increase, and non-oxidation reduction peak.As a result show that the polymer film modified on nm of gold and base electrode surface is tied
Closely, due to including template molecule, hexacyanoferrate is unable to reach electrode surface and carries out electron transmission structure, thus non-oxidation is also
Parent peak.
Curve d occurs in that again redox peaks relative to curve c, shows to be processed through the methanol solution of NaOH
Afterwards, template molecule carbofuran is removed from polymer film, and in electrode surface marking hole and recognizable site, iron cyanogen are left
Radical ion gets enter into trace hole and produces redox peaks.But carbofuran molecular engram film electrode is obtained as working electrode
Curve d in peak point current be still below before modified polymer film that (curve b) shows successfully to prepare carbofuran molecule print
Mark membrane electrode.
Curve e is the carbofuran molecular engram film electrode for having adsorbed 0.1mmol/L carbofurans, due to part imprinted sites quilt
Carbofuran is occupied so that can be for the site relative reduction of hexacyanoferrate identification, so that the peak current of curve e is less than not inhaling
(curve d) shows that the present invention can pass through to determine the change of peak current to the peak current of carbofuran molecular engram film electrode when attached
Value calculates the carbofuran content adsorbed in carbofuran molecular engram film electrode.
Embodiment 7
The carbofuran molecular engram film electrode that embodiment 1 is prepared is working electrode, and platinum electrode is to electrode, calomel
Electrode is that reference electrode constitutes three-electrode system；Electrolyte solution is that the potassium chloride containing the potassium ferricyanide and potassium ferrocyanide is molten
The concentration of liquid, the wherein potassium ferricyanide and potassium ferrocyanide independently is 1mmol/L, and the concentration of potassium chloride is 0.1mol/L；Will be upper
State combination of materials and make carbofuran portable sensor.
Embodiment 8
The carbofuran molecular engram film electrode that embodiment 1 is prepared is working electrode, and platinum electrode is to electrode, calomel
Electrode is that reference electrode constitutes three-electrode system；Electrolyte solution is that the potassium chloride containing the potassium ferricyanide and potassium ferrocyanide is molten
The concentration of liquid, the wherein potassium ferricyanide and potassium ferrocyanide independently is 0.8mmol/L, and the concentration of potassium chloride is 0.05mol/L；Will
Carbofuran portable sensor is made in above-mentioned material combination.
Embodiment 9
The carbofuran molecular engram film electrode that embodiment 1 is prepared is working electrode, and platinum electrode is to electrode, calomel
Electrode is that reference electrode constitutes three-electrode system；Electrolyte solution is that the potassium chloride containing the potassium ferricyanide and potassium ferrocyanide is molten
The concentration of liquid, the wherein potassium ferricyanide and potassium ferrocyanide independently is 1.2mmol/L, and the concentration of potassium chloride is 0.2mol/L；Will
Carbofuran portable sensor is made in above-mentioned material combination.
Comparative example 3
With 30% hydrogen peroxide and concentrated sulfuric acid volume ratio as 1:3 mixed solution immersion glassy carbon electrode 10min, with 0.05 μm
Al2O3Sanding and polishing to electrode surface is mirrored after degree and washes, the ultrasound 10min in water.Electrode after ultrasound is used
Nitrogen is dried up, and in being placed in the dilution heat of sulfuric acid of 0.1mol/L, 15 is scanned in -0.2～1.6V voltage ranges with cyclic voltammetry
Circle.Use water cleaning electrode, nitrogen to dry up after the end of scan, obtain final product pretreated base electrode.
Pretreated base electrode is placed in the phosphate buffer of carbofuran and p-aminobenzoic acid, using circulation volt
Peace method original position electropolymerization prepares molecular engram film, obtains polymer film modified electrode.The electropolymerizatioconditions conditions are：Potential range-
0.4～1.0V, sweeps the rate of hastening for 50mV/S, and the scanning number of turns is 10 to enclose, the carbofuran and p-aminophenyl in the phosphate buffer
The molar concentration rate of formic acid is 1:4.
Polymer film modified electrode is cleaned with water, nitrogen places 1h after drying up.By the polymer film modification electricity after placement
Pole is placed in the methanol solution of 0.1mol/L NaOH and removes template molecule, described to remove the time for 20min.After being cleaned with water
Obtain comparison electrode 3.
With comparison electrode 3 as working electrode, platinum electrode is that, to electrode, calomel electrode is that reference electrode constitutes three electrode bodies
System；Electrolyte solution is the Klorvess Liquid containing the potassium ferricyanide and potassium ferrocyanide, the wherein potassium ferricyanide and potassium ferrocyanide
Concentration independently be 1mmol/L, the concentration of potassium chloride is 0.1mol/L；Contrast portable sensor is made in above-mentioned material combination
1。
The difference of the portable sensor that contrast portable sensor 1 is obtained with embodiment 7 is in contrast portable sensor
The unmodified nanogold particle of working electrode.
Comparative example 4
With 30% hydrogen peroxide and concentrated sulfuric acid volume ratio as 1:3 mixed solution immersion glassy carbon electrode 10min, with 0.05 μm
Al2O3Sanding and polishing to electrode surface is mirrored after degree and washes, the ultrasound 10min in water.Electrode after ultrasound is used
Nitrogen is dried up, and in being placed in the dilution heat of sulfuric acid of 0.1mol/L, 15 is scanned in -0.2～1.6V voltage ranges with cyclic voltammetry
Circle.Use water cleaning electrode, nitrogen to dry up after the end of scan, obtain final product pretreated base electrode.
Pretreated base electrode is placed in the tetrachloro alloy acid solution of 3mmol/L, electricity is carried out using potentiostatic method
Deposition 200s, makes nanogold particle be deposited on base electrode surface, obtains nanogold particle modified electrode.Nanogold particle is repaiied
Decorations electrode is placed in the phosphate buffer of the p-aminobenzoic acid without carbofuran molecule, using cyclic voltammetry original position electropolymerization
Non-imprinted membrane (NIP) is prepared, polymer film modified electrode is obtained.The electropolymerizatioconditions conditions are：Potential range -0.4～
1.0V, it is 50mV/S to sweep the rate of hastening, and the scanning number of turns is 10 circles, and the molar concentration of p-aminobenzoic acid is in the phosphate buffer
4mmol/L。
Polymer film modified electrode is cleaned with water, nitrogen places 1h after drying up.By the polymer film modification electricity after placement
Pole is placed in the methanol solution of 0.1mol/L NaOH and processes, and the process time is 20min.Contrasted after being cleaned with water
Electrode 4.
With comparison electrode 4 as working electrode, platinum electrode is that, to electrode, calomel electrode is that reference electrode constitutes three electrode bodies
System；Electrolyte solution is the Klorvess Liquid containing the potassium ferricyanide and potassium ferrocyanide, the wherein potassium ferricyanide and potassium ferrocyanide
Concentration independently be 1mmol/L, the concentration of potassium chloride is 0.1mol/L；Contrast portable sensor is made in above-mentioned material combination
2。
The difference of the portable sensor that contrast portable sensor 2 is obtained with embodiment 7 is in contrast portable sensor
Working electrode is with the film modified base electrodes that deposited nanogold particle of NIP, and non-imprinted membrane (MIP).
Embodiment 10
This test adopts the range of linearity of cyclic voltammetry portable sensor and draws calibration curve, and contrasts reality
Apply contrast portable sensor 1, contrast portable sensor 2 that the portable sensor that example 7 obtains obtains with comparative example 3, comparative example 4
Detection sensitivity.
It is prepared by standard series：It is 0,0.00005,0.0002,0.0005 to take carbofuran standard items respectively and be formulated as concentration,
0.001,0.006,0.03,0.1,0.2 and 0.4mmol/L standard series.
Detection object：Contrast portable sensor 1, comparative example 4 that portable sensor that embodiment 7 is obtained, comparative example 3 are obtained
The contrast portable sensor 2 for obtaining.
Detection method：The working electrode of each detection object is suspended in testing sample, adsorbs 10min, after the completion of absorption
Cleaned with water.It is measured in three-electrode system using Differential Pulse Voltammetry, with the working electrode after absorption, platinum electrode is
To electrode, calomel electrode is that reference electrode constitutes three-electrode system, and electrochemical gaging, record test are carried out in electrolyte solution
The differential pulse voltammetry voltammetric scan curve for obtaining and peak response current value.The electrochemical response time is 1.5min.
As a result as shown in figure 3, in figure：
■ is the calibration curve that portable sensor with carbofuran molecular engram film electrode as working electrode is determined, curve side
Journey is as follows：
I=3.48logC+16.72,
In formula, I represents that sample current responds changing value, and unit is μ A；
C represents the concentration of carbofuran in sample, unit mmol/L；
The coefficient R of curvilinear equation2=0.985；
● the calibration curve that the contrast portable sensor 1 obtained for comparative example 3 is determined, curvilinear equation is as follows：
I=2.060logC+10.226,
In formula, I represents that sample current responds changing value, and unit is μ A；
C represents the concentration of carbofuran in sample, unit mmol/L；
The coefficient R of curvilinear equation2=0.977；
The calibration curve that ▲ contrast the portable sensor 2 obtained for comparative example 4 is determined, curvilinear equation is as follows：
I=0.096logC+0.396,
In formula, I represents that sample current responds changing value, and unit is μ A；
C represents the concentration of carbofuran in sample, unit mmol/L；
The coefficient R of curvilinear equation2=0.806.
The portable sensor that embodiment 7 is provided carbofuran concentration and current-responsive in the range of 0.0005～0.4mmol/L
Changing value is linear, the maximum phase induced current that current-responsive changing value is obtained when referring to and being tested with the working electrode of unadsorbed sample
The difference of value and the peak response current value to obtain during working electrode test after adsorption sample.
Calibration curve is drawn with the logarithm value of current-responsive changing value and carbofuran concentration, as shown in figure 4, ■ curves with ●
Curve, ▲ curve are compared, and slope is higher, and the detection sensitivity for showing the portable sensor of present invention offer is received relative to unmodified
Rice gold grain or modified NIP films electrode detection sensitivity it is higher.
Embodiment 11
Differential Pulse Voltammetry evaluates the selectivity of the portable sensor of carbofuran quantitative determination.
Detection object：The contrast portable sensor 2 that portable sensor that embodiment 7 is obtained, comparative example 4 are obtained.
Sample preparation：The standard items of carbofuran, Mobucin, Methomyl, Aphox, Aldicarb and MTMC are taken respectively, are matched somebody with somebody
Make the sample solution of 0.1mmol/L.
Quantitative determination：Working electrode is suspended in testing sample solution, adsorbs 10min, cleaned with water after the completion of absorption.
Be measured in three-electrode system using Differential Pulse Voltammetry, with the working electrode after absorption, platinum electrode be to electrode, it is sweet
Mercury electrode is that reference electrode constitutes three-electrode system, and electrochemical gaging is carried out in electrolyte solution, and record test is obtained most
Big response current value.The electrochemical response time is 1.5min.
Test result is as shown in figure 5, in figure：MIP is that the current-responsive that the portable sensor that embodiment 7 is obtained is determined is poor
Value, NIP is the current-responsive difference that the portable sensor that comparative example 4 is obtained is determined, and IF is electric current of each compound in MIP electrodes
Response difference with its current-responsive difference of NIP electrodes ratio, be mainly used in evaluate MIP electrode pair target compounds and its
The selectivity of analog.
As a result show, the portable sensor that the present invention is provided is significantly higher than Mobucin, goes out to the response of carbofuran sample
Many prestige, Aphox, Aldicarb and MTMC, showing the portable sensor of present invention offer has extremely strong specificity to carbofuran,
Impact of the analogue to testing result can be avoided.Meanwhile, the IF values of the portable sensor that the present invention is provided are significantly higher than
The analogue of carbofuran, further demonstrating that the portable sensor of present invention offer can selectively recognize carbofuran point
Son, can be used in the qualitative determination of carbofuran.
Embodiment 12
This test detects the carbofuran content in cowpea using the portable sensor that embodiment 7 is obtained
Sample preparation：After by the broken homogenate of vegetable sample cowpea 500g, 25g (being accurate to 0.01g) cowpea homogenate sample is weighed
Product, are separately added into carbofuran standard items, and the concentration for making carbofuran in cowpea sample is respectively：0.05mg/kg、1.0mg/kg.It is quiet
Put 30min, add 50mL acetonitrile extractions, by mixed solution with high-shear homogenizer homogeneous after, in being transferred to centrifuge tube, 5000rpm
Centrifugation 5min, takes 1mL supernatant extracts, adds 3mL water to carry out sample test.
Detection method：Carbofuran molecular engram film electrode is suspended in testing sample, adsorbs 10min, after the completion of absorption
Cleaned with water.It is measured in three-electrode system using Differential Pulse Voltammetry, with the carbofuran molecular engram film after absorption
Electrode is working electrode, and platinum electrode is that, to electrode, calomel electrode is that reference electrode constitutes three-electrode system, in electrolyte solution
Electrochemical gaging is carried out, differential pulse voltammetry voltammetric scan curve and peak response current value that record test is obtained.Electrochemistry is rung
It is 1.5min between seasonable.
The calibration curve (Fig. 4) drawn using embodiment 10 is calculated the peak response current value that test is obtained to be taken advantage of again
With the content that extension rate obtains final product carbofuran in sample, concrete outcome is shown in Table 1.
The content and the rate of recovery of carbofuran in the cowpea of table 1
| Addition concentration (mg/kg) | Determine concentration (mg/kg) | The rate of recovery (%) | RSD (%, n=3) |
| 0.05 | 0.045 | 90.0 | 4.43 |
| 1.0 | 1.64 | 106 | 9.51 |
It can be seen from the result of table 1, the portable sensor recovery of standard addition that the present invention is provided can reach 90～
106%%, RSD value is less than 10, shows that the accuracy of measurement of the portable sensor of present invention offer is high, disclosure satisfy that residues of pesticides
Site Detection is required.
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 carbofuran molecular engram film electrode, including base electrode, is deposited on the nm of gold of described matrix electrode surface
Grain, is arranged on the carbofuran molecular engram film on the nanogold particle surface；
The carbofuran molecular engram film is the p-aminobenzoic acid polymer film with carbofuran as template molecule.
2. a kind of preparation method of carbofuran 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 nanogold particle；
(2) nanogold particle modified electrode phosphorus of the immersion containing carbofuran and p-aminobenzoic acid for obtaining the step (1)
Electropolymerization is carried out in acid buffer, polymer film modified electrode is obtained；
(3) polymer film modified electrode that step (2) is obtained is placed in the methanol solution of NaOH, in removing polymer film
Carbofuran molecule, obtain carbofuran 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)
Spend for 2.5～3.5mmol/L, the electrodeposition time is 150～300s.
4. the preparation method according to Claims 2 or 3, it is characterised in that in the phosphate buffer solution of the step (2),
Carbofuran is 1 with the mol ratio of p-aminobenzoic acid:3～5.
5. preparation method according to claim 2, it is characterised in that the electropolymerization of the step (2) adopts cyclic voltammetric
Method, the condition of electropolymerization is：Potential range -0.4～1.0V, sweep speed is 40～60mV/S, and the scanning number of turns is 8～12 circles.
6. it is a kind of for carbofuran quantitative determination portable sensor, including working electrode, to electrode, reference electrode and electrolyte
Solution, it is characterised in that the working electrode is carbofuran molecular engram film electrode or claim 2～5 described in claim 1
The carbofuran molecular engram film electrode that preparation method described in any one is obtained, the electrolyte solution is the potassium ferricyanide-ferrous iron
The Klorvess Liquid of potassium cyanide, in the electrolyte solution：The concentration of the potassium ferricyanide and potassium ferrocyanide independently is 0.8～
1.2mmol/L, the concentration of potassium chloride is 0.05～0.2mol/L.
7. portable sensor according to claim 6, it is characterised in that described is platinum electrode to electrode, the reference electricity
Extremely saturated calomel electrode.
8. application of the portable sensor described in claim 6 or 7 in carbofuran quantitative determination.
9. application according to claim 8, it is characterised in that the application is comprised the following steps：
(1) carbofuran molecular engram film electrode is suspended in sample solution, adsorbs 9～11min；
(2) it is and electric to electrode, reference electrode composition three by the carbofuran molecular engram film electrode after absorption in the step (1)
Polar body system, carries out electro-chemical test in electrolyte solution, differential pulse voltammetry voltammetric scan curve and maximum that record test is obtained
Response current value；
(3) it is molten with the sample that the calibration curve of carbofuran concentration and the step (2) are obtained according to predetermined response current value
The peak response current value of liquid, obtains the content of carbofuran in sample solution.
10. application according to claim 8 or claim 9, it is characterised in that carbofuran agricultural chemicals is residual in for determining fruits and vegetables sample
Stay.
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Application publication date: 20170426 |